JP2004292821A - Film adhesive, adhesive sheet, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wafer-rear-side-attaching film adhesive which can apply to an extremely thin wafer and to provide an adhesive sheet obtained by bonding the film adhesive and a UV-type dicing tape. <P>SOLUTION: This film adhesive contains (A) a thermoplastic resin and (B) an epoxy resin. The epoxy resin (B) contains (B1) 10-90 wt%, of the total epoxy resin, of an epoxy resin with at least trifunctional groups and (B2) 10-90 wt%, of the total epoxy resin, of a liquefied epoxy resin. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a film adhesive, an adhesive sheet, and a semiconductor device using the same.

  Conventionally, silver paste has been mainly used to join semiconductor elements and support members for mounting semiconductor elements. However, with the recent trend toward smaller and higher performance semiconductor elements, the size of support members used has also been reduced. In response to these demands, silver paste has been required to meet such demands, causing problems during wire bonding due to protrusion or inclination of semiconductor elements, and difficulty in controlling the thickness of the adhesive layer. Due to the properties and the generation of voids in the adhesive layer, it has become impossible to meet the demand. Therefore, in recent years, a film-like adhesive has been used in order to meet the demand (for example, see Patent Documents 1 and 2).

  This film adhesive is used in an individual piece sticking method or a wafer backside sticking method. In the case of manufacturing a semiconductor device by using the former individual piece type film adhesive, the reel-like film adhesive is cut into individual pieces by cutting or punching and then adhered to a support member, and the film-like adhesive is applied. A semiconductor element singulated by a dicing step is joined to a support member with an agent to produce a support member with a semiconductor element, and thereafter, a semiconductor device is obtained through a wire bonding step, a sealing step, and the like (for example, And Patent Document 3). However, in order to use the film adhesive of the individual piece sticking method, since a special assembly device for cutting out the film adhesive and bonding the film adhesive to the support member is necessary, compared with a method using a silver paste, There is a problem that the manufacturing cost is increased.

  On the other hand, when manufacturing a semiconductor device using a film adhesive of a wafer backside bonding method, first, a film adhesive is attached to the back surface of the semiconductor wafer, and then a dicing tape is attached to the other surface of the film adhesive, and thereafter. , Singulating the semiconductor elements from the wafer by dicing, picking up the singulated semiconductor elements with a film adhesive, joining them to a supporting member, and then passing through steps such as heating, curing, and wire bonding. Thereby, a semiconductor device is obtained. Since the film-like adhesive of the wafer backside bonding method joins the semiconductor element with the film-like adhesive to the supporting member, there is no need for a device for separating the film-like adhesive into individual pieces, and a conventional silver paste assembling apparatus is used. Can be used as it is or by improving a part of the apparatus such as adding a hot plate. For this reason, attention has been paid to a method of relatively low production cost among the assembling methods using a film adhesive (for example, see Patent Document 4).

  However, recently, in addition to the above-mentioned miniaturization and high performance of the semiconductor element, multifunctionality has been advanced, and accordingly, a 3D package in which two or more semiconductor elements are stacked has rapidly increased. Along with this, semiconductor wafers have been further thinned. Along with this, cracking of the wafer during transportation and sticking of the film adhesive to the back surface of the wafer, that is, cracking of the wafer during laminating, have become apparent. In order to prevent this, a method of bonding a polyolefin-based back grinding tape as a protective tape to the wafer surface is being adopted. However, since the softening temperature of the back grinding tape is 100 ° C. or lower, a demand for a film adhesive that can be laminated on the back surface of the wafer at a temperature of 100 ° C. or lower has been increasing.

  Furthermore, good process characteristics at the time of package assembly, such as pick-up properties after dicing, that is, easy peelability between the film adhesive and the dicing tape are required.

There is an increasing demand for a film adhesive that can achieve both the process characteristics including the low-temperature laminating property and the reliability as a package, that is, the reflow resistance.

