JP2008121017A - Adhesive sheet, semiconductor device and manufacturing method thereof - Google Patents

Abstract

An adhesive sheet that acts as a dicing tape in a dicing process and acts as an adhesive sheet having excellent connection reliability in a joining process of a semiconductor element and a support member is provided.
An adhesive sheet comprising an adhesive layer and a base material layer, wherein the adhesive force between the adhesive layer and the base material layer is controlled by irradiation of radiation, the adhesive agent The layer is (A1) an adhesive sheet having an adhesive strength of 200 mN / cm or more between the adhesive layer layer and the base material layer before irradiation, and having at least one of the following properties.
(B1) The flow amount at 160 ° C. before radiation irradiation is 100 to 10,000 μm,
(B2) The melt viscosity at 160 ° C. before radiation irradiation is 50 to 100,000 Pa · s.
[Selection figure] None

Description

  The present invention relates to an adhesive sheet, a semiconductor device using the adhesive sheet, and a manufacturing method thereof.

  Conventionally, a silver paste has been mainly used for joining a semiconductor element and a semiconductor element mounting support member. However, with the recent miniaturization and high performance of semiconductor elements, the support members used are required to be small and fine. In response to these requirements, silver paste meets the above requirements due to the occurrence of defects during wire bonding due to protrusions and inclination of semiconductor elements, difficulty in controlling the thickness of the adhesive layer, and the occurrence of voids in the adhesive layer. It has become impossible to deal with.

  For this reason, film adhesives have recently been used in order to meet the above requirements.

  This film-like adhesive is used in an individual piece attaching method or a wafer back surface attaching method. In the case of manufacturing a semiconductor device using the former piece-of-piece adhesive film adhesive, a reel-like adhesive film is cut into pieces by cutting or punching, and then the pieces are bonded to a support member; A semiconductor element separated by a dicing process is joined to a support member with an adhesive to produce a support member with a semiconductor element; a semiconductor device is obtained by performing a wire bonding process, a sealing process, and the like as necessary. Will be. However, in order to use the film adhesive of the piece pasting method, a dedicated assembly device that cuts out the adhesive film and adheres it to the support member is necessary, so that the manufacturing cost is compared with the method using silver paste. There was a problem that became high.

  On the other hand, when manufacturing a semiconductor device using the film adhesive of the latter wafer back surface application method, first, a film adhesive is applied to the back surface of the semiconductor wafer, and a dicing tape is attached to the other surface of the film adhesive; Thereafter, the semiconductor element is separated from the wafer by dicing; the separated semiconductor element with a film-like adhesive is picked up and joined to a support member; by subsequent steps such as heating, curing, and wire bonding. A semiconductor device is obtained. This wafer back surface adhesive system film adhesive does not require a device for separating the film adhesive in order to join the semiconductor element with the film adhesive to the support member, and does not require a conventional assembly device for silver paste. It can be used as it is or by modifying a part of the apparatus such as adding a hot platen. For this reason, it has been attracting attention as a method that can suppress the manufacturing cost relatively inexpensively among the assembling methods using a film adhesive.

  The dicing tape used together with the film adhesive on the wafer back surface is roughly divided into a pressure-sensitive type and a UV type dicing tape.

  The former pressure-sensitive dicing tape is usually obtained by applying an adhesive to a polyvinyl chloride or polyolefin base film. This dicing tape is required to have a sufficient adhesive force so that each element does not scatter due to rotation by the dicing saw during cutting in the dicing process, and the adhesive does not adhere to each element during pick-up so as not to damage the element. Therefore, a low adhesive strength that can be picked up is required. However, since there was no pressure-sensitive dicing tape having sufficient two conflicting performances as described above, an operation of switching the dicing tape for each size and processing condition of the semiconductor element has been performed. In addition, since a wide variety of dicing tapes having various adhesive strengths according to the element size and processing conditions are required, the inventory management of the dicing tapes is complicated. Further, in recent years, semiconductor elements tend to increase in size as a result of increasing capacities of CPUs and memories, and in products such as IC cards and memory cards, the memory used is becoming thinner. . With the increase in size and thickness of these semiconductor elements, the pressure-sensitive dicing tape has a high adhesive strength at the time of pick-up, which causes problems such as cracking of the element at the time of pick-up. Force) and peeling force (low adhesive force) at the time of pick-up are becoming unable to satisfy the conflicting requirements.

  On the other hand, the latter UV-type dicing tape has a high adhesive strength during dicing, but has a low adhesive strength when irradiated with ultraviolet rays (UV) before picking up. Therefore, the problem which the said pressure-sensitive type tape has is improved, and it has come to be widely adopted as a dicing tape.

  The use of this UV-type dicing tape, although the problem of the pressure-sensitive dicing tape is improved to some extent, is not sufficient, and further, there remains a problem to be improved in the film adhesive of the wafer back surface pasting method. That is, in the method using the film adhesive on the wafer back surface attachment method, two application steps such as attaching the film adhesive and the dicing tape are required before the dicing step. In addition, the adhesive of the dicing tape is transferred to the film adhesive and there is a problem that the adhesiveness is lowered. For this reason, an adhesive sheet having the functions of a film adhesive and a dicing tape is required. However, the adhesive sheet has sufficient adhesive strength that does not scatter semiconductor elements during dicing, and does not damage each element during pick-up. An adhesive sheet that satisfies the conflicting requirement of having strength has not been obtained.

  From the above, there has been a demand for an adhesive sheet that acts as a dicing tape in the dicing process and acts as an adhesive sheet having excellent connection reliability in the joining process of the semiconductor element and the support member. In addition, there has been a demand for an adhesive sheet having heat resistance and moisture resistance required for mounting a semiconductor element having a large difference in thermal expansion coefficient on a semiconductor element mounting support member and having excellent workability. Furthermore, there has been a demand for a method of manufacturing a semiconductor device that can simplify the manufacturing process.

  The present invention relates to an adhesive sheet provided with an adhesive layer containing a predetermined component.

<1> An adhesive sheet comprising an adhesive layer and a base material layer, wherein an adhesive force between the adhesive layer and the base material layer is controlled by radiation irradiation, and the adhesive The adhesive layer is an adhesive sheet containing the following components.
(A) a thermoplastic resin,
(B) a thermopolymerizable component, and (c) a compound that generates a base upon irradiation. The present invention also relates to an adhesive sheet having the following parameters.

<2> The adhesive layer has (A1) an adhesive strength between the adhesive layer interface and the base material layer interface before irradiation of radiation of 200 mN / cm or more, or (A2) before irradiation. The said adhesive sheet which the tack strength in 25 degreeC by the 5.1 mm (PHI) probe measurement of the said adhesive layer is 0.5N or more, and has at least 1 characteristic among the following characteristics.
(B1) The flow amount at 160 ° C. before radiation irradiation is 100 to 10,000 μm,
(B2) The melt viscosity at 160 ° C. before radiation irradiation is 50 to 100,000 Pa · s.
The present invention further relates to an adhesive sheet having the following parameters.

<3> An adhesive sheet comprising an adhesive layer and a base material layer, wherein an adhesive force between the adhesive layer and the base material layer is controlled by radiation irradiation, and the adhesive The adhesive layer (A2) has a tack strength at 25 ° C. measured by a 5.1 mmΦ probe of the adhesive layer before irradiation of radiation of 0.5 N or more, and at least one of the following properties: An adhesive sheet.
(B1) The flow amount at 160 ° C. before radiation irradiation is 100 to 10,000 μm,
(B2) The melt viscosity at 160 ° C. before radiation irradiation is 50 to 100,000 Pa · s.
<4> An adhesive sheet comprising an adhesive layer and a base material layer, wherein the adhesive force between the adhesive layer and the base material layer is controlled by radiation irradiation, and the adhesive The adhesive layer (C1) has an adhesive strength difference (adhesive strength before radiation irradiation-adhesive strength after radiation irradiation) at the interface between the adhesive layer and the base material layer before and after radiation irradiation of 100 mN / cm or more, and An adhesive sheet having at least one of the following characteristics.
(D1) tan δ at 120 ° C. before irradiation is 0.1 or more, tan δ at 180 ° C. after irradiation is 0.1 or more,
(D2) The storage elastic modulus at 120 ° C. before radiation irradiation is 10 MPa or less, the storage elastic modulus at 180 ° C. after radiation irradiation is 100 MPa or less, and <5> an adhesive layer and a base material layer, An adhesive sheet in which the adhesive force between the agent layer and the base material layer is controlled by irradiation with radiation, and the adhesive layer is (C2) 25 ° C. of the adhesive layer before and after irradiation with radiation. The difference in tack strength (tack strength at 25 ° C. before radiation irradiation—tack strength at 25 ° C. after radiation irradiation) is 0.1 N / 5.1 mmΦ probe or more, and at least one of the following characteristics An adhesive sheet comprising:
(D1) tan δ at 120 ° C. before irradiation is 0.1 or more, tan δ at 180 ° C. after irradiation is 0.1 or more,
(D2) The storage elastic modulus at 120 ° C. before irradiation is 10 MPa or less, and the storage elastic modulus at 180 ° C. after irradiation is 100 MPa or less. By adopting the above configuration, the adhesive sheet of the present invention is a semiconductor during dicing. The device has sufficient adhesive strength that does not scatter, and then irradiates with radiation to control the adhesive force between the adhesive layer and the substrate so that each device is not damaged during pick-up. It satisfies the conflicting requirement of having a low adhesive strength. Therefore, by producing an electronic component using the adhesive sheet of the present invention, it is possible to obtain an operational effect that each process of dicing and die bonding can be completed with a single film.

  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 joining process of the semiconductor element and the support member, and has a thermal expansion coefficient of the support element for mounting the semiconductor element. It has heat resistance and moisture resistance necessary for mounting a semiconductor element having a large difference, and is excellent in workability.

  Moreover, the manufacturing method of the semiconductor device using the adhesive sheet of the present invention can simplify the manufacturing process, and the manufactured semiconductor device mounts a semiconductor element having a large difference in thermal expansion coefficient on the semiconductor element mounting support member. It combines heat resistance, moisture resistance and workability necessary for the case.

  As a result of examining the composition of the adhesive sheet, the present inventors have found that an adhesive sheet including an adhesive layer containing a predetermined component solves the above-described problem. Further, as a result of studying from the viewpoint of characteristics and chemicals in order to improve the workability and reliability of the adhesive sheet, the present inventors can further improve the workability and reliability by the adhesive sheet having a predetermined characteristic. I found.

<Base material layer>
The component constituting the base material layer used in the adhesive sheet of the present invention is not particularly limited as long as it transmits radiation, and can be appropriately selected according to the use process or the like (for example, whether to expand at the time of pickup). . Specifically, for example, polyester film such as polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polymethylpentene film, polyolefin film such as polyvinyl acetate film, polyvinyl chloride film, polyimide film Such as plastic film.

  The base material layer may be a laminate of two or more different films. In this case, the film on the side in contact with the adhesive layer preferably has a tensile elastic modulus at 25 ° C. of 2000 MPa or more, more preferably 2200 MPa or more, from the viewpoint of improving the pick-up workability of the semiconductor element. 2400 MPa or more is particularly preferable.

  Moreover, the base film on the side that is not in direct contact with the other adhesive layer has a large elongation of the film and good workability in the expanding process, and the tensile elastic modulus at 25 ° C. is 1000 MPa or less. Preferably, it is 800 MPa or less, more preferably 600 MPa or less. This tensile elastic modulus is measured according to JIS K7113.

  When using a substrate layer in which two or more types of substrate films are laminated, there is no particular limitation on the lamination method, a method of laminating separately produced substrate films, and another substrate on one substrate film. A method of extruding and laminating a material film, a method of laminating two or more types of base films while extruding them, and dissolving or dispersing a polymer as a raw material of a base film in a solvent to form a varnish on another base film A known method such as a method of applying and heating to remove the solvent and a method of bonding using an adhesive can be used.

<Adhesive layer>
As the adhesive layer used for the adhesive sheet of the present invention, for example, an adhesive layer containing a thermoplastic resin, a thermopolymerizable component, and a compound that generates a base upon irradiation with radiation is preferable. By having such a configuration, the semiconductor element has a sufficient adhesive strength that does not scatter during dicing, and then controls the adhesive force between the adhesive layer and the substrate by irradiating with radiation. It is possible to satisfy the conflicting requirement of having a low adhesive strength that does not damage each element during pickup.

(Thermopolymerizable component)
Further, the thermopolymerizable component is not particularly limited as long as it is polymerized by heat. Compounds having a functional group can be mentioned, and these can be used alone or in combination of two or more. However, in consideration of heat resistance as an adhesive sheet, thermal curing that cures by heat and exerts an adhesive action. It is preferable to use a functional resin. Examples of the thermosetting resin include an epoxy resin, an acrylic resin, a silicone resin, a phenol resin, a thermosetting polyimide resin, a polyurethane resin, a melamine resin, and a urea resin, and in particular, heat resistance, workability, and reliability. It is most preferable to use an epoxy resin in that an adhesive sheet excellent in the above can be obtained. When using an epoxy resin as the thermosetting resin, it is preferable to use an epoxy resin curing agent together.

(Epoxy resin)
The epoxy resin is not particularly limited as long as it is cured and has an adhesive action. Bifunctional epoxy resins such as bisphenol A type epoxy, novolac type epoxy resins such as phenol novolac type epoxy resin and cresol novolac type epoxy resin, and the like can be used. Moreover, what is generally known, such as a polyfunctional epoxy resin, a glycidyl amine type epoxy resin, a heterocyclic ring-containing epoxy resin, or an alicyclic epoxy resin, can be applied.

  As the bisphenol A type epoxy resin, Japan Epoxy Resin Co., Ltd. Epicoat series (Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, Epicoat 1007, Epicoat 1009), Dow The chemical company make, DER-330, DER-301, DER-361, Toto Kasei Co., Ltd. product, YD8125, YDF8170 etc. are mentioned. Examples of the phenol novolac type epoxy resin include Epicoat 152 and Epicoat 154 manufactured by Japan Epoxy Resin Co., Ltd., EPPN-201 manufactured by Nippon Kayaku Co., Ltd., DEN-438 manufactured by Dow Chemical Co., Ltd., and o-cresol novolak. As the type epoxy resin, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027, manufactured by Nippon Kayaku Co., Ltd., YDCN701, YDCN702, manufactured by Toto Kasei Co., Ltd., YDCN703, YDCN704, etc. are mentioned. As the polyfunctional epoxy resin, Epon 1031S manufactured by Japan Epoxy Resin Co., Ltd., Araldite 0163 manufactured by Ciba Specialty Chemicals, Denacor EX-611, EX-614, EX-614B, EX manufactured by Nagase ChemteX Corporation -622, EX-512, EX-521, EX-421, EX-411, EX-321 and the like. As the amine type epoxy resin, Epicoat 604 manufactured by Japan Epoxy Resin Co., Ltd., YH-434 manufactured by Toto Kasei Co., Ltd., TETRAD-X and TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd., Sumitomo Chemical Co., Ltd. ELM-120 manufactured by the company and the like can be mentioned. Examples of the heterocyclic ring-containing epoxy resin include Araldite PT810 manufactured by Ciba Specialty Chemicals, ERL4234, ERL4299, ERL4221, and ERL4206 manufactured by UCC. These epoxy resins can be used alone or in combination of two or more.

(Epoxy resin curing agent)
When using an epoxy resin, it is preferable to use an epoxy resin curing agent. As the epoxy resin curing agent, known curing agents that are usually used can be used. For example, amines, polyamides, acid anhydrides, polysulfides, boron trifluoride, bisphenol A, bisphenol F, and bisphenol S can be used. Examples thereof include bisphenols having two or more phenolic hydroxyl groups in one molecule, phenol resins such as phenol novolac resin, bisphenol A novolac resin, and cresol novolac resin. Phenol resins such as phenol novolac resin, bisphenol A novolac resin, and cresol novolac resin are particularly preferable in terms of excellent electric corrosion resistance when absorbing moisture.

  Preferred examples of the phenol resin curing agent include, for example, Dainippon Ink and Chemicals, trade names: Phenolite LF2882, Phenolite LF2822, Phenolite TD-2090, Phenolite TD-2149, Phenolite. VH-4150, Phenolite VH4170, Meiwa Kasei Co., Ltd., trade name: H-1, Japan Epoxy Resin Co., Ltd., trade name: Epicure MP402FPY, Epicure YL6065, Epicure YLH129B65 and Mitsui Chemicals, Inc. Name: Milex XL, Milex XLC, Milex RN, Milex RS, Milex VR and the like.

(Compounds that generate bases upon irradiation)
A compound that generates a base upon irradiation is a compound that generates a base upon irradiation, and the generated base increases the curing reaction rate of the thermosetting resin. As the base to be generated, a strongly basic compound is preferable in terms of reactivity and curing speed. In general, a pKa value that is a logarithm of an acid dissociation constant is used as a basic index, and a base having a pKa value in an aqueous solution of 7 or more is preferable, and a base of 9 or more is more preferable. In addition, the compound that generates a base by irradiation with radiation is preferably a compound that generates a base by irradiation with light having a wavelength of 150 to 750 nm. In order to generate a base efficiently when a general light source is used. A compound that generates a base upon irradiation with light of 250 to 500 nm is more preferable.

  Examples of such basicity include imidazole derivatives such as imidazole, 2,4-dimethylimidazole and 1-methylimidazole, piperazine derivatives such as piperazine and 2,5-dimethylpiperazine, piperidine, and 1,2-dimethylpiperidine. A piperidine derivative such as, a proline derivative, a trialkylamine derivative such as trimethylamine, triethylamine, and triethanolamine, a pyridine derivative substituted with an amino group or an alkylamino group at the 4-position, such as 4-methylaminopyridine and 4-dimethylaminopyridine, Pyrrolidine derivatives such as pyrrolidine and n-methylpyrrolidine, alicyclic amine derivatives such as triethylenediamine and 1,8-diazabiscyclo (5,4,0) undecene-1 (DBU), benzylmethylamine, benzyldimethylamino Include benzyl amine derivatives such as benzyl diethylamine.

  Examples of those that generate bases by irradiation are Journal of Photopolymer Science and Technology 12, 313-314 (1999), Chemistry of Materials 11, 170-176 (1999), etc. Quaternary ammonium salt derivatives can be used. Since these produce highly basic trialkylamines by irradiation with actinic rays, they are optimal for curing epoxy resins.

  Also, a carbamate derivative described in Journal of American Chemical Society 118, 12925 (1996), Polymer Journal 28, 795 (1996), etc., or a primary amino group is generated by irradiation with actinic rays. An oxime derivative can be used.

  In addition, an α-aminoketone compound can be most preferably used in the present invention as a compound that generates a base upon irradiation with radiation. Specifically, 2-methyl-1 (4- (methylthio) phenyl) -2-morpholinopropan-1-one (Irgacure 907 manufactured by Ciba Specialty Chemicals) commercially available as a photo radical generator, 2-benzyl -2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1-one (Irgacure 369 manufactured by Ciba Specialty Chemicals), hexaarylbisimidazole derivative (substitution such as halogen, alkoxy group, nitro group, cyano group, etc.) Group may be substituted with a phenyl group), benzoisoxazolone derivatives, and the like.

  The α-aminoketone compound does not have a curing accelerating action for the thermosetting resin due to steric hindrance before irradiation with radiation, but irradiation with radiation causes the α-aminoketone compound to dissociate and cause the steric hindrance. Since it decreases, it is presumed that it has the effect of promoting the curing of the thermosetting resin.

  In addition to the base generator by the actinic ray, a basic compound is generated by photo-Fries rearrangement, photo-Claisen rearrangement (photo-Cleisen rearrangement), Curtius rearrangement (Curtius rearrangement), and Stevens rearrangement (Stevens rearrangement), thereby curing the epoxy resin. It can be carried out.

(Amineimide compound)
In addition to the above compounds, amine imide compounds can be used as the compounds that generate bases upon irradiation with radiation used in the present invention. The amine imide compound is not particularly limited as long as it is a compound that generates a base upon irradiation with actinic rays.

（式中Ｒ^１、Ｒ^２、Ｒ^３は独立に水素、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数１〜８のアルキリデン基、炭素数４〜８のシクロアルキル基、炭素数４〜８のシクロアルケニル基、炭素数１〜６のフェノキシアルキル基、フェニル基、電子供与性基及び／又は電子吸引性基が置換したフェニル基、ベンジル基、電子供与性基及び／又は電子吸引性基が置換したベンジル基等が挙げられる。炭素数１〜８のアルキル基としては、直鎖上のアルキル基の他に、イソプロピル基、イソブチル基、ｔ−ブチル基等も含む。これらの置換基の中で、合成の簡便性、アミンイミドの溶解性等の点から、炭素数１〜８のアルキル基、炭素数６〜８のシクロアルキル基、炭素数１〜６のフェノキシアルキル基が好ましい。また、Ｒ^４は独立に炭素数１〜５のアルキル基、水酸基、炭素数４〜８のシクロアルキル基、炭素数１〜５のアルコキシ基、フェニル基を表す。）
で表される化合物が挙げられる。 Specifically, for example, the following general formula (XXV) or (XXVI)

(Wherein R ¹ , R ² and R ³ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylidene group having 1 to 8 carbon atoms, and a cyclohexane having 4 to 8 carbon atoms. An alkyl group, a cycloalkenyl group having 4 to 8 carbon atoms, a phenoxyalkyl group having 1 to 6 carbon atoms, a phenyl group, a phenyl group substituted with an electron-donating group and / or an electron-withdrawing group, a benzyl group, and an electron-donating group And / or a benzyl group substituted with an electron-withdrawing group, etc. Examples of the alkyl group having 1 to 8 carbon atoms include an isopropyl group, an isobutyl group, a t-butyl group and the like in addition to a linear alkyl group. Among these substituents, from the viewpoint of ease of synthesis, solubility of amine imide, etc., an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 8 carbon atoms, and a phenoxy having 1 to 6 carbon atoms. Alkyl groups are preferred, and ⁴ is independently an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, a cycloalkyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group.)
The compound represented by these is mentioned.

Ar ¹ in the general formula (XXV) is an aromatic group represented by general formulas (IV) to (XVI), and Ar ² in the general formula (XXVI) is represented by the following formula (XVII) to An aromatic group represented by (XXV) is preferred. Like Ar ¹ , from the viewpoint of thermal stability and absorption wavelength, the substituent of R ^{29 to} R ³⁶ is preferably an electron-withdrawing group having 1 to 6 carbon atoms, a cyano group, or a nitro group. .