Heretofore, a film adhesive in which a thermoplastic resin having a relatively low Tg and a thermosetting resin are combined to achieve both low-temperature processability and heat resistance has been proposed (for example, see Patent Document 5). However, in order to achieve both the low-temperature laminating property and the reflow resistance, further detailed material design is required.
JP-A-3-192178 JP-A-4-234472 JP-A-9-17810 JP-A-4-196246 Patent No. 3014578

  The present invention has been made in view of the above-described problems of the prior art, and provides a film-like adhesive of a wafer backside sticking method capable of coping with an extremely thin wafer, and an adhesive sheet in which the film-like adhesive and a UV-type dicing tape are bonded. Accordingly, the object is to simplify the attaching process up to the dicing process. Further, when the adhesive sheet is attached to the back surface of the wafer (hereinafter, referred to as lamination), the adhesive is heated to a temperature at which the film adhesive melts, and the heating temperature is set lower than the softening temperature of the UV dicing tape. The present invention provides a film adhesive which can be used. Accordingly, it is an object of the present invention not only to improve workability but also to solve a problem such as a warp of a wafer having a large diameter and a thin film. Further, the present invention provides a film adhesive having heat resistance and moisture resistance required when a semiconductor element having a large difference in thermal expansion coefficient is mounted on a semiconductor element mounting support member, and having excellent workability and low outgassing property. The purpose is to do. Another object of the present invention is to provide a semiconductor device which can simplify the manufacturing process of the semiconductor device and has excellent reliability.

  The present inventors can laminate a protective tape of an ultra-thin wafer on the back surface of the wafer at a temperature lower than the softening temperature of the dicing tape to be bonded, and reduce thermal stress such as warpage of the wafer, thereby reducing the manufacturing process of the semiconductor device. As a result of the development of a film-like adhesive for die bonding which can be simplified, and furthermore excellent in heat resistance and moisture resistance reliability, and an adhesive sheet in which the film-like adhesive is bonded to a UV-type dicing tape, and a thorough study of semiconductor devices, The invention has been completed. That is, the present invention provides the following film adhesive, adhesive sheet, and semiconductor device.

  That is, the present invention relates to the following items.

<1> A film adhesive containing (A) a thermoplastic resin and (B) an epoxy resin,
The (B) epoxy resin is a film comprising (B1) a trifunctional or higher functional epoxy resin in an amount of 10 to 90% by weight of the total epoxy resin, and (B2) a liquid epoxy resin in an amount of 10 to 90% by weight of the total epoxy resin. Glue.

<2> The film adhesive according to <1>, wherein the tan δ peak temperature is 20 to 65 ° C and the flow amount is 200 to 1500 µm.

<3> The film adhesive according to <1> or <2>, further comprising (C) an epoxy resin curing agent.

<4> The film adhesive according to any one of <1> to <3>, further including (D) a filler.

<5> The film adhesive according to <4>, wherein the filler (D) is an insulating filler.

<6> The film adhesive according to <4> or <5>, wherein the (D) filler has an average particle diameter of 10 μm or less and a maximum particle diameter of 25 μm or less.

<7> The thermoplastic resin (A) is a polyimide resin, polyetherimide resin, polyesterimide resin, polyamide resin, polyester resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide resin, polyetherketone resin, or phenoxy resin. The film adhesive according to any one of the above <1> to <6>, which is at least one resin selected from the group consisting of:

（式中、Ｑ^１、Ｑ^２及びＱ^３は各々独立に炭素数１〜１０のアルキレン基を示しｍは２〜８０の整数を示す）
で表される脂肪族エーテルジアミンが全ジアミンの１〜５０モル％、下記一般式（ＩＩ）

（式中、ｎは５〜２０の整数を示す）
で表される脂肪族ジアミンが全ジアミンの２０〜８０モル％、及び下記一般式（III）

（式中、Ｑ^４及びＱ^９は各々独立に炭素数１〜５のアルキレン基又は置換基を有してもよいフェニレン基を示し、Ｑ^５、Ｑ^６、Ｑ^７、及びＱ^８は各々独立に炭素数１〜５のアルキル基、フェニル基又はフェノキシ基を示し、ｐは１〜５の整数を示す）
で表されるシロキサンジアミンが全ジアミンの２０〜８０モル％を含むジアミンとを反応させて得られるポリイミド樹脂である前記＜１＞〜＜７＞のいずれか１つに記載のフィルム状接着剤。 <8> The thermoplastic resin (A) comprises tetracarboxylic dianhydride and the following formula (I)

(Wherein, Q ¹ , Q ² and Q ³ each independently represent an alkylene group having 1 to 10 carbon atoms, and m represents an integer of 2 to 80)
Wherein the aliphatic ether diamine represented by the formula is 1 to 50 mol% of the total diamine, and the following general formula (II)

(Where n represents an integer of 5 to 20)
The aliphatic diamine represented by the formula is 20 to 80 mol% of the total diamine, and the following general formula (III)

(Wherein, Q ⁴ and Q ⁹ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and Q ⁵ , Q ⁶ , Q ⁷ , and Q ⁸ each independently represent Represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and p represents an integer of 1 to 5)
The film adhesive according to any one of <1> to <7>, wherein the siloxane diamine represented by the formula (1) is a polyimide resin obtained by reacting with a diamine containing 20 to 80 mol% of all diamines.