  A known method can be used for the synthesis of the amine imide compound. See, for example, Encyclopedia of Polymer Science and Engineering, John Wiley & Sons Ltd. (1985), Volume 1, p. 740, obtained from the reaction of the corresponding carboxylic acid ester with a halogenated hydrazine and sodium alkoxide or the reaction of the carboxylic acid ester with hydrazine and an epoxy compound. Can do. In view of the ease of synthesis and safety, a synthesis method from the corresponding carboxylic acid ester, hydrazine and an epoxy compound is particularly preferred. The synthesis temperature and synthesis time are not particularly limited as long as the starting materials to be used are not decomposed. Generally, the desired amine imide compound is obtained by stirring at a temperature of 0 to 100 ° C. for 30 minutes to 7 days. Obtainable.

（式中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４は独立に水素、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数１〜８のアルキリデン基、炭素数４〜８のシクロアルキル基、炭素数４〜８のシクロアルケニル基、炭素数１〜６のフェノキシアルキル基、炭素数１〜６のフェニルアルキル基、炭素数１〜６のシアノアルキル基、炭素数１〜６のヒドロキシアルキル基、フェニル基、電子供与性基及び／又は電子吸引性基が置換したフェニル基、ベンジル基、電子供与性基及び／又は電子吸引性基が置換したベンジル基、ニトロ基、シアノ基、メルカプト基、チオメチル基、フッ素、臭素、塩素、ヨウ素を示す。 (Imidazolium salt)
Moreover, as a compound which generate | occur | produces a base by the radiation irradiation used for this invention, an imidazolium salt can be used besides the said compound. Examples of the imidazolium salt include imidazolium salt compounds represented by the general formula (1) or (2).

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylidene group having 1 to 8 carbon atoms, and 4 carbon atoms. A cycloalkyl group having 8 to 8 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, a phenoxyalkyl group having 1 to 6 carbon atoms, a phenylalkyl group having 1 to 6 carbon atoms, a cyanoalkyl group having 1 to 6 carbon atoms, and a carbon number of 1 -6 hydroxyalkyl group, phenyl group, phenyl group substituted with an electron donating group and / or electron withdrawing group, benzyl group, electron donating group and / or benzyl group substituted with electron withdrawing group, nitro group, A cyano group, a mercapto group, a thiomethyl group, fluorine, bromine, chlorine, and iodine are shown.

（式中、Ｒ_５〜Ｒ_２８は独立に、水素、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数１〜８のアルキルチオ基、炭素数１〜８のアルキリデン基、炭素数４〜８のシクロアルキル基、炭素数４〜８のシクロアルケニル基、アミノ基、炭素数１〜６のアルキルアミノ基、炭素数１〜３のジアルキルアミノ基、モルフォリノ基、メルカプト基、水酸基、炭素数１〜６のヒドロキシアルキル基、フッ素、塩素、臭素等のハロゲン、炭素数１〜６のエステル基、炭素数１〜６のカルボニル基、アルデヒド基、シアノ基、トリフルオロメチル基、シアノ基、ニトロ基、フェニル基、電子供与性基及び／又は電子吸引性基が置換したフェニル基、電子供与性基及び／又は電子吸引性基が置換したベンジル基である。また式中、Ｔ、Ｕ、Ｖ、Ｗ、Ｙ、Ｚは独立に、炭素、窒素、酸素、硫黄原子のいずれかを示す。）
またＡｒ_２は、次式（ＸＶ）〜（ＸＸＩＩＩ）で示される芳香族基であり、

（式中、Ｒ_２９〜Ｒ_３６は独立に、水素、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数１〜８のアルキルチオ基、炭素数１〜８のアルキリデン基、炭素数４〜８のシクロアルキル基、炭素数４〜８のシクロアルケニル基、アミノ基、炭素数１〜６のアルキルアミノ基、炭素数１〜３のジアルキルアミノ基、モルフォリノ基、メルカプト基、水酸基、炭素数１〜６のヒドロキシアルキル基、フッ素、塩素、臭素等のハロゲン、炭素数１〜６のエステル基、炭素数１〜６のカルボニル基、アルデヒド基、シアノ基、トリフルオロメチル基、シアノ基、ニトロ基、フェニル基、電子供与性基及び／又は電子吸引性基が置換したフェニル基、電子供与性基及び／又は電子吸引性基が置換したベンジル基である。また式中、Ａ、Ｂ、Ｄ、Ｅは、独立に炭素、窒素、酸素、硫黄原子のいずれかであり、それらは炭素、窒素、炭素数１〜６のアルキル基、酸素、硫黄と結合しても良い。）
また、Ｘ⁻は、炭素数１〜６のジアルキルジチオカルバミド酸、次式（ＸＸＩＶ）で表されるほう酸である。

（式中、Ｒ_３７〜Ｒ_４０は、独立に水素、フッ素、炭素数１〜６のアルキル基、フェニル基、フッ素が少なくとも１つ以上置換したフルオロフェニル基、イミダゾール基である。））
本発明に使用する光照射によって塩基を発生する上記一般式（１）又は（２）で示されるイミダゾリウム塩化合物の合成は、公知の方法を用いることができるが、合成の簡便性、安全性を考慮すると、下式（ＸＸＶＩＩ）に示すように、ハロゲン化アルキルケトン誘導体とイミダゾール誘導体とで、イミダゾリウム・ハロゲン塩を合成した後、アニオン交換反応によって、イミダゾリウム塩を合成する方法が好ましい。

Ar ₁ is an aromatic group represented by the following formulas (I) to (XIV):

(In the formula, R _{5 to} R ₂₈ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, and an alkylidene group having 1 to 8 carbon atoms. , A cycloalkyl group having 4 to 8 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a morpholino group, a mercapto group, Hydroxyl group, C1-C6 hydroxyalkyl group, halogen such as fluorine, chlorine, bromine, C1-C6 ester group, C1-C6 carbonyl group, aldehyde group, cyano group, trifluoromethyl group, A cyano group, a nitro group, a phenyl group, a phenyl group substituted with an electron donating group and / or an electron withdrawing group, and a benzyl group substituted with an electron donating group and / or an electron withdrawing group. , U V, W, Y, Z are independently represents carbon, nitrogen, oxygen, or sulfur atoms.)
Ar ₂ is an aromatic group represented by the following formulas (XV) to (XXIII):

(Wherein R _{29 to} R ₃₆ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, and an alkylidene group having 1 to 8 carbon atoms. , A cycloalkyl group having 4 to 8 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a morpholino group, a mercapto group, Hydroxyl group, C1-C6 hydroxyalkyl group, halogen such as fluorine, chlorine, bromine, C1-C6 ester group, C1-C6 carbonyl group, aldehyde group, cyano group, trifluoromethyl group, A cyano group, a nitro group, a phenyl group, a phenyl group substituted with an electron-donating group and / or an electron-withdrawing group, and a benzyl group substituted with an electron-donating group and / or an electron-withdrawing group. , , D, E are carbon independently nitrogen, oxygen, any of a sulfur atom, they carbon, nitrogen, alkyl group having 1 to 6 carbon atoms, oxygen, may be combined with the sulfur.)
Further, X ^- is a dialkyl dithiocarbamate having 1 to 6 carbon atoms, a boric acid represented by the following formula (XXIV).

(In the formula, R _{37 to} R ₄₀ are independently hydrogen, fluorine, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a fluorophenyl group substituted with at least one or more fluorine atoms, and an imidazole group.)
The synthesis of the imidazolium salt compound represented by the above general formula (1) or (2) that generates a base by light irradiation used in the present invention can be carried out by a known method, but the synthesis is easy and safe. In view of the above, a method of synthesizing an imidazolium salt by an anion exchange reaction after synthesizing an imidazolium / halogen salt with a halogenated alkyl ketone derivative and an imidazole derivative as shown in the following formula (XXVII) is preferable.

  The synthesis temperature and synthesis time are not particularly limited as long as the starting materials to be used are not decomposed. Generally, the desired imidazolium salt is obtained by stirring at a temperature of 0 to 100 ° C. for 30 minutes to 7 days. A compound can be obtained. Since these compounds do not show reactivity with an epoxy resin in a state where they are not irradiated with radiation at room temperature, they have a feature of excellent storage stability at room temperature.

  The amount of the compound that generates a base by irradiation with radiation as exemplified above is preferably 0.01 to 200 parts by weight and more preferably 0.02 to 150 parts by weight with respect to 100 parts by weight of the epoxy resin. If the amount used is less than 0.01 parts by weight, the adhesive strength at the time of pick-up tends to be difficult to decrease, and depending on the compound used, the heat resistance may decrease. Moreover, when the usage-amount exceeds 200 weight part, there exists a tendency for the characteristic as an adhesive film, storage stability, and the physical property of a film to deteriorate.

(Singlet sensitizer, Triplet sensitizer)
Moreover, a sensitizer can also be added to the adhesive layer which forms the adhesive sheet of this invention for the purpose of high absorption and high sensitivity of irradiation light. As a sensitizer to be used, a known singlet sensitizer and triplet sensitizer can be used as long as they do not adversely affect the curable composition.

  As the sensitizer, for example, aromatic compound derivatives such as naphthalene, anthracene, and pyrene, carbazole derivatives, benzophenone derivatives, benzoin derivatives, thioxanthone derivatives, and coumarin derivatives are preferably used.

  The amount of the sensitizer used should be referred to the absorption wavelength and molar extinction coefficient of the sensitizer, but (c) 0.01 to 10 weights per 1 part by weight of the base generated by irradiation. Part is preferable, 0.1 to 5 parts by weight is more preferable, and 0.1 to 2 parts is particularly preferable. If the sensitizer is 0.01 parts by weight or less, the light absorption efficiency is lowered, and if it exceeds 10 parts by weight, the light transmittance tends to deteriorate.

（式中、Ｒ_５〜Ｒ_２８は独立に、水素、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数１〜８のアルキルチオ基、炭素数１〜８のアルキリデン基、炭素数４〜８のシクロアルキル基、炭素数４〜８のシクロアルケニル基、アミノ基、炭素数１〜６のアルキルアミノ基、炭素数１〜３のジアルキルアミノ基、モルフォリノ基、メルカプト基、水酸基、炭素数１〜６のヒドロキシアルキル基、フッ素、塩素、臭素等のハロゲン、炭素数１〜６のエステル基、炭素数１〜６のカルボニル基、アルデヒド基、シアノ基、トリフルオロメチル基、シアノ基、ニトロ基、ベンゾイル基、フェニル基、電子供与性基及び／又は電子吸引性基が置換したフェニル基、電子供与性基及び／又は電子吸引性基が置換したベンジル基である。また式中、Ｔ、Ｕ、Ｖ、Ｗ、Ｙ、Ｚは独立に、炭素、窒素、酸素、硫黄原子のいずれかを示す。）

（式中、Ｒ_２９〜Ｒ_３６は独立に、水素、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数１〜８のアルキルチオ基、炭素数１〜８のアルキリデン基、炭素数４〜８のシクロアルキル基、炭素数４〜８のシクロアルケニル基、アミノ基、炭素数１〜６のアルキルアミノ基、炭素数１〜３のジアルキルアミノ基、モルフォリノ基、メルカプト基、水酸基、炭素数１〜６のヒドロキシアルキル基、フッ素、塩素、臭素等のハロゲン、炭素数１〜６のエステル基、炭素数１〜６のカルボニル基、アルデヒド基、シアノ基、トリフルオロメチル基、シアノ基、ニトロ基、フェニル基、電子供与性基及び／又は電子吸引性基が置換したフェニル基、電子供与性基及び／又は電子吸引性基が置換したベンジル基である。式中Ａ、Ｂ、Ｄ、Ｅは独立に、炭素、窒素、酸素、硫黄原子のいずれかであり、それらは炭素、窒素、炭素数１〜６のアルキル基、酸素、硫黄と結合しても良い。）等が挙げられる。 このほかにも、１−メトキシナフタレン、２−メトキシナフタレン、１，４−ジシアノナフタレン、アントラセン、１，２−ベンズアントラセン、９，１０−ジクロロアントラセン、９，１０−ジブロモアントラセン、９，１０−ジフェニルアントラセン、９−シアノアントラセン、９，１０−ジシアノアントラセン、２，６，９，１０−テトラシアノアントラセン、カルバゾール、９−メチルカルバゾール、９−フェニルカルバゾール、９−プロペ−２−イニル−９Ｈ−カルバゾール、９−プロピル−９Ｈ−カルバゾール、９−ビニルカルバゾール、９Ｈ−カルバゾール−９−エタノール、９−メチル−３−ニトロ−９Ｈ−カルバゾール、９−メチル−３，６−ジニトロ−９Ｈ−カルバゾール、９−オクタノイルカルバゾール、９−カルバゾールメタノール、９−カルバゾールプロピオン酸、９−カルバゾールプロピオニトリル、９−デシル−３，６−ジニトロ−９Ｈ−カルバゾール、９−エチル−３，６−ジニトロ−９Ｈ−カルバゾール、９−エチル−３−ニトロカルバゾール、９−エチルカルバゾール、９−イソプロピルカルバゾール、９−（エトキシカルボニルメチル）カルバゾール、９−（モルホリノメチル）カルバゾール、９−アセチルカルバゾール、９−アリルカルバゾール、９−ベンジル−９Ｈ−カルバゾール、９−カルバゾール酢酸、９−（２−ニトロフェニル）カルバゾール、９−（４−メトキシフェニル）カルバゾール、９−（１−エトキシ−２−メチル−プロピル）−９Ｈ−カルバゾール、３−ニトロカルバゾール、４−ヒドロキシカルバゾール、３，６−ジニトロ−９Ｈ−カルバゾール、３，６−ジフェニル−９Ｈ−カルバゾール、２−ヒドロキシカルバゾール、３，６−ジアセチル−９−エチルカルバゾール、ベンゾフェノン、４−フェニルベンゾフェノン、４，４‘−ビス（ジメトキシ）ベンゾフェノン、４，４‘−ビス（ジメチルアミノ）ベンゾフェノン、４，４‘−ビス（ジエチルアミノ）ベンゾフェノン、２−ベンゾイル安息香酸メチルエステル、２−メチルベンゾフェノン、３−メチルベンゾフェノン、４−メチルベンゾフェノン、３，３‘−ジメチル−４−メトキシベンゾフェノン、２，４，６−トリメチルベンゾフェノン、［４−（４−メチルフェニルチオ）フェニル］−フェニルメタノン、キサントン、チオキサントン、２−クロロチオキサントン、４−クロロチオキサントン、２−イソプロピルチオキサントン、４−イソプロピルチオキサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、１−クロロ−４−プロポキシチオキサントン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインｎ−プロピルエーテル、ベンゾインｎ−ブチルエーテル、ベンゾインイソブチルエーテル、２，２−ジメトキシ−１，２−ジフェニルエタノン、２，２−ジエトキシ−１，２−ジフェニルエタノンが挙げられる。これらは、単独で用いるほかに、複数を組み合わせて用いても良い。 As the sensitizer used in the present invention, known singlet sensitizers and triplet sensitizers can be used as long as they do not adversely affect the curable composition. For example, aromatic compound derivatives such as naphthalene, anthracene, and pyrene, carbazole derivatives, aromatic carbonyl compounds, benzophenone derivatives, benzoin derivatives, thioxanthone derivatives, and coumarin derivatives are preferably used. Among these, naphthalene derivatives, anthracene derivatives, and carbazole derivatives are the most preferable singlet sensitizers, and thioxanthone derivatives, benzophenone derivatives, and benzoin derivatives are most preferable as triplet sensitizers. For example, 1-methylnaphthalene, 2-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, 1-iodonaphthalene, 2-iodonaphthalene, 1-naphthol 2-naphthol, compounds represented by the following general formulas (I) to (XXIII),

(In the formula, R _{5 to} R ₂₈ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, and an alkylidene group having 1 to 8 carbon atoms. , A cycloalkyl group having 4 to 8 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a morpholino group, a mercapto group, Hydroxyl group, C1-C6 hydroxyalkyl group, halogen such as fluorine, chlorine, bromine, C1-C6 ester group, C1-C6 carbonyl group, aldehyde group, cyano group, trifluoromethyl group, A cyano group, a nitro group, a benzoyl group, a phenyl group, an electron donating group and / or a phenyl group substituted with an electron withdrawing group, an electron donating group and / or a benzyl group substituted with an electron withdrawing group. Wherein, T, U, V, W, Y, Z are independently represents carbon, nitrogen, oxygen, or sulfur atoms.)

(Wherein R _{29 to} R ₃₆ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, and an alkylidene group having 1 to 8 carbon atoms. , A cycloalkyl group having 4 to 8 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a morpholino group, a mercapto group, Hydroxyl group, C1-C6 hydroxyalkyl group, halogen such as fluorine, chlorine, bromine, C1-C6 ester group, C1-C6 carbonyl group, aldehyde group, cyano group, trifluoromethyl group, A cyano group, a nitro group, a phenyl group, a phenyl group substituted with an electron donating group and / or an electron withdrawing group, and a benzyl group substituted with an electron donating group and / or an electron withdrawing group, wherein A and B , D E is independently a carbon, nitrogen, oxygen, any of a sulfur atom, they carbon, nitrogen, alkyl group having 1 to 6 carbon atoms, oxygen, may be combined with the sulfur.) And the like. In addition, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dicyanonaphthalene, anthracene, 1,2-benzanthracene, 9,10-dichloroanthracene, 9,10-dibromoanthracene, 9,10-diphenyl Anthracene, 9-cyanoanthracene, 9,10-dicyanoanthracene, 2,6,9,10-tetracyanoanthracene, carbazole, 9-methylcarbazole, 9-phenylcarbazole, 9-prop-2-ynyl-9H-carbazole, 9-propyl-9H-carbazole, 9-vinylcarbazole, 9H-carbazole-9-ethanol, 9-methyl-3-nitro-9H-carbazole, 9-methyl-3,6-dinitro-9H-carbazole, 9-octa Noylcarbazole, 9-carba Methanol, 9-carbazolepropionic acid, 9-carbazolepropionitrile, 9-decyl-3,6-dinitro-9H-carbazole, 9-ethyl-3,6-dinitro-9H-carbazole, 9-ethyl-3-nitro Carbazole, 9-ethylcarbazole, 9-isopropylcarbazole, 9- (ethoxycarbonylmethyl) carbazole, 9- (morpholinomethyl) carbazole, 9-acetylcarbazole, 9-allylcarbazole, 9-benzyl-9H-carbazole, 9-carbazole Acetic acid, 9- (2-nitrophenyl) carbazole, 9- (4-methoxyphenyl) carbazole, 9- (1-ethoxy-2-methyl-propyl) -9H-carbazole, 3-nitrocarbazole, 4-hydroxycarbazole, 3, 6 Dinitro-9H-carbazole, 3,6-diphenyl-9H-carbazole, 2-hydroxycarbazole, 3,6-diacetyl-9-ethylcarbazole, benzophenone, 4-phenylbenzophenone, 4,4′-bis (dimethoxy) benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 2-benzoylbenzoic acid methyl ester, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 3,3 ′ -Dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, [4- (4-methylphenylthio) phenyl] -phenylmethanone, xanthone, thioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, -Isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl Examples include ether, benzoin n-butyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethanone, and 2,2-diethoxy-1,2-diphenylethanone. These may be used alone or in combination.

  As described above, (c) a compound that generates a base upon irradiation with light does not exhibit reactivity with a thermopolymerizable compound such as an epoxy resin in the state where it is not irradiated with radiation at room temperature. The characteristic is that it is very good.

(Thermoplastic resin)
The adhesive layer that forms the adhesive sheet of the present invention may contain a thermoplastic resin for the purpose of improving film formability.

  The thermoplastic resin is not particularly limited as long as it is a resin having thermoplasticity, or at least a resin that has thermoplasticity in an uncured state and forms a crosslinked structure after heating. However, Tg (glass transition temperature) is − It is preferable that the weight average molecular weight is 50 to 10 ° C. and the weight average molecular weight is 100,000 to 1,000,000, or Tg is 10 to 100 ° C. and the weight average molecular weight is 5,000 to 200,000.

  As the former thermoplastic resin, it is preferable to use a polymer containing a functional monomer, and as the latter thermoplastic resin, for example, polyimide resin, polyamide resin, polyetherimide resin, polyamideimide resin, polyester resin, Examples include a polyesterimide resin, a phenoxy resin, a polysulfone resin, a polyethersulfone resin, a polyphenylene sulfide resin, and a polyetherketone resin. Among these, a polyimide resin is preferable.

  Examples of the functional group in the polymer containing the functional monomer include a glycidyl group, an acryloyl group, a methacryloyl group, a hydroxyl group, a carboxyl group, an isocyanurate group, an amino group, and an amide group. Among them, a glycidyl group is preferable. More specifically, a glycidyl group-containing (meth) acrylic copolymer containing a functional monomer such as glycidyl acrylate or glycidyl methacrylate is preferable, and it is further incompatible with a thermosetting resin such as an epoxy resin. preferable.

(High molecular weight component having a functional monomer and a weight average molecular weight of 100,000 or more)
Examples of the high molecular weight component having a weight average molecular weight of 100,000 or more including the functional monomer include a glycidyl group containing a functional monomer such as glycidyl acrylate or glycidyl methacrylate and having a weight average molecular weight of 100,000 or more. (Meth) acrylic copolymers and the like can be mentioned, and among them, those that are incompatible with the epoxy resin are preferable.

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

  The functional monomer means a monomer having a functional description, and as such, it is preferable to use glycidyl acrylate or glycidyl methacrylate. Examples of the glycidyl group-containing (meth) acrylic copolymer having a weight average molecular weight of 100,000 or more include HTR-860P-3 manufactured by Nagase ChemteX Corporation.

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

  Examples of the functional monomer other than glycidyl acrylate and glycidyl methacrylate include ethyl (meth) acrylate and butyl (meth) acrylate, and these may be used alone or in combination of two or more. In the present invention, ethyl (meth) acrylate refers to both ethyl acrylate and ethyl methacrylate. The mixing ratio in the case of using a combination of functional monomers is determined in consideration of Tg of the glycidyl group-containing (meth) acrylic copolymer, and Tg is preferably −10 ° C. or higher. This is because when the Tg is −10 ° C. or higher, the tackiness of the adhesive layer in the B-stage state is appropriate, and there is no problem in handling properties.

  When the above monomer is polymerized to produce a high molecular weight component having a functional monomer-containing weight average molecular weight of 100,000 or more, the polymerization method is not particularly limited, and examples thereof include methods such as pearl polymerization and solution polymerization. Can be used.

  In the present invention, the high molecular weight component containing the functional monomer has a weight average molecular weight of 100,000 or more, preferably 300,000 to 3,000,000, and more preferably 500,000 to 2,000,000. When the weight average molecular weight is in this range, the strength, flexibility, and tackiness of a sheet or film are appropriate, and the circuit fillability of wiring can be ensured because the flow property is appropriate. In the present invention, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve as will be described later in the column of the evaluation method.