で表されるテトラカルボン酸二無水物の含量が全テトラカルボン酸二無水物の４０モル％以上であるテトラカルボン酸二無水物と、ジアミンとを反応させて得られるポリイミド樹脂である前記＜１＞〜＜８＞のいずれか１つに記載のフィルム状接着剤。 <9> The thermoplastic resin (A) is represented by the following general formula (IV)

<1. A polyimide resin obtained by reacting a tetracarboxylic dianhydride having a content of tetracarboxylic dianhydride of 40 mol% or more of all tetracarboxylic dianhydrides and a diamine with a diamine. > The film adhesive according to any one of <8>.

<10> The film adhesive according to any one of <1> to <9>, wherein the (B2) liquid epoxy resin is a bifunctional epoxy resin having a number average molecular weight of 400 to 1500.

（式中、Ｑ^１３及びＱ^１６は各々独立に炭素数１〜５のアルキレン基又は置換基を有してもよいフェニレン基又はフェノキシ基を示し、Ｑ^１４及びＱ^１５は各々独立に炭素数１〜５のアルキル基又は水素を示し、ｔは１〜１０の整数を示す）で表されるビスフェノール型エポキシ樹脂である前記＜１０＞記載のフィルム状接着剤。 <11> The bifunctional epoxy resin has the following general formula (VIII)

(In the formula, Q ¹³ and Q ¹⁶ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group or a phenoxy group which may have a substituent, and Q ¹⁴ and Q ¹⁵ each independently represent 1 carbon atom. Wherein n represents an alkyl group or hydrogen of from 5 to 5, and t represents an integer of from 1 to 10).

（式中、Ｑ^１０、Ｑ^１１及びＱ^１２は各々独立に水素又は炭素数１〜５のアルキレン基又は置換基を有してもよいフェニレン基を示し、ｒは１〜２０の整数を示す）で表されるノボラック型エポキシ樹脂である前記＜１＞〜＜１１＞のいずれか１つに記載のフィルム状接着剤。 <12> The epoxy resin having three or more functional groups (B1) is represented by the following general formula (VII):

(Wherein Q ¹⁰ , Q ¹¹ and Q ¹² each independently represent hydrogen or an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and r represents an integer of 1 to 20) The film adhesive according to any one of <1> to <11>, which is a novolak type epoxy resin represented by the formula:

<13> Any one of <3> to <12>, wherein the (C) epoxy resin curing agent is a phenolic compound having two or more hydroxyl groups in the molecule and having a number average molecular weight of 400 to 1500. A film adhesive according to any one of the above.

<14> The epoxy resin curing agent according to any one of <3> to <12>, wherein the epoxy resin curing agent is a naphthol-based compound having three or more aromatic rings in a molecule or a trisphenol-based compound. Film adhesive.

<15> The film adhesive according to any one of <1> to <14>, wherein the varnish solvent for applying the film adhesive is a nitrogen-containing compound.

<16> The method according to any one of <1> to <15>, wherein, at the stage of laminating the silicon wafer at 80 ° C, the 90 ° peeling force at 25 ° C on the silicon wafer is 5 N / m or more. Film adhesive.

<17> An organic substrate with a film adhesive obtained by die-bonding a chip via the film adhesive onto an organic substrate having an organic resist material provided on the surface thereof has the following requirements:
(1) After the above-mentioned organic substrate with a film-like adhesive is heated and cured, the film is subjected to a moisture absorption treatment at 85 ° C. and 85% relative humidity for 15 hours, and then foaming occurs when heated on a hot plate at 260 ° C. for 30 seconds. unacceptable;
(2) After heat-curing the above-mentioned organic substrate with a film-like adhesive, it was subjected to a moisture absorption treatment at 85 ° C. and a relative humidity of 60% for 168 hours. 5N / chip or more;
The film-like adhesive according to any one of the above <1> to <16>, which satisfies at least one of the following.

<18> A film adhesive used for a die bonding film containing at least a thermoplastic resin and a thermosetting resin,
The residual volatile content of the film adhesive is V (% by weight), the water absorption after heat curing is M (% by weight), the flow amount is F (μm), and the storage elastic modulus at 260 ° C. after heat curing is E ( MPa), the following conditions (1) to (4):
(1) V ≦ 10.65 × E,
(2) M ≦ 0.22 × E,
(3) V ≦ −0.0043F + 11.35,
(4) M ≦ −0.0002F + 0.6,
A film adhesive satisfying at least one of the following.