  Moreover, the usage-amount of the high molecular weight component whose weight average molecular weight containing a functional monomer is 100,000 or more is preferable 10-400 weight part with respect to 100 weight part of thermopolymerizable components. When it is in this range, storage elastic modulus and flowability during molding can be ensured, and handleability at high temperatures can be sufficiently obtained. The amount of the high molecular weight component used is more preferably 15 to 350 parts by weight, and particularly preferably 20 to 300 parts by weight.

(Polyimide resin)
Of the above thermoplastic resins, a polyimide resin, which is one of the preferable ones, can be obtained by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method. That is, in an organic solvent, tetracarboxylic dianhydride and diamine are used in an equimolar or almost equimolar amount (the order of addition of each component is arbitrary), and the addition reaction is carried out at a reaction temperature of 80 ° C. or less, preferably 0 to 60 ° C. As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, which is a polyimide precursor, is generated.

  The polyamic acid can also be adjusted in molecular weight by heating at a temperature of 50 to 80 ° C. to cause depolymerization.

  The polyimide resin can be obtained by dehydrating and ring-closing the reaction product (polyamic acid). The dehydration ring closure can be performed by a thermal ring closure method in which heat treatment is performed and a chemical ring closure method using a dehydrating agent.

  There is no restriction | limiting in particular as tetracarboxylic dianhydride used as a raw material of a polyimide resin, For example, 1, 2- (ethylene) bis (trimellitic anhydride), 1, 3- (trimethylene) bis (trimellitate anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride), 1,6- (hexamethylene) bis (trimellitic anhydride), 1,7- ( Heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- (nonamethylene) bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitic anhydride) Product), 1,12- (dodecamethylene) bis (trimellitate anhydride), 1,16- (hexadeca) Tylene) bis (trimellitic anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride), pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) Propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane anhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane anhydride, bis (2,3-dicarboxyphenyl) Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylene Tracarboxylic 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′-benzophenonetetracarboxylic dianhydride, 3,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 1,2,5,6 -Naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,2,4,5-naphthalene Tetracarboxylic 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, pyrazine-2,3,5,6- Tetracarboxylic dianhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4 '-Biphenyltetracarboxylic dianhydride, 2,3,2', 3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4- Dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene Product, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic anhydride), ethylenetetracarboxylic dianhydride 1,2,3,4-butanetetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5 6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5 -Tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo- [2, 2, ] -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 dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride Etc. can be used, and these 1 type (s) or 2 or more types can also be used together.

（式中、Ｒ_１及びＲ_２は炭素原子数１〜３０の二価の炭化水素基を示し、それぞれ同一でも異なっていてもよく、Ｒ_３及びＲ_４は一価の炭化水素基を示し、それぞれ同一でも異なっていてもよく、ｍは１以上の整数である）
で表されるジアミノポリシロキサン、１，３−ビス（アミノメチル）シクロヘキサン、サン テクノケミカル（株）製 ジェファーミン Ｄ−２３０，Ｄ−４００，Ｄ−２０００，Ｄ−４０００，ＥＤ−６００，ＥＤ−９００，ＥＤ−２００１，ＥＤＲ−１４８等のポリオキシアルキレンジアミン等の脂肪族ジアミン等を使用することができ、これらの１種又は２種以上を併用することもできる。前記ポリイミド樹脂のＴｇとしては、０〜２００℃であることが好ましく、重量平均分子量としては、１万〜２０万であることが好ましい。 Moreover, there is no restriction | limiting in particular as diamine used as a raw material of a polyimide, For example, 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′-diaminodiphenylethermethane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4 -Amino-3,5-diisopropylphenyl) methane, 3,3'-diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone 3,4'-dia Nodiphenyl 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-amino) Phenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-a Nophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3,4 ′-(1,4-phenylene) Bis (1-methylethylidene)) bisaniline, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2 , 2-bis (4- (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) sulfide, bis (4- (4-aminoenoxy) phenyl) sulfur Bis (4- (3-aminoenoxy) phenyl) sulfone, bis (4- (4-aminoenoxy) phenyl) sulfone, 3,5-diaminobenzoic acid and other aromatic diamines, 1,2-diaminoethane, , 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 (3)

(In the formula, R ₁ and R ₂ represent a divalent hydrocarbon group having 1 to 30 carbon atoms, which may be the same or different, and R ₃ and R ₄ represent a monovalent hydrocarbon group, Each may be the same or different, and m is an integer of 1 or more)
Diaminopolysiloxane represented by the formula: 1,3-bis (aminomethyl) cyclohexane, manufactured by Sun Techno Chemical Co., Ltd. Jeffamine D-230, D-400, D-2000, D-4000, ED-600, ED- Aliphatic diamines such as polyoxyalkylene diamines such as 900, ED-2001 and EDR-148 can be used, and one or more of these can also be used in combination. The Tg of the polyimide resin is preferably 0 to 200 ° C., and the weight average molecular weight is preferably 10,000 to 200,000.

(Other ingredients)
By having the components described so far, it is possible to obtain an adhesive sheet having excellent characteristics. However, in order to further optimize the characteristics or depending on the structure of the semiconductor package to be applied, the following other sheets are provided. Ingredients can be used.

（式中、Ｒ_１及びＲ_２は水素又はメチル基を示し、ｑ及びｒは１以上の整数である）
で表される化合物、ジオール類及び、一般式（５）

（式中、ｎは０〜１の整数であり、Ｒ_３は炭素原子数が１〜３０の２価あるいは３価の有機性基である）
で表されるイソシアネート化合物及び、一般式（６）

（式中、Ｒ_４は水素又はメチル基であり、Ｒ_５はエチレン基あるいはプロピレン基である）
で表される化合物からなるウレタンアクリレート又はウレタンメタクリレート、一般式（７）

（式中、Ｒ_６は炭素原子数が２〜３０の２価の有機基を示す）
で表されるジアミン及び、一般式（８）

（式中、ｎは０〜１の整数であり、Ｒ_７は炭素原子数が１〜３０の２価あるいは３価の有機性基である）
で表されるイソシアネート化合物及び、一般式（９）

（式中、ｎは０〜１の整数である）
で表される化合物からなる尿素メタクリレート、官能基を含むビニル共重合体に少なくとも１個のエチレン性不飽和基と、オキシラン環、イソシアネート基、水酸基、カルボキシル基等の１個の官能基を有する化合物を付加反応させて得られる側鎖にエチレン性不飽和基を有する放射線重合性共重合等などを使用することもできる。これらの放射線重合化合物は、単独で又は２種類以上を組み合わせて使用することができる。 (Radiation polymerizable component)
As a component constituting the adhesive layer used in the adhesive sheet of the present invention, a radiation polymerizable component can be included for the purpose of improving the sensitivity of polymerization by radiation irradiation. The radiation polymerizable component is not particularly limited. For example, methyl acrylate, 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 dimethac Rate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, penta Erythritol 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-hydroxyprop , 1,2-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N- dimethyl acrylamide, N- methylol acrylamide, tris (beta-hydroxyethyl) triacrylate isocyanurate represented by the following general formula (4)

(Wherein R ₁ and R ₂ represent hydrogen or a methyl group, and q and r are integers of 1 or more)
And the diols represented by the general formula (5)

(In the formula, n is an integer of 0 to 1, and R ₃ is a divalent or trivalent organic group having 1 to 30 carbon atoms)
And an isocyanate compound represented by the general formula (6)

(Wherein R ₄ is hydrogen or a methyl group, and R ₅ is an ethylene group or a propylene group)
Urethane acrylate or urethane methacrylate comprising the compound represented by the general formula (7)

(Wherein R ₆ represents a divalent organic group having 2 to 30 carbon atoms)
A diamine represented by the general formula (8)

(In the formula, n is an integer of 0 to 1, and R ₇ is a divalent or trivalent organic group having 1 to 30 carbon atoms)
And an isocyanate compound represented by the general formula (9)

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

  Moreover, it can also be made radiation-polymerizable using the compound which generate | occur | produces the base which accelerates | stimulates hardening of the said epoxy resin by irradiation.

(Curing accelerator)
Moreover, a hardening accelerator can also be added to the adhesive layer which forms the adhesive sheet of this invention. There are no particular limitations on the curing accelerator, and imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazoletetraphenylborate, 1,8-diazabicyclo ( 5,4,0) undecene-7-tetraphenylborate and the like can be used. These can be used alone or in combination of two or more.

  0.1-5 weight part is preferable with respect to 100 weight part of thermopolymerizable components, and, as for the addition amount of a hardening accelerator, 0.2-3 weight part is more preferable. When the addition amount is within this range, both curability and storage stability can be achieved. When the addition amount is less than 0.1 parts by weight, the curability tends to be inferior, and when it exceeds 5 parts by weight, the storage stability tends to decrease.

  In addition, a photopolymerization initiator that generates free radicals upon irradiation with active light for initiating polymerization of the radiation-polymerizable compound can be added to the adhesive layer that forms the adhesive sheet of the present invention. . Examples of such a photopolymerization initiator include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler 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-diphenylethane-1-one, 1- Aromatic ketones such as hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1,2,4-diethylthioxanthone, 2-ethylanthraquinone, phenanthrenequinone , Benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin ether such as nyl ether, benzoin such as methyl benzoin and ethyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, 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-mer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxy) 2,4,5-triarylimidazole dimer such as phenyl) -4,5-diphenylimidazole dimer , 9-phenyl acridine, 1,7-bis (9,9'-acridinyl) can be used, such as acridine derivatives such as heptane, it can be used alone or in combination of two or more. Although there is no restriction | limiting in particular as the usage-amount of the said photoinitiator, 0.01-30 weight part is preferable with respect to 100 weight part of radiation polymerizable compounds.

  Moreover, a filler can also be added to the adhesive layer which forms the adhesive sheet of this invention for the purpose of the handling property improvement, thermal conductivity improvement, adjustment of melt viscosity, and thixotropic property provision. The 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 whisker, nitriding Boron, crystalline silica, amorphous silica and the like can be mentioned, and the shape of the filler is not particularly limited. These fillers can be used alone or in combination of two or more.

  Among these, aluminum oxide, aluminum nitride, boron nitride, crystalline silica, amorphous silica and the like are preferable for improving thermal conductivity. For the purpose of adjusting 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 filler used is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the adhesive layer. If the amount is less than 1 part by weight, the addition effect tends not to be obtained. If the amount exceeds 20 parts by weight, problems such as an increase in storage elastic modulus of the adhesive layer, a decrease in adhesiveness, and a decrease in electrical characteristics due to residual voids are caused. Tend.

  In addition, various coupling agents can be added to the adhesive layer forming the adhesive sheet of the present invention in order to improve interfacial bonding between different materials. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based, and among them, a silane-based coupling agent is preferable because it is highly effective.

  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-glycidoxypropylmethyldi Ethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyl Limethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltri Methoxysilane, 3-aminopropyl-tris (2-methoxy-ethoxy-ethoxy) silane, N-methyl-3-aminopropyltrimethoxysilane, triaminopropyltrimethoxysilane, 3-4,5-dihydroimidazole-1- Yl-propyltrimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyldimethoxysilane, 3 Cyanopropyltriethoxysilane, hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide, methyltrimethoxysilane, methyltriethoxysilane, ethyltrichlorosilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, amyltrichlorosilane , Octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltri (methacryloyloxyethoxy) silane, methyltri (glycidyloxy) silane, N-β (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane , Octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldichlorosilane, γ-chloropropylmethyldimeth Sisilane, γ-chloropropylmethyldiethoxysilane, trimethylsilyl isocyanate, dimethylsilyl isocyanate, methylsilyl triisocyanate, vinylsilyl triisocyanate, phenylsilyl triisocyanate, tetraisocyanate silane, ethoxysilane isocyanate, etc. can be used alone. Alternatively, two or more types can be used in combination.

  Examples of the titanium-based coupling agent include isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl 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-diallyl) Oxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, dic Ruphenyloxyacetate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium Octylene glycolate, Titanium lactate ammonium salt, Titanium lactate, Titanium lactate ethyl ester, Titanium chili ethanolamate, Polyhydroxy titanium stearate, Tetramethyl orthotitanate, Tetraethyl orthotitanate, Tetarapropyl orthotitanate, Tetraisobutyl orthotitanate, Stearyl Titanate, cresyl titanate monomer, cresyl titanate , Diisopropoxy-bis (2,4-pentadionate) titanium (IV), diisopropyl-bis-triethanolamino titanate, octylene glycol titanate, tetra-n-butoxy titanium polymer, tri-n-butoxy titanium mono A stearate polymer, tri-n-butoxy titanium monostearate, etc. can be used, and it can be used individually or in combination of 2 or more types.

  Examples of the aluminum coupling agent include ethyl acetoacetate aluminum diisopropylate, aluminum toys (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris (acetylacetate). Nate), aluminum = monoisopropoxy monooroxyethyl acetoacetate, aluminum-di-n-butoxide monoethyl acetoacetate, aluminum chelate compounds such as aluminum-di-iso-propoxide-monoethyl acetoacetate, aluminum isopropylate, Mono-sec-butoxyaluminum diisopropylate, aluminum-sec-butyrate, aluminum It can be used such as aluminum alcoholate such Muechireto, alone or in combination of two or more kinds may be used.

  It is preferable that the usage-amount of the said coupling agent shall be 0.001-10 weight part with respect to 100 weight part of adhesive agent layers from the surface of the effect, heat resistance, and cost.

  An ion scavenger can 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, for example, triazine thiol compound, bisphenol-based reducing agent, etc., a compound known as a copper damage preventing agent for preventing copper ionization and dissolution, zirconium-based And inorganic ion adsorbents such as antimony bismuth-based magnesium aluminum compounds.

  The amount of the ion scavenger used is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the adhesive layer from the viewpoint of the effect of addition, heat resistance, cost, and the like.

(Storage modulus)
The adhesive layer forming the adhesive sheet of the present invention has a storage elastic modulus of 10 to 2000 MPa at 25 ° C. and preferably 3 to 50 MPa at 260 ° C. at the stage of heat curing. The storage elastic modulus at 25 ° C. is more preferably 20 to 1900 MPa, and particularly preferably 50 to 1800 MPa. Further, the storage elastic modulus at 260 ° C. is more preferably 5 to 50 MPa, and particularly preferably 7 to 50 MPa. When the storage elastic modulus is within this range, the effect of relaxing the thermal stress generated by the difference in the thermal expansion coefficient between the semiconductor element and the support member is maintained, and the occurrence of peeling and cracking can be suppressed, and the handling property of the adhesive can be suppressed. And can suppress the occurrence of reflow cracks. Although the conditions of the said heat-hardening differ also with compositions of an adhesive agent layer, they are the range of 120-240 degreeC and 5-600 minutes normally.

  This storage elastic modulus is, for example, using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology Co., Ltd.), applying a tensile load to the cured adhesive, and having a frequency of 10 Hz and a heating rate of 5 to 10 ° C./min. It can be measured by a temperature dependence measurement mode in which measurement is performed from −50 ° C. to 300 ° C. under the following conditions.

<Description of parameters>
The adhesive sheet of the present invention has a sufficient adhesive force that prevents the semiconductor elements from scattering during dicing, and then irradiates with radiation to control the adhesive force between the adhesive layer and the base material layer. It sometimes satisfies the conflicting requirement of having a low adhesive strength that does not damage each element. Therefore, it has the effect | action and effect that each process of dicing and die-bonding can be completed with one film. The adhesive sheet of the present invention has heat resistance and moisture resistance required when a semiconductor element having a large difference in thermal expansion coefficient is mounted on the semiconductor element mounting support member.

  As a result of examining from the viewpoint of characteristics and chemicals to further optimize the adhesive sheet of the present invention having such actions and effects, the present inventors specified predetermined parameters as described below. The inventors have found that the above-described effects can be obtained more appropriately regardless of the raw materials used for the adhesive sheet.

  That is, the present invention relates to an adhesive sheet having predetermined parameters.

  First, the significance of parameters in the present invention will be described for the purpose of facilitating understanding of the present invention. In addition, each measurement object of the flow amount in this invention, a melt viscosity, and a storage elastic modulus shall be an adhesive layer.

  In the present invention, the flow amount is an index of fluidity. For example, the adhesive sheet is cut into a size of 10 × 20 mm, placed on a slide glass, and heated at 160 ° C. and 0.8 MPa for 18 seconds. This is a value obtained by measuring with an optical microscope the length that protrudes from the initial size to the periphery.

  In the present invention, the adhesive strength refers to 90 ° peel strength at the interface between the adhesive layer and the base material layer unless otherwise specified. For example, after the adhesive sheet is bonded to the back surface of the semiconductor wafer to be diced at room temperature or while being heated and bonded, only the base material layer is pulled at a pulling angle of 90 ° and a pulling speed of 50 mm / min. It is a value obtained by measuring the peel peel force when pulled with.

  In the present invention, the melt viscosity is an index of film fluidity, and is a value obtained by measuring and calculating by, for example, a parallel plate plastometer method. The melt viscosity is obtained by, for example, laminating 8 sheets of adhesive sheets, producing a film having a thickness of about 400 μm, and punching it into a circle having a diameter of 11.3 mm as a sample at 160 ° C. with a load of 2.5 kgf for 5 seconds. The pressure is calculated by using Equation 1 described later from the thickness of the sample before and after pressurization.

In the present invention, the tack strength is an index of the adhesive property of the adhesive layer. For example, using a RHESCA tacking tester, the peeling speed is measured by the method described in JISZ0237-1991. It is a value obtained by measuring at a measurement temperature of 25 ° C. under conditions of 10 mm / s, a contact load of 100 gf / cm ² , and a contact time of 1 s.

  In the present invention, tan δ is a loss elastic modulus / storage elastic modulus, which is an energy dissipation term, that is, an index of fluidity at that temperature. For example, using a dynamic viscoelastic device, the rate of temperature rise It is a value measured under conditions of 5 ° C./min, tensile mode, and frequency 10 Hz.

  In the present invention, the storage elastic modulus is an index of the hardness (softness) of the film, and for example, using a dynamic viscoelastic device, the heating rate is 5 ° C./min, the tensile mode, and the frequency is 10 Hz. It is a value obtained by measuring under conditions.

  The parameters used in the present invention have been outlined above, but more specific measurement methods will be described in detail in the subsequent Examples section.

  Next, the significance of the critical value of the parameter will be described with some preferred embodiments of the present invention. Needless to say, the present invention is not limited to the following embodiments.

(First aspect)
One aspect of the present invention is an adhesive sheet that includes an adhesive layer and a base material layer, and an adhesive force between the adhesive layer and the base material layer is controlled by radiation irradiation. The adhesive layer (A1) has an adhesive strength of 200 mN / cm or more between the adhesive layer interface before irradiation and the base material layer interface, and (B1) 160 before irradiation. An adhesive sheet having a flow rate at 100 ° C. of 100 to 10,000 μm is mentioned.

(Second aspect)
According to another aspect of the present invention, there is provided an adhesive sheet including an adhesive layer and a base material layer, wherein an adhesive force between the adhesive layer and the base material layer is controlled by radiation irradiation. In the adhesive layer, (A1) the adhesive strength between the adhesive layer interface before radiation irradiation and the base material layer interface is 200 mN / cm or more, and (B2) 160 before radiation irradiation. Examples thereof include an adhesive sheet having a melt viscosity at 50 ° C. of 50 to 100,000 Pa · s.

  In the adhesive sheet as one aspect of the present invention, the flow amount of the adhesive layer is 100 to 10,000 μm, more preferably 100 to 6000 μm, and more preferably 200 to 4000 μm before radiation irradiation. Preferably, it is 500-4000 micrometers. If the flow amount is less than 100 μm, the adhesive sheet may not be sufficiently adhered to the semiconductor wafer to be diced, and if it exceeds 10,000 μm, the workability such as handling may be reduced.

  In the adhesive sheet as one aspect of the present invention, the flow amount ratio (post-irradiation flow amount / pre-irradiation flow amount) before and after radiation irradiation of the adhesive layer is preferably 0.1 or more. Is more preferably 15 or more, and further preferably 0.2 or more. If this value is less than 0.1, the semiconductor element may not be sufficiently bonded in the bonding process of the semiconductor element and the support member. The maximum value of the flow rate ratio is not particularly limited, but the maximum value that can normally be taken is 1.0.

  In the adhesive sheet as one aspect of the present invention, the adhesive strength before irradiation (during dicing) is preferably 200 mN / cm or more, and is preferably 250 mN / cm in that the semiconductor element does not scatter during dicing. More preferably, it is more preferably 300 mN / cm or more, and most preferably 350 mN / cm or more. Higher adhesive strength can prevent scattering of semiconductor elements, so there is no upper limit, but materials that can be easily obtained and those that can be manufactured with an appropriate manufacturing process are usually 25000 mN / cm or less, and 10000 mN / cm or less. Is relatively easy to manufacture.

  Moreover, in the adhesive sheet as one embodiment of the present invention, the adhesive strength ratio (adhesive strength after irradiation / adhesive strength before irradiation) of the adhesive layer / base material layer interface before and after irradiation with the 90 ° peel release force is 0. 0.5 or less, more preferably 0.4 or less, and even more preferably 0.3 or less. If this value is larger than 0.5, each element tends to be damaged during pick-up. On the other hand, the lower limit of the adhesive strength ratio (adhesive strength after irradiation / adhesive strength before irradiation) is not particularly limited, but is preferably 0.0001 or more, for example, from the viewpoint of workability.

  Further, in the adhesive sheet as one aspect of the present invention, the difference in adhesive strength (adhesive strength before irradiation-adhesive strength after irradiation) due to the 90 ° peel peeling force at the adhesive / substrate layer interface before and after irradiation is 100 mN. / Cm or more, more preferably 150 mN / cm or more, further preferably 200 mN / cm, and most preferably 250 mN / cm or more. If this value is less than 100 mN / cm, each element tends to be damaged during pick-up.

  The adhesive sheet as one embodiment of the present invention has a flow rate of 100 to 10,000 μm at 160 ° C. before radiation irradiation of the adhesive layer, a 90 ° peel peeling force before radiation irradiation of 200 mN / cm or more, and radiation. Dicing should be performed at a low temperature by setting the difference in adhesive strength (adhesive strength before irradiation-adhesive strength after irradiation) to be greater than or equal to 100 mN / cm at the 90 ° peel peel force at the adhesive / substrate layer interface before and after irradiation. Despite the fact that the adhesive sheet can be pressure-bonded to a semiconductor wafer, there is a conflicting characteristic that the semiconductor element has sufficient adhesive strength that does not scatter during dicing, and has low adhesive strength that does not damage each element during pick-up. Is also very advantageous in terms of process cost, and the flow rate ratio before and after irradiation (flow rate after irradiation / flow before irradiation). By over amount) is 0.1 or more, the bonding process between the semiconductor element and the support member to act as an adhesive sheet excellent in connection reliability.

  In the adhesive sheet of the present invention, the adhesive layer has a melt viscosity at 160 ° C. before irradiation of radiation of 50 to 100,000 Pa · s, more preferably 50 to 10,000 Pa · s, and more preferably 50 to 1000 Pa · s. More preferably, it is s. If the melt viscosity is less than 50 Pa · s, the adhesive sheet may not be sufficiently adhered to the semiconductor wafer to be diced, and if it exceeds 100,000 Pa · s, workability such as handling may be reduced. .

  Moreover, in the adhesive sheet as one embodiment of the present invention, the melt viscosity ratio (post-irradiation melt viscosity / pre-irradiation melt viscosity) of the adhesive layer before and after radiation irradiation is 100 or less and more preferably 95 or less. Preferably, it is 90 or less. If this value exceeds 100, the semiconductor element may not be sufficiently bonded in the bonding process between the semiconductor element and the support member.

  The adhesive sheet as one embodiment of the present invention has a melt viscosity of 50 to 100000 Pa · s at 160 ° C. before radiation irradiation of the adhesive layer, and the 90 ° peel peeling force of radiation irradiation is 200 mN / cm or more, Furthermore, the adhesive strength difference (adhesive strength before irradiation−adhesive strength after irradiation) due to the 90 ° peel peeling force at the adhesive layer / substrate layer interface before and after irradiation is set to 100 mN / cm or more at low temperature. Despite the fact that the adhesive sheet can be crimped to the semiconductor wafer to be diced, it has a sufficient adhesive strength that does not scatter semiconductor elements during dicing, and has a low adhesive strength that does not damage each element during pick-up. Satisfying the conflicting characteristics is extremely advantageous in terms of process costs, and the melt viscosity ratio before and after irradiation (melt viscosity after irradiation) (Degree of melt viscosity before irradiation) is 100 or less, it acts as an adhesive sheet having excellent connection reliability in the bonding step between the semiconductor element and the support member.

(Third aspect)
According to another aspect of the present invention, there is provided an adhesive sheet including an adhesive layer and a base material layer, wherein an adhesive force between the adhesive layer and the base material layer is controlled by radiation irradiation. The adhesive layer has (A2) tack strength at 25 ° C. measured by 5.1 mmΦ probe of the adhesive layer before radiation irradiation is 0.5 N or more, and (B1) radiation irradiation. An adhesive sheet having a flow rate of 100 to 10000 μm at the previous 160 ° C. is exemplified.

(Fourth aspect)
According to another aspect of the present invention, there is provided an adhesive sheet including an adhesive layer and a base material layer, wherein an adhesive force between the adhesive layer and the base material layer is controlled by radiation irradiation. The adhesive layer (A2) has a tack strength at 25 ° C. measured by 5.1 mmΦ probe of the adhesive layer before irradiation of (A2) of 0.5 N or more, and (B2) irradiation of radiation. The adhesive sheet whose melt viscosity in previous 160 degreeC is 50-100000 Pa.s is mentioned.

  The adhesive sheet as one aspect of the present invention has a tack strength at 25 ° C. measured by a 5.1 mmφ probe measurement before irradiation of the adhesive layer of 0.5 N or more and 0.6 N or more. More preferably, it is more preferably 0.7N or more, and most preferably 0.8N or more. If this value is less than 0.5N, the semiconductor element may be scattered during dicing.

  Further, the adhesive sheet as one embodiment of the present invention has a tack strength difference (post-irradiation tack strength-pre-irradiation tack strength) at 25 ° C. by a 5.1 mmφ probe measurement before and after radiation irradiation of the adhesive layer. 0.1N or more, more preferably 0.15N or more, and further preferably 0.2N or more. If this value is less than 0.1 N, each element tends to be damaged during pick-up.

  In the fourth aspect, from the viewpoint that the semiconductor element can be suitably bonded in the bonding step of the semiconductor element and the support member, the flow rate ratio before and after radiation irradiation (flow amount after irradiation / irradiation) in the adhesive sheet. The pre-flow amount) is preferably 0.1 or more, and the melt viscosity ratio before and after irradiation (melt viscosity after irradiation / melt viscosity before irradiation) is preferably 100 or less.

  The adhesive sheet as one embodiment of the present invention has a flow rate of 100 to 10,000 μm at 160 ° C. before irradiation of the adhesive layer, and 5.1 mmφ probe measurement before irradiation of the adhesive layer. The tack strength at 25 ° C. is 0.5 N or more, and the tack strength difference at 25 ° C. by the 5.1 mmφ probe measurement before and after irradiation of the adhesive layer (tack strength after irradiation−tack strength before irradiation) is 0. Although the adhesive sheet can be pressure-bonded to a semiconductor wafer to be diced at a low temperature by setting it to 1N or more, it has a sufficient adhesive force that the semiconductor elements do not scatter during dicing, and each element may be damaged during pick-up. It can satisfy the conflicting property of having low adhesive strength, which is very advantageous in terms of process cost and By flow amount ratio between the front and rear lines irradiation (flow amount / before irradiation flow amount after irradiation) to 0.1 or more, the bonding process between the semiconductor element and the support member to act as an adhesive sheet excellent in connection reliability.

  The adhesive sheet as one embodiment of the present invention has a melt viscosity of 50 to 100,000 Pa · s at 160 ° C. before irradiation of the adhesive layer, and 5 before irradiation of the adhesive layer. The tack strength at 25 ° C. measured by 1 mmφ probe is 0.5 N or more, and the tack strength difference at 25 ° C. measured by 5.1 mmφ probe before and after irradiation of the adhesive layer (tack strength after irradiation−tack before irradiation) (Strength) is 0.1 N or more, the adhesive sheet can be pressure-bonded to a semiconductor wafer to be diced at a low temperature. Since it can satisfy the conflicting property of having a low adhesive strength that will not damage the film, it will be very advantageous in terms of process cost. In both cases, by setting the melt viscosity ratio before and after irradiation (melt viscosity after irradiation / melt viscosity before irradiation) to 100 or less, it acts as an adhesive sheet having excellent connection reliability in the bonding step between the semiconductor element and the support member.

  In the first to fourth aspects described above, the adhesive strength after irradiation is preferably 100 mN / cm or less in order not to damage each element during pick-up. However, when bonding to a relatively thick semiconductor wafer, it may be more than this. 100 mN / cm or less is listed as a value applicable to any thickness of semiconductor wafer (for example, a very thin semiconductor wafer having a thickness of 20 μm, for example).

  As a method of adjusting the adhesive strength and tack strength of the adhesive layer before irradiation to the desired ranges, the adhesive strength and tack strength can be increased by increasing the fluidity of the adhesive layer at room temperature. What is necessary is just to utilize that there exists a tendency which rises and there exists a tendency for adhesive strength and tack strength to fall, if fluidity | liquidity is reduced. For example, in order to increase fluidity, there are methods such as increasing the plasticizer content and increasing the tackifier content. Conversely, when the fluidity is lowered, the content of the compound may be reduced. Examples of the plasticizer include monofunctional acrylic monomers, monofunctional epoxy resins, liquid epoxy resins, acrylic resins, and epoxy-based so-called diluents.

  Moreover, as a method of improving the flow amount before the radiation irradiation of the adhesive layer or a method of reducing the melt viscosity before the radiation irradiation, for example, addition of a diluent, use of a thermoplastic resin having a lower Tg, Use of an epoxy resin having a lower Tg and a curing agent can be mentioned. More specifically, when polyimide is used as the thermoplastic resin, an acid monomer and a diamine monomer are selected so that the imide group concentration of the polyimide is reduced, and a polyimide having a relatively low Tg is obtained by synthesizing the polyimide. It is done. When acrylic rubber is used, Tg can be lowered by increasing the number of carbon atoms of the alkyl group in the side chain of the acrylic rubber or increasing the flexibility of the main chain.

(Fifth aspect)
According to another aspect of the present invention, there is provided an adhesive sheet including an adhesive layer and a base material layer, wherein an adhesive force between the adhesive layer and the base material layer is controlled by radiation irradiation. The adhesive layer (C1) has an adhesive strength difference between the adhesive layer / base material layer interface before and after irradiation (adhesive strength before irradiation-adhesive strength after irradiation) of 100 mN / cm. Examples thereof include (D1) an adhesive sheet in which tan δ at 120 ° C. before irradiation is 0.1 or more and tan δ at 180 ° C. after irradiation is 0.1 or more.

(Sixth aspect)
According to another aspect of the present invention, there is provided an adhesive sheet including an adhesive layer and a base material layer, wherein an adhesive force between the adhesive layer and the base material layer is controlled by radiation irradiation. The adhesive layer (C1) has an adhesive strength difference between the adhesive layer / base material layer interface before and after irradiation (adhesive strength before irradiation-adhesive strength after irradiation) of 100 mN / cm. Examples thereof include (D2) an adhesive sheet having a storage elastic modulus at 120 ° C. before radiation irradiation of 10 MPa or less and a storage elastic modulus at 180 ° C. after radiation irradiation of 100 MPa or less.

  In the fifth and sixth embodiments, an adhesive sheet having the characteristic (D1) is used from the viewpoint of controlling the fluidity of the adhesive layer, and sufficient adhesive strength when the adhesive sheet is laminated on a semiconductor wafer. From the viewpoint of having sufficient adhesion at a temperature of 200 ° C. or lower when the semiconductor element is bonded, an adhesive sheet having the characteristic (D2) is used. Further, in the adhesive sheet, from the viewpoint of achieving good workability at the time of dicing and picking up, the adhesive strength ratio of the adhesive layer / substrate layer interface before and after radiation irradiation (adhesive strength after radiation irradiation / radiation) The adhesive strength before irradiation) is preferably 0.5 or less. Furthermore, in the adhesive sheet, the adhesive strength before radiation irradiation at the interface between the adhesive layer and the base material layer is 200 mN / cm or more from the viewpoint of achieving better workability at the time of dicing and picking up. The adhesive strength after radiation irradiation is preferably 100 mN / cm or less.

  In the adhesive sheet as one embodiment of the present invention, the tan δ at 120 ° C. of the adhesive layer before radiation irradiation is preferably 0.1 or more, and more preferably 0.3 or more. Further, the tan δ at 180 ° C. of the adhesive layer after radiation irradiation is preferably 0.1 or more. When each tan δ is less than 0.1, when the adhesive sheet is laminated to the semiconductor wafer via the adhesive layer at any temperature of room temperature to 150 ° C., the former is applied to the semiconductor wafer. A sufficient adhesive strength cannot be ensured. Moreover, about the latter, when bonding a semiconductor element to a supporting member through an adhesive layer, sufficient adhesiveness cannot be ensured at the temperature of 200 degrees C or less. In this way, by defining tan δ, the fluidity of the adhesive layer at a certain temperature can be accurately quantified, and the fluidity of the adhesive layer required for lamination to a semiconductor wafer and subsequent die bonding. Can be managed.

  In the adhesive sheet, the adhesive strength before radiation irradiation at the interface between the adhesive layer and the base material layer is 200 mN / cm or more, more preferably 250 mN / cm or more, and 300 mN / cm or more. More preferably it is. If this value is less than 200 mN / cm, the semiconductor element may be scattered during dicing. On the other hand, the adhesive strength after radiation irradiation is preferably 100 mN / cm or less. If this value is larger than 100 mN / cm, each element tends to be damaged during pickup.

  Further, in the adhesive sheet, the adhesive strength difference and the adhesive strength ratio at the adhesive layer / base material layer interface before and after radiation irradiation are the same values as those described in the first to fourth aspects. Can be applied for reasons of

  Further, in the adhesive sheet as one embodiment of the present invention, the storage elastic modulus at 120 ° C. before irradiation of the adhesive layer is 10 MPa or less, more preferably 5 MPa or less, further preferably 2 MPa or less, 180 after irradiation. The storage elastic modulus at ° C. is 100 MPa or less, more preferably 50 MPa or less, and still more preferably 10 MPa or less. As for the former, when the storage elastic modulus is larger than 10 MPa, when the adhesive sheet is laminated on the semiconductor wafer through the adhesive layer at any temperature of room temperature to 150 ° C., the semiconductor wafer is sufficient. The adhesive strength cannot be secured. As for the latter, if the storage elastic modulus is larger than 100 MPa, sufficient adhesion cannot be secured at a temperature of 200 ° C. or lower when the semiconductor element is bonded to the support member via the adhesive layer.

(Seventh aspect)
According to another aspect of the present invention, there is provided an adhesive sheet including an adhesive layer and a base material layer, wherein an adhesive force between the adhesive layer and the base material layer is controlled by radiation irradiation. The adhesive layer is (C2) the difference in tack strength at 25 ° C. between the adhesive layer before and after radiation irradiation (tack strength at 25 ° C. before radiation irradiation−tack strength at 25 ° C. after radiation irradiation). ) Is 0.1N / 5.1 mmΦ probe or more, and (D1) tan δ at 120 ° C. before irradiation is 0.1 or more, and tan δ at 180 ° C. after irradiation is 0.1 or more. Is mentioned.

(Eighth aspect)
According to another aspect of the present invention, there is provided an adhesive sheet including an adhesive layer and a base material layer, wherein an adhesive force between the adhesive layer and the base material layer is controlled by radiation irradiation. The adhesive layer is (C2) the difference in tack strength at 25 ° C. between the adhesive layer before and after radiation irradiation (tack strength at 25 ° C. before radiation irradiation−tack strength at 25 ° C. after radiation irradiation). ) Is 0.1 N / 5.1 mmΦ probe or more, and (D2) an adhesive sheet having a storage elastic modulus at 120 ° C. before irradiation of 10 MPa or less and a storage elastic modulus at 180 ° C. after irradiation of 100 MPa or less. Is mentioned.

  In the seventh and eighth embodiments, an adhesive sheet having the characteristic (D1) is used from the viewpoint of controlling the fluidity of the adhesive layer, and sufficient adhesive strength is obtained when the adhesive sheet is laminated on a semiconductor wafer. From the viewpoint of having sufficient adhesion at a temperature of 200 ° C. or lower when the semiconductor element is bonded, an adhesive sheet having the characteristic (D2) is used. In addition, in the adhesive sheet, from the viewpoint of achieving good workability at the time of dicing and picking up, from the viewpoint, the adhesive strength ratio of the adhesive layer / substrate layer interface before and after irradiation (adhesion after irradiation) (Strength / adhesive strength before irradiation) is preferably 0.5 or less. From the viewpoint of achieving better workability at the time of dicing and picking up, the adhesive sheet has an adhesive strength of 200 mN / before irradiation at the interface between the adhesive layer and the base material layer. It is preferable that the adhesive strength after irradiation is 100 mN / cm or less.

  In the adhesive sheet, the difference in tack strength at 25 ° C. of the adhesive layer before and after radiation irradiation (tack strength at 25 ° C. before radiation irradiation−tack strength at 25 ° C. after radiation irradiation) It is characterized by being 0.1N / 5.1mmΦ probe or more in that it can be picked up without being damaged, preferably 0.15N / 5.1mmΦ probe or more, and more than 0.2N / 5.1mmΦ probe. Is more preferable.

  Further, in the adhesive sheet, the tack strength at 25 ° C. of the adhesive layer before radiation irradiation is 0.5 N / 5.1 mmΦ probe or more, and the tack strength at 25 ° C. of the adhesive layer after radiation irradiation. Is preferably 0.4 N / 5.1 mmΦ probe or less. If the tack strength at 25 ° C. of the adhesive layer before irradiation is less than 0.5 N / 5.1 mmΦ probe, semiconductor elements may be scattered during dicing. On the other hand, if the tack strength at 25 ° C. of the adhesive layer after irradiation is greater than that of the 0.4 N / 5.1 mmΦ probe, each element tends to be damaged during pick-up.

  In the fifth to eighth aspects described above, the adhesive strength before radiation irradiation (during dicing) is preferably 200 mN / cm or more in terms of preventing the semiconductor element from scattering during dicing. 250 mN / cm or more, more preferably 300 mN / cm or more, and most preferably 350 mN / cm or more. Higher adhesive strength can prevent scattering of semiconductor elements, so there is no upper limit, but materials that can be easily obtained and those that can be manufactured with an appropriate manufacturing process are usually 25000 mN / cm or less, and 10000 mN / cm or less. Is relatively easy to manufacture. Moreover, in order not to damage each element at the time of pick-up, the adhesive strength after irradiation is preferably 100 mN / cm or less. However, when bonding to a relatively thick semiconductor wafer, it may be more than this. 100 mN / cm or less is listed as a value applicable to any thickness of semiconductor wafer (for example, a very thin semiconductor wafer having a thickness of 20 μm, for example).

  Examples of the method (C1) for increasing the difference in adhesive strength before and after radiation irradiation or the method (C2) for increasing the difference in tack strength before and after radiation irradiation include, for example, thermoplastic resins, thermosetting resins, and radiation irradiation. This can be achieved by increasing the proportion of the thermosetting resin and the compound generating the base in the adhesive layer containing the compound generating the base as an essential component. However, if the difference in the adhesive strength and the difference in tack strength are increased, the ratio of the flow amount before and after the irradiation and the ratio of the melt viscosity tend to increase at the same time. It is preferable to determine the proportion of the compound that generates the base.

  As a method of increasing tan δ at 120 ° C. before irradiation and tan δ at 180 ° C. after irradiation, or a method of decreasing storage elastic modulus at 120 ° C. before irradiation and storage elastic modulus at 180 ° C. after irradiation. May be any known technique that increases the fluidity of the adhesive layer. Specific examples include addition of a diluent, use of a thermoplastic resin having a lower Tg, use of a thermosetting resin and a curing agent having a lower Tg, and the like. If the material is selected so that the Tg of the entire adhesive layer is about 120 ° C. before irradiation and about 180 ° C. after irradiation, subsequent optimization is facilitated.

(Ninth aspect)
According to another aspect of the present invention, there is provided an adhesive sheet including an adhesive layer and a base material layer, wherein an adhesive force between the adhesive layer and the base material layer is controlled by radiation irradiation. The adhesive layer has a storage elastic modulus at 50 ° C. of 0.1 MPa to 200 MPa in an uncured or semi-cured state, and a storage elasticity at 50 ° C. after irradiation with a certain amount of radiation. Examples thereof include an adhesive sheet having a rate of at least twice that before irradiation and a flow amount at 160 ° C. after irradiation with a certain amount of radiation of 100 μm or more and 10,000 μm or less.

(Tenth aspect)
According to another aspect of the present invention, there is provided an adhesive sheet including an adhesive layer and a base material layer, wherein an adhesive force between the adhesive layer and the base material layer is controlled by radiation irradiation. The adhesive layer has a storage elastic modulus at 50 ° C. of 0.1 MPa to 200 MPa in an uncured or semi-cured state, and a storage elasticity at 50 ° C. after irradiation with a certain amount of radiation. Examples thereof include an adhesive sheet having a rate of 2 times or more before irradiation and a melt viscosity at 160 ° C. of 50 Pa · s to 10 ⁶ Pa · s.

(Eleventh aspect)
According to another aspect of the present invention, there is provided an adhesive sheet including an adhesive layer and a base material layer, wherein an adhesive force between the adhesive layer and the base material layer is controlled by radiation irradiation. The adhesive layer has a storage elastic modulus at 50 ° C. of 0.1 MPa to 200 MPa in an uncured or semi-cured state, and a storage elasticity at 50 ° C. after irradiation with a certain amount of radiation. Examples thereof include an adhesive sheet having a rate of 2 times or more of that before irradiation and a storage elastic modulus at 180 ° C. of 100 MPa or less.

  In the adhesive sheets of the ninth, tenth, and eleventh aspects, the storage elastic modulus at 50 ° C. of the uncured or semi-cured adhesive sheet needs to be 0.1 to 200 MPa. 0.5 to 150 MPa is preferable, 1.0 to 100 MPa is more preferable, and 2 to 50 MPa is particularly preferable. If the storage elastic modulus is less than 0.1 MPa, the semiconductor element is easily damaged during dicing, which is inappropriate. If it exceeds 200 MPa, lamination with the wafer cannot be performed, which is inappropriate. In the case of 2-50 Mpa, it is preferable at a point with the most favorable dicing property and laminating property with a wafer.

  Moreover, the storage elastic modulus at 50 ° C. of the adhesive sheet irradiated with a certain amount of radiation needs to be at least twice that before irradiation, and if it is less than twice, the semiconductor element is peeled off from the base film after irradiation. It is not preferable because it is difficult to do. It is more preferably 4 times or more, particularly preferably 10 times or more in that a thin semiconductor element or the like can be easily peeled from the base film.

  In the adhesive sheet of one embodiment of the present invention, the flow amount at 160 ° C. of the adhesive sheet after irradiating a certain amount of radiation to the uncured or semi-cured adhesive sheet needs to be in the range of 100 μm or more and 10,000 μm. It is. When the flow amount is less than 100 μm, the fluidity and wettability are insufficient at the time of pressure bonding of the semiconductor element, which is not preferable in that the adhesiveness is lowered. In addition, when the flow amount is more than 10,000 μm, the resin flows out excessively from the end of the semiconductor element when the semiconductor element is crimped, so that the electrode terminal portion of the support member of the semiconductor element is covered and the process such as wire bonding becomes difficult. Moreover, since the film thickness of an adhesive sheet falls, it is unpreferable at the point which adhesiveness falls.

  The flow amount is preferably in the range of 100 μm or more and 6000 μm or less in terms of smaller resin outflow from the end of the semiconductor element. In addition, when using a tape with a circuit or a substrate with a circuit as a support member of a semiconductor element, the flow amount is in the range of 1000 μm to 4000 μm because the circuit filling property is high and the resin outflow from the end is smaller. It is preferable that it exists in.

  When the flow amount A at 160 ° C. of the uncured or semi-cured adhesive sheet and the flow amount B after irradiating the adhesive sheet with a certain amount of radiation satisfy the relationship of B / A ≧ 1/10, radiation irradiation Even if there is some variation in the amount and condition, it is preferable in that the variation in the flow amount after irradiation is small. Further, the point B / A ≧ 1/5 with less variation in the flow amount after irradiation is more preferable, and B / A ≧ 1/2 is most preferable.

  In the adhesive sheet of one embodiment of the present invention, the melt viscosity at 160 ° C. after the adhesive layer is irradiated with a certain amount of radiation needs to be 50 to 100,000 Pa · s. When the melt viscosity is less than 50 Pa · s, the fluidity is excessive, the resin outflow from the end portion is large, and the film thickness of the adhesive sheet is reduced, so that the adhesiveness tends to be reduced. . On the other hand, when it exceeds 100,000 Pa · s, the fluidity is low, and the adhesiveness and the circuit filling property tend to be lowered.