<19> The film adhesive according to any one of <1> to <18>, which is an adhesive material for die bonding for bonding a semiconductor element and a semiconductor mounting support member.

<20> The film adhesive according to <19>, wherein the support member for mounting a semiconductor is an organic substrate including an organic resist layer.

<21> An adhesive sheet in which a base material layer, an adhesive layer, and the film-like adhesive layer according to any one of <1> to <20> are formed in this order.

<22> The adhesive sheet according to <21>, wherein the adhesive layer is a radiation-curable adhesive layer.

<23> At the stage of laminating at 80 ° C. on a silicon wafer, the film adhesive was subjected to UV irradiation at 25 ° C. with a 90 ° peeling force at 25 ° C. under the conditions of an exposure amount of 500 mJ / cm ^2. The bond according to <22>, wherein the value of AB is 1 N / m or more, where B is a 90 ° peeling force at 25 ° C. of the radiation-curable adhesive layer with respect to the film-form adhesive layer. Sheet.

<24> via the film adhesive according to any one of <1> to <20>,
(1) a semiconductor element and a support member for mounting a semiconductor; and (2) semiconductor elements,
A semiconductor device having a structure in which at least one of the above is bonded.

  The film adhesive of the present invention can be laminated on the back surface of a wafer at a temperature lower than the softening temperature of a protective tape for a very thin wafer or a dicing tape to be bonded. In addition, the film adhesive of the present invention can reduce thermal stress such as warpage of a wafer, does not fly a chip at the time of dicing, and has good pick-up properties, so that the manufacturing process of a semiconductor device can be simplified. Furthermore, the film adhesive of the present invention is excellent in heat resistance and humidity resistance reliability.

  The film adhesive of the present invention can be laminated on the back surface of the wafer at a temperature lower than the softening temperature of the protective tape of the ultra-thin wafer or the dicing tape to be bonded, and can ensure good pickup with the dicing tape after dicing. And it has excellent heat resistance and humidity resistance reliability.

  The present invention relates to a film adhesive containing (A) a thermoplastic resin, (B) an epoxy resin, (C) an epoxy resin curing agent, and (D) a filler, wherein the (B) epoxy resin is (B1) A film adhesive comprising 10 to 90% by weight of the total epoxy resin, and (B2) 10 to 90% by weight of the total epoxy resin.

(A) Thermoplastic resin The thermoplastic resin (A) is a polyimide resin, polyetherimide resin, polyesterimide resin, polyamide resin, polyester resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide resin, polyetherketone resin, It is at least one resin selected from the group consisting of phenoxy resins, and among them, polyimide resins and polyetherimide resins are preferred.

  The polyimide resin can be obtained, for example, by subjecting a tetracarboxylic dianhydride and a 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 manner (addition order of each component is arbitrary), and the addition reaction is carried out at a reaction temperature of 80 ° C or lower, preferably 0 to 60 ° C. As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, which is a precursor of polyimide, is generated. The acid dianhydride is preferably subjected to recrystallization purification treatment with acetic anhydride in order to suppress the deterioration of various properties of the film adhesive.

  The molecular weight of the polyamic acid can also be adjusted 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 above reactant (polyamic acid). The dehydration ring closure can be carried out by a thermal ring closure method using a heat treatment and a chemical ring closure method using a dehydrating agent.