  In addition, when the storage elastic modulus at 50 ° C. after irradiating a certain amount of radiation to the uncured or semi-cured adhesive sheet is 15 MPa or more, a thin semiconductor element or the like can be easily peeled from the base film. Is particularly preferable.

  Furthermore, the storage elastic modulus at 100 ° C. of the uncured or semi-cured adhesive sheet is 0.0001 to 2 MPa because it can be laminated at a low temperature, and the storage elastic modulus at 50 ° C. is easy to dice. The storage elastic modulus at 50 ° C. is 15 to 200 MPa after radiation irradiation because it is 0.1 to 200 MPa and easy to peel off, and the storage elastic modulus at 180 ° C. is 100 MPa or less in terms of high fluidity. Further, it is particularly preferable that the storage elastic modulus at 50 ° C. after curing is 100 to 5000 MPa in view of good heat resistance. The storage elastic modulus at 50 ° C. of the uncured or semi-cured adhesive sheet is preferably 5 to 100 MPa, and more preferably 7.5 to 50 MPa in terms of further excellent dicing workability.

  In the adhesive sheet of one embodiment of the present invention, the adhesive layer has a storage elastic modulus of 10 to 2000 MPa at 25 ° C. and preferably 3 to 50 MPa at 260 ° C. at the stage of heat curing. The storage elastic modulus at 25 ° C. is more preferably 20 to 1900 MPa, and particularly preferably 50 to 1800 MPa. Further, the storage elastic modulus at 260 ° C. is more preferably 4 to 50 MPa, and particularly preferably 5 to 50 MPa. When the storage elastic modulus is within this range, the effect of relaxing the thermal stress generated by the difference in the thermal expansion coefficient between the semiconductor element and the support member is maintained, and the occurrence of peeling and cracking can be suppressed, and the handling property of the adhesive can be suppressed. The thickness accuracy of the adhesive layer and the occurrence of reflow cracks can be suppressed.

  The storage elastic modulus of the adhesive layer at the stage of heat curing is, for example, increasing the amount of epoxy resin used, using an epoxy resin with a high glycidyl group concentration or a phenol resin with a high hydroxyl group concentration, etc. It can be increased by increasing the crosslink density. Needless to say, the storage elastic modulus is lowered if the reverse of the above measures is taken.

  In the adhesive sheet of one embodiment of the present invention, the adhesive strength (pulling) at 250 ° C. of a laminated cured product in which a 5 mm square semiconductor element and a support member are bonded via the adhesive layer of the adhesive sheet after radiation irradiation. The peel strength is preferably 3.0 N / chip or more. The peeling method between the semiconductor element and the supporting member is roughly divided into an interface failure that peels between the adhesive layer and the supporting member, and a cohesive failure that breaks and peels off the adhesive layer. . In order to suppress interfacial fracture, it is effective to increase the fluidity of the adhesive layer or increase the flow rate of the adhesive layer after irradiation. It is effective to select materials so that the crosslinking density of the adhesive layer is increased, increase the molecular weight of the thermoplastic resin, and adjust the elastic modulus at 260 ° C. to a range of 0.01 to 50 MPa.

  As described above, some specific embodiments have been described. However, since the various characteristics are effective characteristics for obtaining a more excellent adhesive sheet, more appropriate adhesion can be achieved by appropriately combining them. Needless to say, a sheet can be obtained.

(Adjustment of curing degree)
When the adhesive sheet as one aspect of the present invention contains a thermoplastic resin and a thermosetting resin as main components in the adhesive layer, the adhesive sheet when the adhesive sheet is irradiated with radiation. It is preferable that (B−A) /B=0.1 to 0.7 when the heat generation amount by DSC of the layer is A and the heat generation amount before radiation irradiation is B.

  In the adhesive sheet, when the amount of heat generated by DSC of the adhesive layer when irradiated with radiation is A, and the amount of heat generated before radiation irradiation is B, (BA) / B = 0 to 0.1. 7 is preferable, and more preferably 0.2 to 0.5. In order not to damage the semiconductor element at the time of picking up after irradiation, it is preferably 0.1 or more. Moreover, when picking up and heat-bonding a semiconductor element to a support member via an adhesive layer after picking up, 0.7 or more is preferable in order to ensure sufficient fluidity.

  The calorific value generated by the DSC is measured by using a suggested scanning calorimeter (also referred to as “DSC” in this specification) as described later in the column of the evaluation method, at a heating rate of 10 ° C./min. It is a value obtained when measured under conditions of a temperature of 20 ° C to 300 ° C.

  Further, the adhesive layer contains a photoreactive compound that accelerates the curing reaction of the thermosetting resin by irradiation with radiation. Furthermore, the photoreactive compound is a compound that generates a base upon irradiation with radiation having a wavelength of 150 to 750 nm.

  The compound that generates a base upon irradiation is not particularly limited as long as it is a compound that generates a base upon irradiation. As the base to be generated, a strongly basic compound is preferable in terms of reactivity and curing speed. In general, a pKa value that is a logarithm of an acid dissociation constant is used as a basic index, and a base having a pKa value in an aqueous solution of 7 or more is preferable, and a base of 9 or more is more preferable. Examples of the photobase generator used are as described above.

  In the adhesive sheet, the thermoplastic resin used has a Tg of −50 to 10 ° C. and a weight average molecular weight of 100,000 to 1,000,000. When Tg is lower than −50 ° C., the self-supporting property as an adhesive layer is lost and a problem occurs in handling properties. When Tg exceeds 10 ° C., the temperature required for adhesion increases, and neither is preferable. (Tg in the present invention indicates a value measured using DSC as will be described later in the evaluation method column.) When the weight average molecular weight is within this range, the sheet or film is formed. The strength, flexibility, and tackiness are appropriate, and since the flow property is appropriate, good circuit filling property of wiring can be secured. If the weight average molecular weight is out of the above range, the above-mentioned properties when formed into a sheet or film are impaired. In the present invention, the weight average molecular weight is measured by gel permeation chromatography (also referred to as “GPC” in the present specification) as described later in the column of evaluation method, and a standard polystyrene calibration curve is used. The converted value is shown.

  Moreover, in the said adhesive sheet, Tg of the thermoplastic resin to be used is 10-100 degreeC, and a weight average molecular weight is 5000-200000. About said Tg, More preferably, it is 10-80 degreeC. When Tg is less than 10 ° C., the self-supporting property as an adhesive layer is lost, and there is a problem in handleability. When Tg exceeds 100 ° C., the temperature required for adhesion increases, which is not preferable. In addition, Tg in this invention shows the value calculated | required by DSC. Moreover, about the said weight average molecular weight, More preferably, it is 20000-150,000, More preferably, it is 20000-80000. When the weight average molecular weight is within this range, the strength, flexibility, and tackiness of a sheet or film are appropriate, and the flowability is appropriate, ensuring good circuit filling of wiring. it can. If the weight average molecular weight is out of the above range, the above-mentioned properties when formed into a sheet or film are impaired. The weight average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

(Chemical structure of adhesive layer)
As a result of studying from the chemical structural aspect of the adhesive layer in order to further optimize the adhesive sheet of the present invention having the above-mentioned actions and effects such that the work process can be simplified, the present inventors have The present inventors have found that the above-described effects can be obtained more suitably by using an adhesive layer having characteristics as described below.

  That is, the adhesive sheet as one aspect of the present invention and the resin composition constituting the same are a resin that forms a crosslinked network structure by radiation irradiation in a sea-island phase separation resin that does not have a crosslinked network structure before irradiation and heating. It does not form a crosslinked network structure by irradiation with radiation, but preferably has a sea phase composed of a resin that forms a crosslinked structure by heating.

  In order to impart adhesiveness in the B-stage state, it is preferable that the structure does not have a crosslinked network structure before irradiation. Furthermore, as a result of examining the molecular structure after radiation irradiation, when the sea phase forms a network structure, the fluidity tends to decrease and the adhesiveness tends to decrease, and when the island phase does not form a network structure, It was found that there is a tendency to be highly adhesive and difficult to peel. That is, when the adhesive sheet is irradiated with radiation, the island phase preferably forms a crosslinked network structure in terms of adhesiveness, while the sea phase makes it easy to peel the adhesive layer from the base material layer. It is preferable not to form a crosslinked network structure.

  After radiation irradiation and heat curing, it is necessary to provide a crosslinked network structure for both the sea phase and the island phase in order to impart heat resistance. Regarding the sea-island structure, the cross section of the sample was observed by SEM, and the dispersed portion was determined as the island phase and the continuous phase as the island phase. The radiation dose and wavelength are adjusted so that the above effects are exhibited.

  The formation of the crosslinked network structure of each phase was determined as follows. That is, a sample (weight Xg) was infiltrated into 10 g of MEK at 25 ° C. for 1 h, and then insoluble matters were removed with a 200-mesh nylon cloth. The weight Y of the filtrate (dissolved component) dried at 170 ° C. for 1 h was measured, and the dissolved component ratio (%) was measured from the initial sample and the weight ratio Y / X × 100 (%). When the dissolved component ratio was less than 80%, a network structure was formed and an insoluble part was formed, so it was determined that the sea phase formed a crosslinked network structure. In addition, when the dissolved component ratio is 80% or more, it is judged that a filter having a visible light transmittance of 80% or more in a 5 mm-thick cell has a crosslinked network structure in both the sea phase and the island phase. did. When the visible light transmittance in a 5 mm-thick cell of the filtrate was less than 80%, the sea phase did not have a crosslinked network structure, but the island phase was judged to have a crosslinked network structure.

  Examples of the combination of resins that form a sea-island structure having the above-mentioned characteristics by radiation irradiation include, for example, a combination of a low-molecular-weight thermosetting component that is compatible with a high-molecular-weight component in the initial stage. A combination of a glycidyl group-containing (meth) acrylic copolymer and an epoxy resin is preferable in terms of excellent adhesiveness.

  Adhesive strength ratio (adhesive strength after irradiation / adhesive strength before irradiation) of the adhesive layer / substrate layer interface before and after irradiation with the 90 ° peel peel force is 0.5 or less and 0.4 or less. Is more preferable, and it is further more preferable that it is 0.3 or less. If this value is larger than 0.5, each element tends to be damaged during pick-up. On the other hand, the lower limit of the adhesive strength ratio (adhesive strength after irradiation / adhesive strength before irradiation) is not particularly limited, but is preferably 0.0001 or more, for example, from the viewpoint of workability. The adhesive force at the interface between the adhesive layer and the base material layer at the time of dicing (before radiation irradiation) is bonded to the semiconductor wafer to be diced by pressing the adhesive sheet at room temperature or while heating, Only the base material layer can be measured by the peel peel force when pulled at a pulling angle of 90 ° and a pulling speed of 50 mm / min.

  Further, in the adhesive sheet, the difference in adhesive strength due to the 90 ° peel peel force at the interface between the adhesive layer and the base material layer before and after irradiation (adhesive strength before irradiation-adhesive strength after irradiation) is 100 mN / cm or more, More preferably, it is 150 mN / cm or more, further preferably 200 mN / cm, and most preferably 250 mN / cm or more. If this value is less than 100 mN / cm, each element tends to be damaged during pick-up.

  The flow amount at 160 ° C. of the adhesive sheet after irradiating a certain amount of radiation to the uncured or semi-cured adhesive sheet is preferably in the range of 100 μm or more and 10,000 μm.

<Manufacturing method>
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 composition on a base film and heating to remove the solvent.

  The adhesive sheet of the present invention irradiates the adhesive sheet with an actinic ray having a wavelength range of 150 to 750 nm after the dicing step, polymerizes and cures the radiation-polymerizable adhesive sheet, and the adhesive force between the adhesive sheet and the substrate interface This makes it possible to pick up semiconductor elements.

  Further, the solvent for varnishing is not particularly limited, but considering the volatility during film production, for example, methanol, ethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, It is preferable to use a solvent having a relatively low boiling point such as methyl ethyl ketone, acetone, methyl isobutyl ketone, toluene, and xylene. For the purpose of improving the coating properties, for example, a solvent having a relatively high boiling point such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone and cyclohexanone can be used. These solvents can be used alone or in combination of two or more.

  For the production of the varnish when the inorganic filler is added, it is preferable to use a raking machine, a three-roll, a ball mill, a bead mill or the like in consideration of the dispersibility of the inorganic filler, or a combination thereof. You can also. Moreover, after mixing an inorganic filler and a low molecular weight raw material beforehand, the mixing time can also be shortened by mix | blending a high molecular weight raw material. Further, after the varnish is formed, the bubbles in the varnish can be removed by vacuum degassing 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. .

  Although there is no restriction | limiting in particular in the thickness of an adhesive sheet, 5-250 micrometers is preferable for both an adhesive layer and a base material layer. If the thickness is less than 5 μm, the stress relaxation effect tends to be poor. If the thickness is more than 250 μm, it is not economical and the demand for miniaturization of the semiconductor device cannot be met.

  Moreover, in order to obtain a desired sheet thickness, the adhesive sheet of the present invention is further provided so as to sandwich one or more adhesive layers or adhesive layers between the semiconductor wafer and the adhesive layer. May be. In this case, as the adhesive layer provided as desired, in addition to those prepared by the above method, those prepared by a conventionally known method can be used. As the adhesive layer provided as desired, a commercially available adhesive sheet such as a polyimide-based, silicon oligomer-based, rubber-epoxy-based, or epoxy-based adhesive can be used. However, it is necessary to consider a bonding condition that does not cause peeling between the adhesive layers based on a conventionally known technique.

<How to use>
When radiation is applied to the adhesive sheet having the configuration as described above, the adhesive strength of the adhesive layer to the base material layer is greatly reduced after radiation irradiation. Therefore, as will be described later, by using the adhesive sheet of the present invention in a dicing process when manufacturing a semiconductor device, the adhesive layer and the base material layer are easily peeled, resulting in an adhesive contact. A semiconductor element with an adhesive layer can be suitably picked up.

The radiation irradiated in the present invention is an actinic ray having a wavelength range of 150 to 750 nm, and includes ultraviolet rays, far ultraviolet rays, near ultraviolet rays, visible rays, electron beams, infrared rays, near infrared rays, and the like. For example, 0.01-10000 J / cm ² can be irradiated using a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, or a metal halide lamp.

  Since a part of the thermopolymerizable resin contained in the adhesive layer is cured by the radiation irradiation, it is considered that the adhesive force between the adhesive layer and the base material layer is reduced. When a sufficient decrease in adhesive strength cannot be obtained only by irradiation with radiation, it is preferable to accelerate the curing reaction by heating together. The heating temperature varies depending on the progress of the curing reaction by radiation irradiation and also depends on the composition of the adhesive layer, but the adhesive sheet may be usually exposed to an atmosphere of 30 to 100 ° C. For the heating, a heater or an oven may be used. However, a general radiation irradiation source often generates heat upon irradiation, and it is preferable to use this heat generation because it is not necessary to prepare a heating device separately.

  In addition, the adhesive force between the adhesive layer layer and the base material layer after irradiation of the present invention is, for example, after the adhesive sheet is bonded to a semiconductor wafer to be diced by pressure bonding at room temperature or while heating. The peel peel force (adhesive strength) when only the base material layer is pulled at a pulling angle of 90 ° and a pulling speed of 50 mm / min is 100 mN / cm or less, more preferably 90 mN / cm or more. More preferably, it is 80 mN / cm or more. If this value exceeds 100 mN / cm, each element tends to be damaged during pick-up.

  Then, although the usage method of the adhesive sheet which concerns on this invention is demonstrated referring FIGS. 1-8, it cannot be overemphasized that the usage method of this invention is not limited to the following method. In addition, about the thing which has the same function in a figure, the same code | symbol is attached | subjected and the description is abbreviate | omitted.

  FIG. 1 discloses an adhesive sheet 10 including a base film 1 and a first adhesive layer 2, and FIG. 2 further shows a second adhesive layer 3 in addition to the above-described constituent elements. An adhesive sheet 20 is disclosed.

When these adhesive sheets 10 and 20 are used as a dicing tape, first, the adhesive sheets 2 and 3 of the adhesive sheets 10 and 20 are placed on a predetermined work table so that the wafer surface is in close contact.

  In addition, when the peelable sheet is provided on the upper surface of the adhesive sheet according to the present invention, the peelable sheet is peeled and removed, and then the adhesive sheet 2 and 3 of the adhesive sheet is faced upward. Place on the work table.

  Next, as shown in FIG. 3, the semiconductor wafer A to be diced is attached to the upper surface of the second adhesive layer 3. At this time, as described above, one or more adhesive layers or adhesive layers are further sandwiched between the semiconductor wafer A and the second adhesive layer 3 in order to obtain a desired sheet thickness. It may be provided as follows.

  Subsequently, dicing, cleaning, and drying steps are added to the semiconductor wafer A in this attached state. At this time, since the semiconductor wafer A is sufficiently adhered and held on the adhesive sheet by the second adhesive layer 3, the semiconductor wafer A does not fall off during each of the above steps.

  FIG. 4 shows that the dicing cutter 6 is used to dice the wafer A to provide the cuts indicated by bold lines, and the semiconductor elements A1, A2, and A3 are obtained.

  Next, as shown in FIG. 5, radiation B is applied to the adhesive layers 2 and 3 of the adhesive sheet, and a part or most of the radiation-polymerizable adhesive sheet is polymerized and cured. In this case, heating may be used in combination with the purpose of accelerating the curing reaction simultaneously with irradiation or after irradiation. By using heating together, the adhesive strength can be reduced at a lower temperature and in a shorter time. Although heating temperature will not be restrict | limited especially if it is below the thermal decomposition temperature of an adhesive agent layer, The temperature of 50-170 degreeC is preferable.

  Irradiation to the adhesive sheet is performed from the surface of the base film 1 on which the adhesive layer 2 is not provided as indicated by an arrow B in FIG. Therefore, as described above, when UV is used as the radiation, the base film 1 needs to be light transmissive, but when EB is used as the radiation, the base film 1 is not necessarily light transmissive. There is no need.

  After irradiation, semiconductor elements A1, A2, A3 to be picked up are picked up by, for example, a suction collet 4 as shown in FIG. At this time, instead of the suction collet 4 or in combination with the suction collet 4, the semiconductor elements A1, A2, A3 to be picked up can be pushed up from the lower surface of the base film 1 by, for example, a needle rod.

  Since the adhesive force between the semiconductor element A1 and the adhesive layer 3 is larger than the adhesive force between the adhesive layer 2 and the base film 1, when the semiconductor element A1 is picked up, the adhesive force The adhesive layer 2 is peeled off while being attached to the lower surface of the semiconductor element A1 (see FIG. 7).

  Next, the semiconductor elements A1, A2, and A3 are placed on the semiconductor element mounting support member 5 through the adhesive layer 2 and heated. By heating, the adhesive layer 2 exhibits an adhesive force, and the bonding between the semiconductor elements A1, A2, A3 and the semiconductor element mounting support member 5 is completed (see FIG. 8).

  The adhesive sheet of the present invention described above is obtained by irradiating the adhesive sheet with radiation such as ultraviolet rays (UV) or electron beams (EB) after the dicing step, and polymerizing and curing the radiation-polymerizable adhesive sheet. The semiconductor element can be picked up by reducing the adhesive force between the (layer) and the substrate film interface. In the case of the conventional adhesive sheet, when the surface tension of the substrate exceeds 40 mN / m, the adhesive force between the adhesive sheet and the substrate is not sufficiently lowered, and the pickup property tends to be inferior. However, even if the surface tension of the base material exceeds 40 mN / m, the adhesive sheet of the present invention has an adhesive force between the adhesive sheet and the base material after irradiation with ultraviolet rays (UV) or electron beams (EB). It is sufficiently reduced and the pickup of the semiconductor element becomes good. Therefore, conventionally, in order to make the surface tension of the base material 40 mN / m or less, the base film to be used is surface-treated, but in the adhesive sheet of the present invention, it is necessary to surface-treat the base film. This is advantageous in terms of cost.

  Although the present invention has been described above, the following adhesive sheet is further exemplified as a preferred embodiment of the adhesive sheet of the present invention.

(Twelfth aspect)
As a preferable aspect of the adhesive sheet of the present invention, the adhesive sheet includes an adhesive layer and a base material layer, and an adhesive force between the adhesive layer and the base material layer is controlled by irradiation with radiation. 10 to 400 parts by weight of a high molecular weight component having a weight average molecular weight of 100,000 or more and (b) a thermally polymerizable component, wherein the adhesive layer is an adhesive sheet, And (c) an adhesive sheet containing 0.01 to 200 parts by weight of a compound capable of generating a base upon irradiation with radiation.

(13th aspect)
Moreover, as a preferable aspect of the adhesive sheet of the present invention, the adhesive sheet includes an adhesive layer and a base material layer, and the adhesive force between the adhesive layer and the base material layer is controlled by irradiation with radiation. An adhesive sheet, wherein the adhesive layer comprises 100 parts by weight of a polyimide resin, (b) 1 to 200 parts by weight of a thermopolymerizable component, and (c) a compound that generates a base upon irradiation with radiation. Examples thereof include an adhesive sheet containing 0.01 to 200 parts by weight. Here, in the twelfth and thirteenth aspects, it is preferable to use an epoxy resin and an epoxy resin curing agent as the thermopolymerizable component from the viewpoint of workability and heat resistance.

(14th aspect)
One embodiment of the present invention is an adhesive sheet that includes an adhesive layer and a base material layer, and an adhesive force between the adhesive layer and the base material layer is controlled by irradiation of radiation. The adhesive layer has (A2) tack strength at 25 ° C. measured by 5.1 mmΦ probe of the adhesive layer before radiation irradiation is 0.5 N or more, and (B1) radiation irradiation. The adhesive sheet whose flow amount in the previous 160 degreeC is 100-10000 micrometers is mentioned.

(15th aspect)
According to another aspect of the present invention, there is provided an adhesive sheet including an adhesive layer and a base material layer, wherein an adhesive force between the adhesive layer and the base material layer is controlled by radiation irradiation. The adhesive layer (A2) has a tack strength at 25 ° C. measured by 5.1 mmΦ probe of the adhesive layer before irradiation of (A2) of 0.5 N or more, and (B2) irradiation of radiation. The adhesive sheet whose melt viscosity in previous 160 degreeC is 50-100000 Pa.s is mentioned.

(Sixteenth aspect)
Furthermore, as a preferable aspect of the adhesive sheet of the present invention, the adhesive sheet includes an adhesive layer and a base material layer, and the adhesive force between the adhesive layer and the base material layer is controlled by irradiation with radiation. In the adhesive sheet, the adhesive layer is (C1) difference in adhesive strength between the adhesive layer / substrate layer interface before and after irradiation (adhesive strength before irradiation-adhesion after irradiation) Strength) is 100 mN / cm or more, and an adhesive sheet having at least one of the following properties is exemplified.

(D1) tan δ at 120 ° C. before irradiation is 0.1 or more, tan δ at 180 ° C. after irradiation is 0.1 or more,
(D2) The storage elastic modulus at 120 ° C. before irradiation is 10 MPa or less, and the storage elastic modulus at 180 ° C. after irradiation is 100 MPa or less. From the viewpoint of controlling the fluidity of the adhesive layer, the characteristic (D1 From the viewpoint of having sufficient adhesive strength when the adhesive sheet is laminated to a semiconductor wafer and having sufficient adhesiveness at a temperature of 200 ° C. or lower when the semiconductor element is bonded. An adhesive sheet having D2) is used.

(17th aspect)
Furthermore, as a preferable aspect of the adhesive sheet of the present invention, the adhesive sheet includes an adhesive layer and a base material layer, and the adhesive force between the adhesive layer and the base material layer is controlled by irradiation with radiation. The adhesive sheet, wherein the adhesive layer is (C2) the difference in tack strength at 25 ° C. of the adhesive layer before and after radiation irradiation (tack strength at 25 ° C. before radiation irradiation−after radiation irradiation) And an adhesive sheet having at least one of the following characteristics.

(D1) tan δ at 120 ° C. before irradiation is 0.1 or more, tan δ at 180 ° C. after irradiation is 0.1 or more,
(D2) The storage elastic modulus at 120 ° C. before irradiation is 10 MPa or less, and the storage elastic modulus at 180 ° C. after irradiation is 100 MPa or less. From the viewpoint of controlling the fluidity of the adhesive layer, the characteristic (D1 From the viewpoint of having sufficient adhesive strength when the adhesive sheet is laminated to a semiconductor wafer and having sufficient adhesiveness at a temperature of 200 ° C. or lower when the semiconductor element is bonded. An adhesive sheet having D2) is used.

(18th aspect)
Moreover, as a preferable aspect of the adhesive sheet of the present invention, the adhesive sheet includes an adhesive layer and a base material layer, and the adhesive force between the adhesive layer and the base material layer is controlled by irradiation with radiation. In the adhesive sheet, the adhesive layer has an uncured or semi-cured storage elastic modulus at 50 ° C. of 0.1 MPa or more and 200 MPa or less, and a certain amount of radiation. After the irradiation, the storage elastic modulus at 50 ° C. is more than twice that before the irradiation, and the adhesive layer after irradiation with a certain amount of radiation has the following (E), (F) and (G It is preferable to have at least one of the characteristics shown in (1).
(E) The flow amount at 160 ° C. is 100 μm or more and 10,000 μm or less,
(F) The melt viscosity at 160 ° C. is 50 Pa · s or more and 10 ⁶ Pa · s or less, and (G) the storage elastic modulus at 180 ° C. is 100 MPa or less.

(19th aspect)
Furthermore, as a preferable aspect of the adhesive sheet of the present invention, the adhesive sheet includes an adhesive layer and a base material layer, and the adhesive force between the adhesive layer and the base material layer is irradiated by radiation. In the adhesive sheet to be controlled, the adhesive layer (A1) has an adhesive strength between the adhesive layer interface and the base material layer interface before irradiation of radiation of 200 mN / cm or more, and the following: An adhesive sheet having at least one of the above characteristics can be mentioned.

(B1) The flow amount at 160 ° C. before radiation irradiation is 100 to 10,000 μm,
(B2) The melt viscosity at 160 ° C. before radiation irradiation is 50 to 100,000 Pa · s.
Here, an adhesive sheet having characteristics (B1) is used from the viewpoint of dicing workability, and an adhesive sheet having characteristics (B2) is used from the viewpoint of adhesiveness. Moreover, in the said adhesive sheet, it is preferable that the flow amount ratio (flow amount after irradiation / flow amount before irradiation) before and behind radiation irradiation is 0.1 or more. In the adhesive sheet, it is preferable that an adhesive strength ratio (post-irradiation adhesive strength / pre-irradiation adhesive strength) before and after radiation irradiation at the interface between the adhesive layer and the base material layer is 0.5 or less. Furthermore, in the adhesive sheet, it is preferable that a difference in adhesive strength before and after radiation irradiation (adhesive strength before irradiation−adhesive strength after irradiation) at the interface between the adhesive layer and the base material layer is 100 mN / cm or more. Furthermore, in the adhesive sheet, the melt viscosity ratio (post-irradiation melt viscosity / pre-irradiation melt viscosity) before and after radiation irradiation is preferably 100 or less.

(20th aspect)
Furthermore, as a preferable aspect of the adhesive sheet of the present invention, the adhesive sheet includes an adhesive layer and a base material layer, and the adhesive force between the adhesive layer and the base material layer is controlled by irradiation with radiation. In the adhesive sheet, the adhesive layer has an uncured or semi-cured storage elastic modulus at 50 ° C. of 0.1 MPa to 200 MPa, and 50 ° C. after irradiation with a certain amount of radiation. And the adhesive layer after irradiating a certain amount of radiation has the characteristics shown in the following (E), (F) and (G). Among them, an adhesive sheet having at least one characteristic can be mentioned.

(E) The flow amount at 160 ° C. is 100 μm or more and 10,000 μm or less,
(F) The melt viscosity at 160 ° C. is 50 Pa · s or more and 10 ⁶ Pa · s or less, and (G) the storage elastic modulus at 180 ° C. is 100 MPa or less.

  Further, in the adhesive sheet, from the viewpoint of obtaining good adhesiveness, a flow amount A at 160 ° C. of the adhesive layer of the uncured or semi-cured adhesive sheet and a certain amount of radiation are irradiated to the adhesive sheet. It is preferable that the flow amount B of the adhesive layer after satisfying the relationship of B / A ≧ 1/10. Moreover, it is preferable that the storage elastic modulus in 50 degreeC of the adhesive layer after irradiating a fixed amount of radiation to the unhardened or semi-hardened adhesive sheet is 15 Mpa or more. Furthermore, it is preferable that the adhesive layer satisfies the following conditions.

1) Storage elastic modulus at 100 ° C. in an uncured or semi-cured state is 0.001 MPa or more and 2 MPa or less, 2) Storage elastic modulus at 50 ° C. is 7.5 MPa or more and 50 MPa or less, and 3) after irradiation The storage elastic modulus at 50 ° C. is 15 MPa or more and 100 MPa or less, and 4) The storage elastic modulus at 50 ° C. after curing is 100 MPa or more and 5000 MPa or less. Furthermore, the adhesive strength at 250 ° C. of the laminated cured product of the 5 mm square semiconductor element and the support member using the adhesive layer of the adhesive sheet after irradiation is preferably 3.0 N / chip or more. . The storage elastic modulus of the adhesive layer when measured using a dynamic viscoelasticity measuring device of the adhesive sheet after heat curing is 10 MPa to 2000 MPa at 25 ° C., and 3 MPa to 50 MPa at 260 ° C. It is preferable.

  Further, as another aspect of the present invention, the following semiconductor device manufacturing method and semiconductor device are provided.

  A method for manufacturing a semiconductor device, comprising a semiconductor element and a semiconductor element mounting support member or a semiconductor element bonded together using the adhesive sheet of the present invention.

  A step of adhering the adhesive sheet of the present invention having an adhesive layer and a base material layer to a semiconductor wafer with the adhesive layer interposed therebetween; and dicing the semiconductor wafer to provide an adhesive layer A step of forming a semiconductor element; a step of irradiating the adhesive sheet after dicing to cure the adhesive layer and then peeling off the base film layer; and a semiconductor element with the adhesive layer; A step of bonding a semiconductor element mounting support member or semiconductor elements to each other via the adhesive sheet.

  A semiconductor device having a structure in which a semiconductor element and a semiconductor element mounting support member or semiconductor elements are bonded to each other using the adhesive sheet of the present invention.

EXAMPLES Hereinafter, the present invention will be described in more detail using examples. The present invention is not limited to these. In addition, evaluation about an adhesive sheet was performed in accordance with the method demonstrated in the column of the evaluation method demonstrated later unless it mentions specially in each Example.

(Synthesis Example 1) [Synthesis of photobase generator]
30 g of 2-nitrobenzyl alcohol was stirred and dissolved in 300 g of tetrahydrofuran at room temperature using a magnetic stirrer. A solution consisting of 24.5 g of 4,4′-diphenylmethane diisocyanate and 100 g of tetrahydrofuran was added dropwise to this solution over 30 minutes, followed by stirring at room temperature for 1 hour. Thereafter, a Liebig cooling tube was set and reacted for 2 hours while heating to 60 ° C. in an oil bath. After the reaction, the reaction solution was cooled to room temperature and concentrated using a rotary evaporator until the reaction solution was halved.

  When the obtained concentrate was added to 1000 parts by weight of n-hexane, a white precipitate was obtained. The precipitate was filtered by suction and dried overnight at 60 ° C. under vacuum to obtain the desired 2-nitrobenzylcarbamic acid derivative (PB-1). The yield was 49.5 g (yield 91%).

(Synthesis Example 2) [Synthesis of photobase generator]
Add p-nitrobenzoic acid methyl ester (2.00 g, 11 mmol), N, N-dimethylhydrazine (0.66 g, 11 mmol), phenylglycidyl ether (1.66 g, 11 mmol) to tert-butanol (15.0 g). After stirring at 50 ° C. for 10 hours, the mixture was further stirred at room temperature (25 ° C.) for 48 hours, resulting in the formation of a white precipitate. This was filtered off, washed twice with ethyl acetate, and dried with a vacuum dryer to obtain an amine imide compound (PB-2). The yield was 3.67 g, the yield was 85%, and the melting point was 146-147 ° C.

(Synthesis Example 3) [Synthesis of photobase generator]
p-Cyanobenzoic acid methyl ester (2.00 g, 12 mmol), N, N-dimethylhydrazine (0.75 g, 12 mmol), phenylglycidyl ether (1.86 g, 12 mmol) are added to tert-butanol (10 g), After stirring at 50 ° C. for 72 hours, the mixture was further stirred at room temperature for 48 hours. After removing tert-butanol from the obtained reaction solution with a rotary evaporator, 10 g of ethyl acetate was added and recrystallization was performed to obtain a white amine imide compound (PB-3). The yield was 2.74 g, the yield was 65%, and the melting point was 148 to 149 ° C.

(Synthesis Example 4) [Synthesis of Photobase Generator]
A solution of 1-benzyl-2-methylimidazole (1.73 g, 10.5 mmol) dissolved in acetone (20 g) in which phenacyl bromide (2.00 g, 10.5 mmol) was dissolved. Was added slowly, followed by stirring at room temperature (25 ° C.) for 2 hours to precipitate white crystals. This was filtered, washed twice with acetone, and then dried under vacuum at 60 ° C. for 5 hours to obtain imidazolium bromide salt 1 (yield 3.54 g).

The above-mentioned imidazole bromide salt 1 (2.00 g, 5.4 mmol) was dissolved in a methanol / water (15 g / 15 g) solution, and sodium tetraphenylborate (1.84 g) dissolved in water (5.0 g). 5.4 mmol) was added slowly. A white slurry-like precipitation was observed with the addition, and the mixture was further stirred at room temperature for 5 hours. This precipitate was filtered, dissolved in acetone (20 g) and recrystallized to obtain the desired imidazolium tetraphenylborate (PB-4) (yield 2.86 g). The ¹ H-NMR of this compound is shown in FIG. Moreover, when the melting point and thermal decomposition start temperature in an oxygen atmosphere were measured by TG-DTA, the melting point was 187 ° C. and the decomposition start temperature was 224 ° C.

(Synthesis Example 5) [Synthesis of photobase generator]
p-Nitrophenacyl bromide (2.00 g, 8.2 mmol) was dissolved in acetone (20 g) and 1,2-dimethylimidazole (0.79 g, 8.2 mmol) dissolved in acetone (5 g) was dissolved therein. The solution was slowly added, and then stirred at room temperature for 2 hours to precipitate white crystals. This was filtered, washed twice with acetone, and then dried under vacuum at 60 ° C. for 5 hours to obtain imidazolium bromide salt 2 (yield 2.62 g).

  The above-mentioned imidazole bromide salt (2.00 g, 5.8 mmol) was dissolved in a methanol / water (15 g / 15 g) solution, and tetraphenylborate sodium salt (2.01 g) dissolved in water (5.0 g). 5.8 mmol) solution was added slowly. A white slurry-like precipitation was observed with the addition, and the mixture was further stirred at room temperature for 5 hours. This was filtered, dissolved in acetone (20 g) and recrystallized to obtain the target imidazolium tetraphenylborate (PB-5) (yield 2.83 g).

The ¹ H-NMR of this compound is shown in FIG. Moreover, when the melting point and thermal decomposition start temperature in an oxygen atmosphere were measured by TG-DTA, the melting point was 165 ° C. and the decomposition start temperature was 195 ° C.

(Synthesis Example 6) [Synthesis of Polyimide Resin]
In a 500 ml flask equipped with a thermometer, stirrer and calcium chloride tube, 41.05 g (0.1 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 150 g of N-methyl-2-pyrrolidone Were stirred. After dissolution of the diamine, 52.2 g (0.1 mol) of 1,10- (decamethylene) bis (trimellitate anhydride) was added in small portions while the flask was cooled in an ice bath. After reacting at room temperature for 3 hours, 30 g of xylene was added and heated at 150 ° C. while blowing nitrogen gas to azeotropically remove xylene together with water. The reaction solution was poured into water, and the precipitated polymer was filtered off and dried to obtain a polyimide resin (PI-1).

(Synthesis Example 7) [Synthesis of polyimide resin]
In a 500 ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, 5.41 g (0.045 mol) of 1,12-diaminododecane, 11.54 g of ether diamine (manufactured by BASF, ether diamine 2000 (molecular weight: 1923)) ( 0.01 mol), 24.3 g (0.045 mol) of polysiloxane diamine (manufactured by Shin-Etsu Silicone, KF-8010 (molecular weight: 900)) and 169 g of N-methyl-2-pyrrolidone were charged and stirred. After dissolution of the diamine, a small amount of 31.23 g (0.1 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic dianhydride) was cooled in the ice bath. Added in increments. After reacting at room temperature for 8 hours, 112.7 g of xylene was added and heated at 180 ° C. while blowing nitrogen gas, and xylene was removed azeotropically with water. The reaction solution was poured into water, and the precipitated polymer was filtered off and dried to obtain a polyimide resin (PI-2).

(Synthesis Example 8) [Synthesis of polyimide resin]
Into a 1 liter four-necked flask equipped with a stirrer, a nitrogen introducing tube, and a drying tube was placed 41.0 g (0.10 mol) of 2,2-bis (4- (4-aminophenoxy) phenyl) propane. In a nitrogen stream, 250 g of N-methyl-2-pyrrolidone was added to make a solution. The flask was transferred to a water bath, and 41.0 g (0.10 mol) of 1,2- (ethylene) bis (trimellitate dianhydride) was added little by little with vigorous stirring. When the acid dianhydride was almost dissolved, the reaction was performed for 6 hours with slow stirring to obtain a polyamic acid solution. Next, a distillation apparatus was attached to the four-necked flask containing the polyamic acid solution, and 220 g of xylene was added. Condensed water produced by imidization was distilled off azeotropically with xylene under vigorous stirring on a 180 ° C. oil bath under a nitrogen stream. The reaction solution was poured into water, and the precipitated polymer was filtered and dried to obtain a polyimide resin (PI-3).

  The composition and physical properties of the obtained polyimide resins (PI-1 to PI-3) are shown together in Table 1. Each physical property was measured under the following conditions.

(12) 'Tg
Measurement was carried out using a suggested scanning calorimeter (hereinafter abbreviated as DSC) (Perkin Elmer, DSC-7 type) at a temperature elevation rate of 10 ° C./min.

尚、表１中の記号は下記のものを示す。 (13) ′ Weight average molecular weight Measured by gel permeation chromatography (hereinafter abbreviated as GPC) and converted to standard polystyrene.

In addition, the symbol in Table 1 shows the following.

BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane DDO: 1,12-diaminododecane EDA: ether diamine 2000 (molecular weight: 1923)
KF-8010: polysiloxane diamine (molecular weight: 900)
DBTA: 1,10- (decamethylene) bis (trimellitate anhydride)
BPADA: 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic dianhydride)
EBTA: 1,2- (ethylene) bis (trimellitate dianhydride)
Next, adhesive sheets 1 to 25 having the compositions shown in Tables 2 and 3 in Production Examples 1 to 25 were produced. The compositions of the adhesive sheets 1 to 25 are summarized in Tables 2 and 3.

(Production Example 1)
YDCN-703 (trade name, manufactured by Toto Kasei Co., Ltd., o-cresol novolac type epoxy resin, epoxy equivalent 210) 42.3 parts by weight, Phenolite LF2882 (trade name, manufactured by Dainippon Ink & Chemicals, Inc., bisphenol A novolak) Resin) 23.9 parts by weight, HTR-860P-3 (trade name, manufactured by Nagase ChemteX Corporation, epoxy group-containing acrylic rubber, molecular weight 1 million, Tg-7 ° C.) 44.1 parts by weight, Curazole 2PZ-CN ( Shikoku Kasei Kogyo Co., Ltd. trade name, 1-cyanoethyl-2-phenylimidazole) 0.4 parts by weight, NUC A-187 (Nihon Unicar Co., Ltd. trade name, γ-glycidoxypropyltrimethoxysilane) 0 7 parts by weight of 2-nitrobenzylcarbamic acid derivative (PB-1) 0.5 parts by weight Stirring and mixing, and the mixture was deaerated under vacuum. This adhesive varnish was applied onto a polyethylene terephthalate having a thickness of 50 μm (manufactured by Teijin DuPont Films, Teijin Tetron film: G2-50, surface tension 50 dyne / cm), and heated and dried at 140 ° C. for 5 minutes. An adhesive sheet having a base material (polyethylene terephthalate film) and a film thickness of 50 μm (adhesive sheet thickness excluding the base material is 50 μm) (adhesive sheet 1) was prepared.

  Storage elastic modulus when this adhesive sheet 1 was cured at 170 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology) (sample size: length 20 mm, width 4 mm, film thickness) 80 μm, temperature rising rate 5 ° C./min, tensile mode 10 Hz, automatic static load). As a result, it was 360 MPa at 25 ° C. and 30 MPa at 260 ° C.

(Production Example 2)
In Production Example 1, 2-nitrobenzylcarbamic acid derivative (PB-1) was converted to 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanon-1-one (manufactured by Ciba Specialty Chemicals, product) Name: Irgacure 369), except that the same operation as in Production Example 1 was performed, and an adhesive sheet with a base material (polyethylene terephthalate film) having a thickness of 50 μm (the thickness of the adhesive sheet excluding the base material was 50 μm) (Adhesive sheet 2) was produced.

  Storage elastic modulus when this adhesive sheet 2 was cured at 170 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology) (sample size: length 20 mm, width 4 mm, film thickness) 80 μm, temperature rising rate 5 ° C./min, tensile mode 10 Hz, automatic static load). As a result, it was 350 MPa at 25 ° C. and 25 MPa at 260 ° C.

(Production Example 3)
Denacol EX-411 (trade name, manufactured by Nagase ChemteX Corporation, aliphatic epoxy resin, tetrafunctional, epoxy equivalent 231), 76.0 parts by weight, Phenolite LF2882 (trade name, manufactured by Dainippon Ink & Chemicals, Inc., bisphenol A novolac resin) 39.0 parts by weight, HTR-860P-3) trade name, manufactured by Nagase ChemteX Corporation, epoxy group-containing acrylic rubber, molecular weight 1 million, Tg-7 ° C) 76.7 parts by weight, Curesol 2PZ- CN (trade name, 1-cyanoethyl-2-phenylimidazole) manufactured by Shikoku Chemicals Co., Ltd., NUC A-187 (trade name, manufactured by Nippon Unicar Co., Ltd., γ-glycidoxypropyltrimethoxysilane) ) 0.7 parts by weight, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1-one (C Methyl ethyl ketone was added to a composition consisting of 1.0 part by weight of Iba Specialty Chemicals, trade name: Irgacure 369), and the mixture was stirred and mixed, followed by vacuum degassing. This adhesive varnish was applied onto a polyethylene terephthalate having a thickness of 50 μm (manufactured by Teijin DuPont Films, Teijin Tetron film: G2-50, surface tension 50 dyne / cm), and heated and dried at 140 ° C. for 5 minutes. An adhesive sheet having a base material (polyethylene terephthalate film) and a film thickness of 50 μm (adhesive sheet thickness excluding the base material is 50 μm) (adhesive sheet 3) was produced.

  Storage elastic modulus when this adhesive sheet 3 was cured at 170 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology) (sample size: length 20 mm, width 4 mm, film thickness) 80 μm, temperature rising rate 5 ° C./min, tensile mode 10 Hz, automatic static load). As a result, it was 360 MPa at 25 ° C. and 10 MPa at 260 ° C.

(Production Example 4)
Epicoat 828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 190), 45.0 parts by weight, ESCN195 (trade name, Sumitomo Chemical Co., Ltd., o-cresol novolac type epoxy resin, epoxy equivalent) 195) 15.0 parts by weight, Priofen LF2882 (trade name, manufactured by Dainippon Ink and Chemicals, bisphenol A novolac resin) 40.0 parts by weight, HTR-860P-3 (trade name, manufactured by Nagase ChemteX Corporation) Epoxy group-containing acrylic rubber, molecular weight 1 million, Tg-7 ° C.) 66.7 parts by weight, Curesol 2PZ-CN (trade name, 1-cyanoethyl-2-phenylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) Part, NUC A-187 (trade name, γ-glycidoxypropyl manufactured by Nippon Unicar Co., Ltd.) (Rimethoxysilane) 0.7 parts by weight, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1-one (Ciba Specialty Chemicals, trade name: Irgacure 369) 1.0 Methyl ethyl ketone was added to the composition consisting of parts by weight, mixed with stirring, and vacuum degassed. This adhesive varnish was applied onto a polyethylene terephthalate having a thickness of 50 μm (manufactured by Teijin DuPont Films, Teijin Tetron film: G2-50, surface tension 50 dyne / cm), and heated and dried at 140 ° C. for 5 minutes. An adhesive sheet having a base material (polyethylene terephthalate film) and a film thickness of 50 μm (adhesive sheet thickness excluding the base material is 50 μm) (adhesive sheet 3) was produced.