（式中、ｎは２〜２０の整数を示す）
で表されるテトラカルボン酸二無水物、下記式（ＩＶ）

で表されるテトラカルボン酸二無水物等が挙げられ、上記一般式（IＸ）で表されるテトラカルボン酸二無水物は、例えば、無水トリメリット酸モノクロライド及び対応するジオールから合成することができ、具体的には１，２−（エチレン）ビス（トリメリテート無水物）、１，３−（トリメチレン）ビス（トリメリテート無水物）、１，４−（テトラメチレン）ビス（トリメリテート無水物）、１，５−（ペンタメチレン）ビス（トリメリテート無水物）、１，６−（ヘキサメチレン）ビス（トリメリテート無水物）、１，７−（ヘプタメチレン）ビス（トリメリテート無水物）、１，８−（オクタメチレン）ビス（トリメリテート無水物）、１，９−（ノナメチレン）ビス（トリメリテート無水物）、１，１０−（デカメチレン）ビス（トリメリテート無水物）、１，１２−（ドデカメチレン）ビス（トリメリテート無水物）、１，１６−（ヘキサデカメチレン）ビス（トリメリテート無水物）、１，１８−（オクタデカメチレン）ビス（トリメリテート無水物）等が挙げられる。中でも、優れた耐湿信頼性を付与できる点で上記式（ＩＶ）で表されるテトラカルボン酸二無水物が好ましい。これらテトラカルボン酸二無水物は単独で又は二種類以上を組み合わせて使用することができる。 The tetracarboxylic dianhydride used as a raw material of the polyimide resin is not particularly limited, and examples thereof include 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 Anhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) ) Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic acid Dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenonetetracarboxylic acid Dianhydride, 2,3,2 ', 3'-benzophenonetetracarboxylic dianhydride, 3,3,3', 4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetra Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid Dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2, 3,6,7-tetrachlorona Taren-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 acid Dianhydride, 2,3,2 ', 3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenyl Silane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3 4-di (Ruboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitate anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic acid Acid dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,2 5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,2 3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo- [2,2,2] -oct-7- En-2,3 5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2, -bis [4- (3,4-dicarboxyphenyl) phenyl] Propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2, -bis [4- (3,4-dicarboxyphenyl) phenyl] hexafluoropropane dianhydride Anhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide 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, the following general formula (IX)

(Where n represents an integer of 2 to 20)
A tetracarboxylic dianhydride represented by the following formula (IV):

The tetracarboxylic dianhydride represented by the above general formula (IX) can be synthesized from, for example, trimellitic anhydride monochloride and the corresponding diol. Specifically, 1,2- (ethylene) bis (trimellitate anhydride), 1,3- (trimethylene) bis (trimellitate anhydride), 1,4- (tetramethylene) bis (trimellitate anhydride), 1 1,5- (pentamethylene) bis (trimellitate anhydride), 1,6- (hexamethylene) bis (trimellitate anhydride), 1,7- (heptamethylene) bis (trimellitate anhydride), 1,8- (octa Methylene) bis (trimellitate anhydride), 1,9- (nonamethylene) bis (trimellitate anhydride), 1,10- (decamethylene) bis ( Trimellitate anhydride), 1,12- (dodecamethylene) bis (trimellitate anhydride), 1,16- (hexadecamethylene) bis (trimellitate anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride) ) And the like. Among them, the tetracarboxylic dianhydride represented by the above formula (IV) is preferable in that excellent moisture resistance reliability can be imparted. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

  Further, the content of the tetracarboxylic dianhydride represented by the general formula (IV) is preferably at least 40 mol%, more preferably at least 50 mol%, and more preferably at least 70 mol% based on all the tetracarboxylic dianhydrides. The above is extremely preferred. If the amount is less than 40 mol%, the effect of moisture resistance reliability due to the use of the tetracarboxylic dianhydride represented by the above formula (IV) cannot be sufficiently secured.

（式中、Ｑ^１、Ｑ^２及びＱ^３は各々独立に炭素数１〜１０のアルキレン基を示しｍは２〜８０の整数を示す）
で表される脂肪族エーテルジアミン、下記一般式（II）

（式中、ｎは５〜２０の整数を示す）
で表される脂肪族ジアミン、下記一般式（III）

（式中、Ｑ^４及びＱ^９は各々独立に炭素数１〜５のアルキレン基又は置換基を有してもよいフェニレン基を示し、Ｑ^５、Ｑ^６、Ｑ^７、及びＱ^８は各々独立に炭素数１〜５のアルキル基、フェニル基又はフェノキシ基を示し、ｐは１〜５の整数を示す）
で表されるシロキサンジアミン等が挙げられ、中でも低応力性、低温ラミネート性、低温接着性を付与できる点で、上記一般式（Ｉ）、又は（II）が好ましい。また、低吸水性、低吸湿性を付与できる点で、上記一般式（III）が好ましい。これらのジアミンは単独で、又は２種以上を組み合わせて使用することができる。この場合、下記式（Ｉ）

（式中、Ｑ^１、Ｑ^２及びＱ^３は各々独立に炭素数１〜１０のアルキレン基を示しｍは２〜８０の整数を示す）
で表される脂肪族エーテルジアミンが全ジアミンの１〜５０モル％、下記一般式（II）