  The storage elastic modulus when this adhesive sheet 4 is cured at 170 ° C. for 1 hour is measured using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology) (sample size: length 20 mm, width 4 mm, film thickness). 80 μm, temperature rising rate 5 ° C./min, tensile mode, 10 Hz, automatic static load). As a result, it was 360 MPa at 25 ° C. and 14 MPa at 260 ° C.

(Production Example 5)
In Production Example 1, the same operation as in Production Example 1 was carried out except that 2-nitrobenzylcarbamic acid derivative (PB-1) was changed to amine imide compound (PB-2), and a substrate (polyethylene terephthalate film) was provided. An adhesive sheet having a film thickness of 50 μm (the thickness of the adhesive sheet excluding the substrate is 50 μm) (adhesive sheet 5) was produced.

  Storage elastic modulus when this adhesive sheet 5 was cured at 170 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology) (sample size: length 20 mm, width 4 mm, film thickness) 80 μm, temperature rising rate 5 ° C./min, tensile mode 10 Hz, automatic static load). As a result, it was 350 MPa at 25 ° C. and 35 MPa at 260 ° C.

(Production Example 6)
In Production Example 1, the same operation as in Production Example 1 was performed except that 0.1 part by weight of benzophenone was added, and an adhesive sheet having a base material (polyethylene terephthalate film) having a thickness of 50 μm (excluding the base material). The thickness of the adhesive sheet was 50 μm) (adhesive sheet 6).

  Storage elastic modulus when this adhesive sheet 6 was cured at 170 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology) (sample size: length 20 mm, width 4 mm, film thickness). 80 μm, temperature rising rate 5 ° C./min, tensile mode 10 Hz, automatic static load). As a result, it was 350 MPa at 25 ° C. and 35 MPa at 260 ° C.

(Production Example 7)
In Production Example 1, the same operation as in Production Example 1 was performed except that the 2-nitrobenzylcarbamic acid derivative (PB-1) was changed to an amine imide compound (PB-3), and a substrate (polyethylene terephthalate film) was provided. An adhesive sheet having a thickness of 50 μm (the thickness of the adhesive sheet excluding the base material is 50 μm) (adhesive sheet 7) was produced.

  Storage modulus when this adhesive sheet 7 is cured at 170 ° C. for 1 hour is measured using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology) (sample size: length 20 mm, width 4 mm, film thickness) 80 μm, temperature rising rate 5 ° C./min, tensile mode 10 Hz, automatic static load). As a result, it was 350 MPa at 25 ° C. and 35 MPa at 260 ° C.

(Production Example 8)
A substrate (polyethylene terephthalate film) was prepared in the same manner as in Production Example 1 except that the 2-nitrobenzylcarbamic acid derivative (PB-1) was changed to imidazolium tetraphenylborate (PB-4). ) With a film thickness of 50 μm (the thickness of the adhesive sheet excluding the substrate is 50 μm) (adhesive sheet 8).

  Storage elastic modulus when this adhesive sheet 8 was cured at 170 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology) (sample size: length 20 mm, width 4 mm, film thickness) 80 μm, temperature rising rate 5 ° C./min, tensile mode 10 Hz, automatic static load). As a result, it was 340 MPa at 25 ° C. and 30 MPa at 260 ° C.

(Production Example 9)
The same procedure as in Production Example 1 was performed except that the 2-nitrobenzylcarbamic acid derivative (PB-1) was changed to imidazolium tetraphenylborate (PB-5) in Production Example 1, and a base material (polyethylene terephthalate film) ) With a film thickness of 50 μm (adhesive sheet thickness excluding the substrate is 50 μm) (adhesive sheet 9).

  Storage adhesive modulus when this adhesive sheet 9 is cured at 170 ° C. for 1 hour is measured using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology) (sample size: length 20 mm, width 4 mm, film thickness) 80 μm, temperature rising rate 5 ° C./min, tensile mode 10 Hz, automatic static load). As a result, it was 360 MPa at 25 ° C. and 35 MPa at 260 ° C.

(Production Example 10)
In Production Example 1, the same operation as in Production Example 1 was carried out except that the amount of 2-nitrobenzylcarbamic acid derivative (PB-1) was 0.005 part by weight, and the film thickness provided with a substrate (polyethylene terephthalate film). Was prepared as an adhesive sheet (adhesive sheet 10 excluding the base material having a thickness of 50 μm) (adhesive sheet 10).

  The storage elastic modulus when this adhesive sheet 10 was cured at 170 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology) (sample size: length 20 mm, width 4 mm, film thickness). 80 μm, temperature rising rate 5 ° C./min, tensile mode 10 Hz, automatic static load). As a result, it was 380 MPa at 25 ° C. and 30 MPa at 260 ° C.

(Production Example 11)
In Production Example 1, the same operation as in Production Example 1 was performed except that the 2-nitrobenzylcarbamic acid derivative (PB-1) was changed to 150.0 parts by weight, and the film thickness provided with the base material (polyethylene terephthalate film). Produced an adhesive sheet (adhesive sheet 11 having a thickness of 50 μm excluding the base material) (adhesive sheet 11).

  The storage elastic modulus when this adhesive sheet 11 was cured at 170 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology) (sample size: length 20 mm, width 4 mm, film thickness). 80 μm, temperature rising rate 5 ° C./min, tensile mode 10 Hz, automatic static load). As a result, it was 30 MPa at 25 ° C. and 1 MPa at 260 ° C.

(Production Example 12)
In Production Example 1, the same operation as in Production Example 1 was carried out except that the 2-nitrobenzylcarbamic acid derivative (PB-1) was removed. (The thickness of the adhesive sheet excluding the substrate was 50 μm) (adhesive sheet 12) was produced.

  Storage modulus when this adhesive sheet 12 was cured at 170 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology) (sample size: length 20 mm, width 4 mm, film thickness). 80 μm, temperature rising rate 5 ° C./min, tensile mode 10 Hz, automatic static load). As a result, it was 380 MPa at 25 ° C. and 30 MPa at 260 ° C.

(Production Example 13)
YDCN-703 (trade name, manufactured by Toto Kasei Co., Ltd., o-cresol novolac type epoxy resin, epoxy equivalent 210) 42.3 parts by mass, Phenolite LF2882 (trade name, manufactured by Dainippon Ink & Chemicals, Inc., bisphenol A novolak) Resin) 23.9 parts by mass, HTR-860P-3) Product name, manufactured by Nagase ChemteX Corporation, epoxy group-containing acrylic rubber, molecular weight 1 million, Tg-7 ° C.) 44.1 parts by mass, Curazole 2PZ-CN ( Shikoku Kasei Kogyo Co., Ltd. trade name, 1-cyanoethyl-2-phenylimidazole) 0.4 parts by mass, NUC A-187 (Nihon Unicar Co., Ltd. trade name, γ-glycidoxypropyltrimethoxysilane) 0 .7 parts by mass, 4G (trade name, tetraethylene glycol dimethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) and 22.05 parts by mass - a composition comprising 0.5 parts by hydroxycyclohexyl phenyl ketone, and stirred mixed with methyl ethyl ketone and vacuum degassed. This adhesive varnish was coated on a polyethylene terephthalate film having a thickness of 50 μm, dried by heating at 140 ° C. for 5 minutes, and an adhesive sheet having a substrate (polyethylene terephthalate film) having a thickness of 50 μm (excluding the substrate) The thickness of the adhesive sheet was 50 μm) (adhesive sheet 13).

  The storage elastic modulus when this adhesive sheet 13 was cured at 170 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology) (sample size: length 20 mm, width 4 mm, film thickness). 80 μm, heating rate 5 ° C./min, tensile mode, 10 Hz, automatic static load). As a result, it was 400 MPa at 25 ° C. and 50 MPa at 260 ° C.

(Production Example 14)
50 parts by weight of the polyimide resin (PI-1) obtained in Production Example 6, 10 parts by weight of o-cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: ESCN-195), phenol novolac resin (Maywa) Made by Kasei Co., Ltd., trade name: H-1) 5.3 g, tetraphenylphosphinium tetraphenylborate (Hokuko Chemical Co., Ltd., trade name: TPPK) 0.2 parts by weight, obtained in Synthesis Example 1 0.2 parts by weight of the obtained 2-nitrobenzylcarbamic acid derivative (PB-1) is added and dissolved in 200 parts by weight of N-methyl-2-pyrrolidone as a solvent. This was stirred well and dispersed uniformly to obtain an adhesive varnish. This adhesive varnish was applied onto a polyethylene terephthalate having a thickness of 50 μm (manufactured by Teijin DuPont Films, Teijin Tetron film: G2-50, surface tension 50 dyne / cm), and heated and dried at 150 ° C. for 20 minutes. An adhesive sheet having a base material (polyethylene terephthalate film) and a film thickness of 50 μm (adhesive sheet thickness excluding the base material is 50 μm) (adhesive sheet 14) was prepared.

(Production Example 15)
In Production Example 14, 2-nitrobenzylcarbamic acid derivative (PB-1) was converted to 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanon-1-one (manufactured by Ciba Specialty Chemicals, product) Name: Irgacure 369), except that the same operation as in Production Example 14 was performed, and an adhesive sheet with a base material (polyethylene terephthalate film) having a thickness of 50 μm (the thickness of the adhesive sheet excluding the base material was 50 μm) (Adhesive sheet 15) was produced.

(Production Example 16)
In Production Example 14, the same operation as in Production Example 14 was performed except that the 2-nitrobenzylcarbamic acid derivative (PB-1) was changed to an amine imide compound (PB-2), and a substrate (polyethylene terephthalate film) was provided. An adhesive sheet having a thickness of 50 μm (the thickness of the adhesive sheet excluding the base material is 50 μm) (adhesive sheet 16) was produced.

(Production Example 17)
In Production Example 16, the same operation as in Production Example 16 was carried out except that 0.05 part by weight of benzophenone was added. The thickness of the adhesive sheet was 50 μm) (adhesive sheet 17).

(Production Example 18)
In Production Example 14, the same operation as in Production Example 14 was carried out except that the 2-nitrobenzylcarbamic acid derivative (PB-1) was changed to an amine imide compound (PB-3), and a substrate (polyethylene terephthalate film) was provided. An adhesive sheet having a thickness of 50 μm (the thickness of the adhesive sheet excluding the base material is 50 μm) (adhesive sheet 18) was produced.

(Production Example 19)
The same procedure as in Production Example 14 was performed except that the 2-nitrobenzylcarbamic acid derivative (PB-1) was changed to imidazolium tetraphenylborate (PB-4) in Production Example 14, and a substrate (polyethylene terephthalate film) ) With a film thickness of 50 μm (adhesive sheet thickness excluding the base material is 50 μm) (adhesive sheet 19).

(Production Example 20)
In Production Example 14, the same operation as in Production Example 14 was carried out except that the 2-nitrobenzylcarbamic acid derivative (PB-1) was changed to imidazolium tetraphenylborate (PB-5), and a base material (polyethylene terephthalate film) ) With a film thickness of 50 μm (adhesive sheet thickness excluding the substrate is 50 μm) (adhesive sheet 20).

(Production Example 21)
50 parts by weight of the polyimide resin (PI-2) obtained in Production Example 7, 13 parts by weight of o-cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: ESCN-195), phenol novolac resin (Maywa) 6.9 parts by weight, manufactured by Kasei Co., Ltd., trade name: H-1), 0.13 parts by weight of tetraphenylphosphinium tetraphenylborate (manufactured by Hokuko Chemical Co., Ltd., trade name: TPPK), 2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1-one (trade name: Irgacure 369, manufactured by Ciba Specialty Chemicals) was added in an amount of 4.0 parts by weight as a solvent, N-methyl-2- Add to 200 parts by weight of pyrrolidone and dissolve. This was stirred well and dispersed uniformly to obtain an adhesive varnish. This adhesive varnish was applied onto a polyethylene terephthalate having a thickness of 50 μm (manufactured by Teijin DuPont Films, Teijin Tetron film: G2-50, surface tension 50 dyne / cm), and heated and dried at 150 ° C. for 20 minutes. An adhesive sheet having a base material (polyethylene terephthalate film) and a film thickness of 50 μm (adhesive sheet thickness excluding the base material is 50 μm) (adhesive sheet 21) was prepared.

(Production Example 22)
In Production Example 15, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1-one (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 369) was 0.004 part by weight. Except for the above, the same operation as in Production Example 15 was performed to produce an adhesive sheet having a base material (polyethylene terephthalate film) and a film thickness of 50 μm (the thickness of the adhesive sheet excluding the base material was 50 μm) (adhesive sheet 22). did.

(Production Example 23)
In Production Example 15, 120.0 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1-one (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 369) was used. Except for the above, the same operation as in Production Example 15 was performed to prepare an adhesive sheet having a base material (polyethylene terephthalate film) and a film thickness of 50 μm (the thickness of the adhesive sheet excluding the base material was 50 μm) (adhesive sheet 23). did.

(Production Example 24)
In Production Example 14, except for the 2-nitrobenzylcarbamic acid derivative (PB-1), the same operation as in Production Example 14 was performed, and an adhesive sheet having a base material (polyethylene terephthalate film) having a film thickness of 50 μm (The thickness of the adhesive sheet excluding the substrate was 50 μm) (adhesive sheet 24) was produced.

(Production Example 25)
50 parts by weight of the polyimide resin (PI-3) obtained in Production Example 8, 13 parts by weight of an o-cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: ESCN-195), phenol novolac resin (Maywa) 6.9 parts by weight made by Kasei Co., Ltd., trade name: H-1), 0.13 parts by weight of tetraphenylphosphinium tetraphenylborate (made by Hokuko Chemical Co., Ltd., trade name: TPPK), with a solvent Add to 200 parts by weight of N-methyl-2-pyrrolidone and dissolve. This was stirred well and dispersed uniformly to obtain an adhesive varnish. This adhesive varnish was applied onto a polyethylene terephthalate having a thickness of 50 μm (manufactured by Teijin DuPont Films, Teijin Tetron film: G2-50, surface tension 50 dyne / cm), and heated and dried at 150 ° C. for 20 minutes. An adhesive sheet having a base material (polyethylene terephthalate film) and a film thickness of 50 μm (adhesive sheet thickness excluding the base material is 50 μm) (adhesive sheet 25) was produced.

  The adhesive sheets 1 to 25 produced in Production Examples 1 to 25 were evaluated as shown in the following Examples 1 to 45 and Comparative Examples 1 to 11.

(Examples 1 to 11)
Using the adhesive sheets 1 to 11 obtained in Production Examples 1 to 11, a semiconductor device sample in which a wiring board using a semiconductor chip and a polyimide film having a thickness of 25 μm as a base material is bonded with an adhesive sheet (with solder balls on one side) Formation) and the heat resistance and moisture resistance were examined. As a heat resistance evaluation method, reflow crack resistance and a temperature cycle test were applied. The evaluation of reflow crack resistance was repeated twice by passing the sample through an IR reflow furnace set at a maximum temperature of 240 ° C. and holding this temperature for 20 seconds, and then allowing it to cool at room temperature. The cracks in the samples were observed visually and with an ultrasonic microscope. The probability of occurrence of cracks (% / 100 chips) is shown. The temperature cycle resistance is that the sample is left in an atmosphere at -55 ° C for 30 minutes and then left in an atmosphere at 125 ° C for 30 minutes. After 1000 cycles, the sample is destroyed by peeling or cracking using an ultrasonic microscope. The probability that no occurrence occurred (% / 100 chips). The moisture resistance was evaluated by observing peeling after 72 hours of treatment in an atmosphere (pressure cooker test: PCT treatment) at a temperature of 121 ° C., humidity of 100%, and 2.03 × 10 ⁵ Pa. It was shown by the probability (% / 100 chip) that peeling did not occur.

  On the other hand, the adhesive sheets 1 to 11 were stuck on a silicon wafer having a thickness of 150 μm, and the silicon wafer with the adhesive sheet was placed on a dicing apparatus. Next, the semiconductor wafer was fixed on a dicing apparatus and diced to 5 mm × 5 mm at a speed of 100 mm / sec, and then 500 mJ / cm 2 using a UV-330 HQP-2 type exposure machine manufactured by Oak Manufacturing Co., Ltd. The chip was exposed from the support film side of the adhesive sheet with the exposure amount and diced with a pickup device, and the chip skipping and pick-up properties during dicing were evaluated. Pickup performance is indicated by the probability (% / 100 chips) of picking up a chip after dicing with a pickup die bonder. It was.

Further, the silicon wafer with an adhesive sheet was exposed from the support film side of the adhesive sheet at an exposure amount of 500 mJ / cm ² , and the adhesive strength at the adhesive sheet / substrate interface before and after exposure was measured at 90 ° peel strength ( (Tensile speed 50 mm / min). These evaluation results are summarized in Table 4.

(Comparative Examples 1-2)
The adhesive sheets 12 and 13 obtained in Production Examples 12 and 13 were evaluated under the same conditions as in Example 1. The results are shown in Table 4.

(Examples 12 to 21)
The adhesive sheets 14 to 23 obtained in Production Examples 14 to 23 were evaluated under the same conditions as in Examples and 1. The results are shown in Table 5.

(Comparative Examples 3-4)
The adhesive sheets 24 and 25 obtained in Production Examples 24 and 25 were evaluated under the same conditions as in Examples 1 and 1. The results are shown in Table 5.

  From Tables 4 and 5, it was found that the adhesive sheet of the present invention was excellent in heat resistance and moisture resistance, had no chip skipping during dicing, and had good pickup properties. Furthermore, since the difference in adhesive strength before and after exposure was large, it was found that the working condition margin was large and the workability was excellent.

(Example 22)
The tack strength, flow amount, and melt viscosity before and after irradiation of the adhesive sheet 1 produced in Production Example 1 were measured under the following conditions. The results are shown in Table 6 together with the evaluation results in Tables 4 and 5 described above.

(10) Tack strength The tack strength of the adhesive layer of the adhesive sheet 1 was measured at 25 ° C. by the method described in JISZ0237-1991 using a tacking tester manufactured by RHESCA. The measurement conditions were a probe diameter of 5.1 mmφ, a peeling speed of 10 mm / s, a contact load of 9.81 × 10 ³ Pa (100 gf / cm ² ), and a contact time of 1 s.

（式中、Z0は荷重を加える前の接着フィルムの厚さ、Zは荷重を加えて後の接着フィルムの厚さ、Vは接着フィルムの体積、Fは加えた荷重、tは荷重を加えた時間を表す）
（実施例２３〜２５）
製造例２〜４で作製した接着シート２〜４の放射線照射前後のタック強度、フロー量及び溶融粘度を実施例２２と同様の条件で測定した。結果を表６に示す。 (2) 'Flow amount The adhesive sheet 1 is cut to a size of 10 x 20 mm and placed on a glass slide so that the adhesive layer side of the adhesive sheet is in close contact, and a thermocompression test apparatus (Tester Sangyo Co., Ltd.) The maximum distance that protruded from the end of a 20 mm long piece to the periphery of the four samples with the optical microscope was measured for each sample with an optical microscope. 2 points, a total of 8 points were measured, and the flow amount consisting of the average value was measured. (3) ′ Melt viscosity Eight adhesive layers of the adhesive sheet 1 were laminated to produce a film having a thickness of about 400 μm. After that, this was punched into a circle with a diameter of 11.3 mm as a sample, pressurized at 160 ° C. with a load of 24.5 N (2.5 kgf) for 5 seconds, measured by a parallel plate plus and meter method, It was calculated melt viscosity (η) I.

(In the formula, Z0 is the thickness of the adhesive film before applying the load, Z is the thickness of the adhesive film after applying the load, V is the volume of the adhesive film, F is the applied load, and t is the applied load. Time)
(Examples 23 to 25)
The tack strength, flow amount, and melt viscosity of the adhesive sheets 2 to 4 produced in Production Examples 2 to 4 were measured under the same conditions as in Example 22. The results are shown in Table 6.

(Examples 26 to 29)
The tack strength, flow amount, and melt viscosity of the adhesive sheets 14 to 17 produced in Production Examples 14 to 17 before and after irradiation were measured under the same conditions as in Example 22. The results are shown in Table 6.

(Comparative Examples 5-6)
The tack strength, flow amount, and melt viscosity of the adhesive sheets 12 and 25 produced in Production Examples 12 and 25 before and after irradiation were measured under the same conditions as in Example 22. The results are shown in Table 6.

From Table 6, it was found that the adhesive sheet of the present invention has excellent adhesion to the wafer before exposure, and thus does not cause chip fly during dicing.

  Further, it was found that the adhesive sheet of the present invention is excellent in pick-up property because of a large decrease in adhesive strength with the semiconductor chip interface after irradiation.

  Moreover, since the adhesive sheet of this invention has little fall of the film fluidity | liquidity before and behind radiation irradiation, it turned out that it is excellent in reliability, such as heat resistance and moisture resistance.

(Example 30)
The adhesive sheet 1 produced in Production Example 1 was exposed from the base film side of the adhesive sheet with an exposure amount of 500 mJ / cm ² using a UV-330 HQP-2 type exposure machine manufactured by Oak Manufacturing Co., Ltd. In the same manner as in Example 22, the tack strength after irradiation was measured.

  In addition, the adhesive sheet 1 is exposed in the same manner as described above, and the tan δ and the storage elastic modulus before and after the radiation irradiation are measured using a dynamic viscoelasticity measuring apparatus (DVE-V4, automatic static load) manufactured by the following conditions. It was measured. The results are shown in Table 7 together with the reliability evaluation results shown in Tables 4 and 5.

Sample size: length 20mm, width 4mm, film thickness 80μm
Temperature increase rate: 5 ° C./min,
Measurement mode: tension mode,
Frequency: 10Hz
(Examples 31-33)
The tack strength, tan δ, and storage elastic modulus of the adhesive sheets 2 to 4 produced in Production Examples 2 to 4 were measured under the same conditions as in Example 30. The results are shown in Table 7 together with the reliability evaluation results shown in Tables 4 and 5.

(Examples 34 to 37)
The tack strength, tan δ and storage elastic modulus of the adhesive sheets 14 to 16 and 21 produced in Production Examples 14 to 16 and 21 before and after irradiation were measured under the same conditions as in Example 30. The results are shown in Table 7 together with the reliability evaluation results shown in Tables 4 and 5.

(Comparative Examples 7-9)
The tack strength, tan δ and storage elastic modulus of the adhesive sheets 12, 13 and 25 produced in Production Examples 12, 13 and 25 before and after irradiation were measured under the same conditions as in Example 30. The results are shown in Table 7 together with the reliability evaluation results shown in Tables 4 and 5.

From Table 7, it turned out that the adhesive sheet of this invention is excellent in pick-up property, since adhesiveness with a base film fully falls after irradiation. Furthermore, since the decrease in fluidity was small even after irradiation, it was found that the heat resistance, moisture resistance and other reliability were excellent.

(Example 38)
The adhesive sheet 1 produced in Production Example 1 was exposed from the base film side of the adhesive sheet with an exposure amount of 500 mJ / cm ² using a UV-330 HQP-2 type exposure machine manufactured by Oak Manufacturing Co., Ltd. Using the same apparatus as in Example 30, the storage elastic modulus before and after irradiation was measured. Moreover, the storage elastic modulus of the adhesive layer cured at 170 ° C. for 1 hour was also measured. On the other hand, the flow amount and melt viscosity after irradiation were measured under the same conditions as in Example 22. Further, a semiconductor device sample (a solder ball is formed on one side) in which a wiring substrate using a semiconductor chip (5 mm × 5 mm × 400 μm thickness) and a polyimide film having a thickness of 25 μm as a base material is bonded with an adhesive sheet after radiation irradiation. The adhesive strength at 250 ° C. was measured using an automatic adhesive strength tester (manufactured by Hitachi Chemical Technoplant Co., Ltd.) as shown in FIG. Table 8 shows the results together with the results shown in Table 2.

(Examples 39 to 45)
Storage elastic modulus before and after irradiation of adhesive sheets 2-4 and 14-17 produced in Production Examples 2-4 and 14-17, storage elastic modulus of adhesive layer cured at 170 ° C. for 1 hour, after irradiation The flow amount, melt viscosity, and adhesive strength at 250 ° C. were measured under the same conditions as in Example 38. Table 8 shows the results together with the results shown in Table 4 and Table 5.

(Comparative Examples 10 and 11)
Adhesive sheets 12 and 13 produced in Production Examples 12 and 13 Storage elastic modulus before and after irradiation, storage elastic modulus of adhesive layer cured at 170 ° C. for 1 hour, flow amount after irradiation, melt viscosity and 250 ° C. The adhesive strength was measured under the same conditions as in Example 38. Table 8 shows the results together with the results shown in Table 4 and Table 5.

From Table 8, it was found that the adhesive sheet of the present invention is excellent in reliability such as heat resistance and moisture resistance because there is little decrease in film fluidity before and after radiation irradiation. Further, since the difference in storage elastic modulus before and after irradiation was large, it was found that there was no chip skipping during dicing and the pickup property was excellent.

<Evaluation method>
(1) Storage elastic modulus The storage elastic modulus of the adhesive sheet was measured using a dynamic viscoelasticity measuring apparatus (DVE-V4, manufactured by Rheology) (sample size: length 20 mm, width 4 mm, film thickness 80 μm, temperature rise). (Speed 5 ° C / min, tensile mode, 10 Hz, automatic static load).

(2) Measurement of flow amount Thickness (adhesive sheet excluding the base material layer) comprising an adhesive layer and a base material layer (PET film (Teijin DuPont Films Teijin Tetron film G2-50)) (Thickness) A 1 × 2 cm strip-shaped sample S was prepared by punching out a 1 × 2 cm strip from a 50 μm adhesive sheet. And in the thermocompression-bonding test apparatus (made by Tester Sangyo Co., Ltd.), the strip sample S was placed on a stage heated to 160 ° C., and a pressure of 0.8 MPa was applied for 18 seconds. Then, after taking out the sample S from the thermocompression bonding test apparatus, as shown in FIG. 12, among the resins protruding from the end of the long piece (2 cm side) of the sample S, indicated by 55 and 56 in the figure. Thus, the 1st and 2nd longest protrusion distance (longitudinal direction distance a) was measured with the optical microscope. Such an operation was performed on four samples, and an average value of the protruding distances, that is, an average value of a total of eight points was obtained as the flow amount.

（式中、Ｚ０は荷重を加える前の接着シートの厚さ、Ｚは荷重を加えた後の接着シートの厚さ、Ｖは接着シートの体積、Ｆは加えた荷重、ｔは荷重を加えた時間を表す。）
（４）対金めっきピール強度（接着強度）
１２０℃のホットプレート上で接着シートにチップ（５ｍｍ角）及び金めっき基板（銅箔付フレキ基板電解金めっき（Ｎｉ：５μｍ、Ａｕ：０．３μｍ））を積層し、１３０℃３０ｍｉｎ＋１７０℃１ｈキュアした。この試料のついて常態と吸湿後（８５／８５、４８ｈ）の２５０℃でのピール強度を測定した。 (3) Melt viscosity The melt viscosity of the adhesive sheet was measured and calculated by a parallel plate plastometer method. Eight adhesive sheets are laminated to produce a film having a thickness of about 400 μm. This was punched into a circular shape with a diameter of 11.3 mm. The sample was pressed at 160 ° C. with a load of 2.5 kgf for 5 seconds, and the melt viscosity was calculated using Equation 1 from the thickness of the sample before and after pressing.

(In the formula, Z0 is the thickness of the adhesive sheet before the load is applied, Z is the thickness of the adhesive sheet after the load is applied, V is the volume of the adhesive sheet, F is the applied load, and t is the applied load. Represents time)
(4) Peel strength against gold plating (adhesion strength)
A chip (5 mm square) and a gold plating substrate (flexible substrate electrolytic gold plating with copper foil (Ni: 5 μm, Au: 0.3 μm)) are laminated on an adhesive sheet on a 120 ° C. hot plate, and cured at 130 ° C. for 30 min + 170 ° C. for 1 h. did. For this sample, the peel strength at 250 ° C. was measured under normal conditions and after moisture absorption (85/85, 48 h).

(5) Reflow crack resistance and temperature cycle resistance (test)
Using an adhesive sheet exposed from the support film side of the adhesive sheet with an exposure amount of 500 mJ / cm ² using a UV-330 HQP-2 type exposure machine manufactured by Oak Manufacturing Co., Ltd., and a semiconductor element and an adhesive sheet A semiconductor device sample (a solder ball was formed on one surface) in which a wiring substrate using a polyimide film having a thickness of 25 μm as a base material was bonded was prepared, and heat resistance and moisture resistance were examined. As the evaluation method for heat resistance, reflow crack resistance and temperature cycle resistance tests were applied. Evaluation of reflow crack resistance is based on JEDEC standard J-STD-020A, and a semiconductor device sample subjected to moisture absorption treatment corresponding to level 2 (85 ° C., 85% RH, 168 hours) The sample was passed through an IR reflow furnace set at a maximum temperature of 265 ° C. and maintained at 260 ° C. or higher for 10 to 20 seconds, and the sample was allowed to stand at room temperature for cooling twice. And inspected with an ultrasonic microscope. The thing which did not generate | occur | produce the crack was set to (circle), and the thing which had generate | occur | produced was set to x. The temperature cycle resistance is that the sample is left in an atmosphere at -55 ° C for 30 minutes and then left in an atmosphere at 125 ° C for 30 minutes. After 1000 cycles, the sample is destroyed by peeling or cracking using an ultrasonic microscope. The case where no occurred was marked with ◯, and the case where it occurred was marked with ×.

(6) Humidity resistance evaluation It was performed by observing peeling after treatment for 72 hours in an atmosphere (pressure cooker test: PCT treatment) at a temperature of 121 ° C., a humidity of 100%, and 2.03 × 10 ⁵ Pa. The case where peeling was not recognized was marked with ◯, and the case where peeling was observed was marked with ×.

(7) Chip skipping and pick-up property during dicing The adhesive sheet was stuck on a silicon wafer having a thickness of 150 μm, and the silicon wafer with the adhesive sheet was placed on a dicing apparatus. Next, after fixing the semiconductor wafer on a dicing apparatus and dicing to 5 mm × 5 mm at a speed of 100 mm / sec, using a UV-330 HQP-2 type exposure machine manufactured by Oak Manufacturing Co., Ltd., 2000 mJ / cm ^The semiconductor element exposed from the support film side of the adhesive sheet with an exposure amount of ² and diced with a pickup device was picked up, and the semiconductor element jumping and pick-up properties during dicing were evaluated. The probability (% / 100 semiconductor element) that the semiconductor element after dicing was picked up by the pickup die bonder was shown.

(8) Storage elastic modulus, tan δ
The storage elastic modulus and tan δ of the adhesive layer were measured under the following conditions using a dynamic viscoelasticity measuring device (Rheology, DVE-V4, automatic static load).

Sample size: length 20mm, width 4mm, film thickness 80μm
Temperature increase rate: 5 ° C./min, measurement mode: tension mode, frequency: 10 Hz
(9) 90 ° peel peel strength (adhesive strength)
The adhesive sheet is laminated at 120 ° C. on the semiconductor wafer with the adhesive layer interposed therebetween, and the adhesive sheet is exposed from the substrate side to the silicon wafer with the adhesive sheet at an exposure amount of 500 mJ / cm ² before and after the exposure. The adhesive strength at the adhesive layer / substrate interface was measured at 90 ° peel strength (tensile speed: 50 m / min).

(10) Tack strength The tack strength at 25 ° C. was measured by the method described in JISZ0237-1991 using a RHESCA tacking tester.

Probe diameter: 5.1 mmΦ, peeling speed: 10 mm / s, contact load: 100 gf / cm ² , contact time: 1 s
(11) Evaluation of heat resistance and moisture resistance An adhesive sheet exposed from the support film side of the adhesive sheet with an exposure amount of 500 mJ / cm ² using a UV-330 HQP-2 type exposure machine manufactured by Oak Manufacturing Co., Ltd. A semiconductor device sample (a solder ball is formed on one side) in which a semiconductor element and an adhesive sheet and a wiring board using a polyimide film having a thickness of 25 μm as a base material are bonded at 180 ° C., 0.4 N for 5 seconds. Fabricated and examined for heat resistance and moisture resistance. As the evaluation method for heat resistance, reflow crack resistance and temperature cycle resistance tests were applied. Evaluation of reflow crack resistance is based on JEDEC standard J-STD-020A, and a semiconductor device sample subjected to moisture absorption treatment corresponding to level 2 (85 ° C., 85% RH, 168 hours) Cracks and delamination in a sample in which the sample was passed through an IR reflow furnace set at a maximum temperature of 265 ° C. and maintained at 260 ° C. or higher for 10 to 20 seconds, and allowed to cool at room temperature twice. Was observed visually and with an ultrasonic microscope. The thing which did not generate | occur | produce a crack and peeling was set to (circle), and the thing which generate | occur | produced was set to x. The temperature cycle resistance is that the sample is left in an atmosphere at -55 ° C for 30 minutes and then left in an atmosphere at 125 ° C for 30 minutes. After 1000 cycles, the sample is destroyed by peeling or cracking using an ultrasonic microscope. The case where no occurred was marked with ◯, and the case where it occurred was marked with ×. The moisture resistance was evaluated by observing peeling after 72 hours of treatment in an atmosphere (pressure cooker test: PCT treatment) at a temperature of 121 ° C., humidity of 100%, and 2.0.3 × 10 ⁵ Pa. The case where peeling was not recognized was marked with ◯, and the case where peeling was observed was marked with ×.

(12) Tg of thermoplastic resin used
The Tg of the thermoplastic resin used was determined by a suggested scanning calorimeter (DSC) under the condition of a heating rate of 10 ° C./min.

(13) Weight average molecular weight of thermoplastic resin used Measured using gel permeation chromatography and converted using a standard polystyrene calibration curve.

(14) Rate of change in calorific value due to DSC In this adhesive sheet, the rate of change when the calorific value due to DSC of the adhesive layer when irradiated with radiation is A and the calorific value before radiation is B (reaction) Rate) was calculated by the formula: (BA) / B. The DSC measurement conditions are as follows.

Temperature increase rate: 10 ° C./min, measurement temperature: 20 ° C. to 300 ° C.
(15) 90 ° peel release force A silicon wafer with an adhesive sheet obtained by pasting an adhesive sheet on a silicon wafer having a thickness of 150 μm is exposed from the base film side with an exposure amount of 500 mJ / cm ² before and after exposure. The adhesive strength at the adhesive layer / substrate interface was measured by 90 ° peel strength (tensile speed: 50 mm / min).

  This application is a Japanese patent application previously filed by the same applicant, ie, Japanese Patent Application No. 2001-256285 (application date: August 27, 2001), Japanese Patent Application No. 2001-256286 (application date: August 27, 2001). Japanese Patent Application No. 2001-262661 (application date: August 31, 2001), Japanese Patent Application No. 2001-269013 (application date: September 5, 2001), Japanese Patent Application No. 2002-35488 (application date: February 2002) 13), Japanese Patent Application No. 2002-37032 (filing date: February 14, 2002), Japanese Patent Application No. 2002-76577 (filing date: March 19, 2002), Japanese Patent Application No. 2002-83777 (filing date: March 2002) No. 25), Japanese Patent Application No. 2002-83818 (filing date: March 25, 2002), Japanese Patent Application No. 2002-83844 (filing date: Mar. 25, 2002), Japanese Patent Application No. 2002-137 52 No. be those with the priority claim based on (filed May 13, 2002), which is incorporated these specification herein by reference.

It is sectional drawing of an example of the adhesive sheet which concerns on this invention. It is sectional drawing of another example of the adhesive sheet which concerns on this invention. It is a figure which shows the state which stuck the semiconductor wafer to the adhesive sheet which concerns on this invention. It is explanatory drawing at the time of using the adhesive sheet which concerns on this invention for the dicing process of a semiconductor wafer. It is a figure which shows the state which irradiated the radiation to the adhesive sheet from the back surface after the process shown in FIG. It is a figure which shows the process of picking up a semiconductor element after the process shown in FIG. It is a figure which shows the semiconductor element and the adhesive agent layer which were picked up. It is a figure which shows the state which carried out the thermocompression bonding of the semiconductor element to the supporting member for semiconductor element mounting. 6 is a ¹ H-NMR chart of imidazolium tetraphenylborate obtained in Synthesis Example 4. FIG. 6 is a ¹ H-NMR chart of imidazolium tetraphenylborate obtained in Synthesis Example 5. FIG. It is a schematic diagram of an automatic adhesive strength tester. It is a figure which shows the measuring method of a protrusion distance.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base film 2 ... 1st adhesive layer 3 ... 2nd adhesive layer 4 ... Suction collet 5 ... Supporting member 10 for semiconductor element mounting, 11 ... Adhesive sheet A ... Semiconductor wafer A1, A2 A3 ... Semiconductor element B ... Radiation 21 ... Semiconductor chip 22 ... Adhesive sheet 23 ... Wiring board 31 ... Action part 32 ... Main body 40 ... Stopping part 41 ... Thermal plate C ... Automatic adhesive strength tester D ... Semiconductor device sample 50 ... Arrow S ... Test piece

Claims (27)

An adhesive sheet comprising an adhesive layer and a base material layer, wherein the adhesive force between the adhesive layer and the base material layer is controlled by irradiation with radiation,
The adhesive layer (A1) has an adhesive strength between the adhesive layer interface and the base material layer interface before irradiation of radiation of 200 mN / cm or more, and at least one of the following properties: An adhesive sheet.
(B1) The flow amount at 160 ° C. before radiation irradiation is 100 to 10,000 μm,
(B2) The melt viscosity at 160 ° C. before radiation irradiation is 50 to 100,000 Pa · s.   2. The adhesive sheet according to claim 1, wherein in the adhesive sheet, a flow amount ratio before and after irradiation (flow amount after irradiation / flow amount before irradiation) is 0.1 or more.   3. The adhesive sheet according to claim 1, wherein the adhesive sheet has an adhesive strength ratio (adhesive strength after irradiation / adhesive strength before irradiation) of 0.5 or less before and after radiation irradiation at the interface between the adhesive layer and the base material layer. Adhesive sheet.   4. The adhesive sheet according to claim 1, wherein the adhesive sheet has an adhesive strength difference between before and after radiation irradiation (adhesive strength before irradiation−adhesive strength after irradiation) of 100 mN / cm or more at the interface between the adhesive layer and the base material layer. The adhesive sheet according to claim 1.   The adhesive sheet according to any one of claims 1 to 4, wherein the adhesive sheet has a melt viscosity ratio (post-irradiation melt viscosity / pre-irradiation melt viscosity) of 100 or less before and after irradiation. An adhesive sheet comprising an adhesive layer and a base material layer, wherein the adhesive force between the adhesive layer and the base material layer is controlled by irradiation with radiation,
The adhesive layer (A2) has a tack strength at 25 ° C. of 0.5 N or more as measured by 5.1 mmΦ probe of the adhesive layer before irradiation (A2), and at least one of the following characteristics: Adhesive sheet with two characteristics.
(B1) The flow amount at 160 ° C. before radiation irradiation is 100 to 10,000 μm,
(B2) The melt viscosity at 160 ° C. before radiation irradiation is 50 to 100,000 Pa · s.   7. The adhesive sheet has a tack strength difference at 25 ° C. (tack strength before irradiation−tack strength after irradiation) of 0.1 N or more by 5.1 mmΦ probe measurement before and after radiation irradiation of the adhesive layer. Adhesive sheet.   The adhesive sheet according to claim 6 or 7, wherein in the adhesive sheet, a flow amount ratio before and after irradiation (flow amount after irradiation / flow amount before irradiation) is 0.1 or more.   The adhesive sheet according to claim 6 or 7, wherein the adhesive sheet has a melt viscosity ratio before and after irradiation (melt viscosity after irradiation / melt viscosity before irradiation) of 100 or less.   The adhesive sheet according to any one of claims 1 to 9, wherein the adhesive force between the adhesive layer and the base material layer is controlled by irradiation with radiation.   The adhesive sheet according to claim 10, wherein the radiation is light having a wavelength of 150 nm to 750 nm.   The adhesive sheet according to any one of claims 1 to 11, wherein the adhesive strength after radiation irradiation is 100 mN / cm or less. An adhesive sheet comprising an adhesive layer and a base material layer, wherein the adhesive force between the adhesive layer and the base material layer is controlled by irradiation with radiation,
The adhesive layer (C1) has an adhesive strength difference (adhesive strength before radiation irradiation-adhesive strength after radiation irradiation) between the adhesive layer / substrate layer interface before and after radiation irradiation of 100 mN / cm or more. And an adhesive sheet having at least one of the following characteristics:
(D1) tan δ at 120 ° C. before irradiation is 0.1 or more, tan δ at 180 ° C. after irradiation is 0.1 or more,
(D2) The storage elastic modulus at 120 ° C. before irradiation is 10 MPa or less, and the storage elastic modulus at 180 ° C. after irradiation is 100 MPa or less.   14. The adhesive sheet according to claim 13, wherein the adhesive strength ratio (adhesive strength after radiation irradiation / adhesive strength before radiation irradiation) of the adhesive layer / substrate layer interface before and after irradiation is 0.5 or less. Adhesive sheet.   The adhesive strength before irradiation of radiation at the interface between the adhesive layer and the base material layer is 200 mN / cm or more in the adhesive sheet, and the adhesive strength after irradiation is 100 mN / cm or less. Adhesive sheet. An adhesive sheet comprising an adhesive layer and a base material layer, wherein the adhesive force between the adhesive layer and the base material layer is controlled by irradiation with radiation,
The adhesive layer (C2) has a difference in tack strength at 25 ° C. between the adhesive layer before and after radiation irradiation (tack strength at 25 ° C. before radiation irradiation—tack strength at 25 ° C. after radiation irradiation). An adhesive sheet that is 0.1 N / 5.1 mmΦ probe or more and has at least one of the following characteristics.
(D1) tan δ at 120 ° C. before irradiation is 0.1 or more, tan δ at 180 ° C. after irradiation is 0.1 or more,
(D2) The storage elastic modulus at 120 ° C. before irradiation is 10 MPa or less, and the storage elastic modulus at 180 ° C. after irradiation is 100 MPa or less.   The adhesive sheet has an adhesive strength ratio (adhesive strength after radiation irradiation / adhesive strength before radiation irradiation) of 0.5 or less. Adhesive sheet.   18. In the adhesive sheet, the adhesive strength before radiation irradiation at the interface between the adhesive layer and the base material layer is 200 mN / cm or more, and the adhesive strength after radiation irradiation is 100 mN / cm or less. Adhesive sheet. An adhesive sheet comprising an adhesive layer and a base material layer, wherein the adhesive force between the adhesive layer and the base material layer is controlled by irradiation with radiation,
The adhesive layer has an uncured or semi-cured storage elastic modulus at 50 ° C. of 0.1 MPa to 200 MPa, and is irradiated with a storage elastic modulus at 50 ° C. after irradiation with a certain amount of radiation. The adhesive layer after being irradiated with a certain amount of radiation more than twice the previous one has at least one of the characteristics shown in the following (E), (F) and (G). An adhesive sheet.
(E) The flow amount at 160 ° C. is 100 μm or more and 10,000 μm or less,
(F) The melt viscosity at 160 ° C. is 50 Pa · s or more and 10 ⁶ Pa · s or less, and (G) the storage elastic modulus at 180 ° C. is 100 MPa or less.   The flow amount A at 160 ° C. of the adhesive layer of the uncured or semi-cured adhesive sheet and the flow amount B of the adhesive layer after irradiating the adhesive sheet with a certain amount of radiation are B / A. The adhesive sheet according to claim 19, satisfying a relationship of ≧ 1/10.   The adhesive sheet according to claim 20 or 21, wherein a storage elastic modulus at 50 ° C of the adhesive layer after irradiating a predetermined amount of radiation to the uncured or semi-cured adhesive sheet is 15 MPa or more. The adhesive sheet according to any one of claims 19 to 21, wherein the adhesive layer satisfies the following conditions.
1) Storage elastic modulus at 100 ° C. in an uncured or semi-cured state is 0.001 MPa or more and 2 MPa or less, 2) Storage elastic modulus at 50 ° C. is 7.5 MPa or more and 50 MPa or less, and 3) after irradiation The storage elastic modulus at 50 ° C. is 15 MPa or more and 100 MPa or less, and 4) The storage elastic modulus at 50 ° C. after curing is 100 MPa or more and 5000 MPa or less.   23. The adhesive strength at 250 ° C. of a laminated cured product of a 5 mm square semiconductor element and a support member using an adhesive layer of an adhesive sheet after radiation irradiation is 3.0 N / chip or more. The adhesive sheet of any one of Claims.   The storage elastic modulus of the adhesive layer when measured using a dynamic viscoelasticity measuring device of the adhesive sheet after heat curing is 10 MPa to 2000 MPa at 25 ° C., and 3 MPa to 50 MPa at 260 ° C. The adhesive sheet according to any one of claims 19 to 23.   The adhesive sheet according to any one of claims 19 to 24, wherein the adhesive force between the adhesive layer and the base material layer is controlled by irradiation with radiation.   The adhesive sheet according to claim 25, wherein the radiation is light having a wavelength of 150 nm to 750 nm.   The adhesive sheet according to any one of claims 19 to 26, wherein the adhesive strength after radiation irradiation is 100 mN / cm or less.

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