（式中、ｎは５〜２０の整数を示す）
で表される脂肪族ジアミンが全ジアミンの２０〜８０モル％、及び下記一般式（III）

（式中、Ｑ^４及びＱ^９は各々独立に炭素数１〜５のアルキレン基又は置換基を有してもよいフェニレン基を示し、Ｑ^５、Ｑ^６、Ｑ^７、及びＱ^８は各々独立に炭素数１〜５のアルキル基、フェニル基又はフェノキシ基を示し、ｐは１〜５の整数を示す）
で表されるシロキサンジアミンが全ジアミンの２０〜８０モル％であることが好ましい。上記モル％の範囲外であると、低温ラミネート性及び低吸水性の付与の効果が小さくなり好ましくない。 The diamine used as a raw material of the polyimide resin is not particularly limited, and examples thereof include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylatemethane, 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'-di Minodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylketone, 3 , 4'-Diaminodiphenylketone, 4,4'-diaminodiphenylketone, 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- Minophenoxy) 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-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) sulfide, bis (4- (3-aminoenoxy) phenyl) sulfone, Bis (4- (4-aminoenoxy) phenyl) sulfone, aromatic diamine such as 3,5-diaminobenzoic acid, 1,3-bis (aminomethyl) cyclohexane, 2,2-bis (4-aminophenoxyphenyl) propane And the following formula (I)

(Wherein, Q ¹ , Q ² and Q ³ each independently represent an alkylene group having 1 to 10 carbon atoms, and m represents an integer of 2 to 80)
An aliphatic ether diamine represented by the following general formula (II)

(Where n represents an integer of 5 to 20)
An aliphatic diamine represented by the following general formula (III):

(Wherein, Q ⁴ and Q ⁹ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and Q ⁵ , Q ⁶ , Q ⁷ , and Q ⁸ each independently represent Represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and p represents an integer of 1 to 5)
The above-mentioned general formula (I) or (II) is preferable in that low stress property, low-temperature laminating property, and low-temperature adhesive property can be imparted. In addition, the above general formula (III) is preferable in that low water absorption and low moisture absorption can be imparted. These diamines can be used alone or in combination of two or more. In this case, the following formula (I)

(Wherein, Q ¹ , Q ² and Q ³ each independently represent an alkylene group having 1 to 10 carbon atoms, and m represents an integer of 2 to 80)
Wherein the aliphatic ether diamine represented by the formula is 1 to 50 mol% of the total diamine, and represented by the following general formula (II):

(Where n represents an integer of 5 to 20)
The aliphatic diamine represented by the formula is 20 to 80 mol% of the total diamine, and the following general formula (III)

(Wherein, Q ⁴ and Q ⁹ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and Q ⁵ , Q ⁶ , Q ⁷ , and Q ⁸ each independently represent Represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and p represents an integer of 1 to 5)
Is preferably 20 to 80 mol% of the total diamine. If the molar ratio is out of the above range, the effects of providing low-temperature laminating properties and low water absorption are undesirably small.

等があり、中でも、低温ラミネート性と有機レジスト付き基板に対する良好な接着性を確保できる点で、下記式（Ｖ）

（式中、ｍは２〜８０の整数を示す）
で表される脂肪族エーテルジアミンがより好ましい。具体的には、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，ＢＡＳＦ（製）ポリエーテルアミンＤ−２３０，Ｄ−４００，Ｄ−２０００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が挙げられる。 Further, as the aliphatic ether diamine represented by the general formula (I), specifically,

Among them, the following formula (V) is particularly preferred in that low-temperature laminating property and good adhesion to a substrate with an organic resist can be ensured.

(Wherein, m represents an integer of 2 to 80)
Is more preferable. Specifically, Jeffamine D-230, D-400, D-2000, D-4000, ED-600, ED-900, ED-2001, EDR-148, and BASF (manufactured by Sun Techno Chemical Co., Ltd.) And aliphatic diamines such as polyoxyalkylene diamines such as polyetheramines D-230, D-400, and D-2000.

  Examples of the aliphatic diamine represented by the general formula (II) include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2- Examples thereof include diaminocyclohexane, and among them, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane are preferable.

  Examples of the siloxane diamine represented by the general formula (III) include, for example, in the above formula (III), when p is 1, 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis (4-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminobutyl) disiloxane, 1,3-dimethyl −1,3-dimethoxy-1,3-bis (4-aminobutyl) disiloxane, etc., where <when p is 2>, 1,1,3,3,5,5-hexamethyl-1,5- Bis (4-aminophenyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5-tetra Phenyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) Trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy -1,5-bis (4-aminobutyl) Polysiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-1, 5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5 5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane and the like.

  The above polyimide resins may be used alone or as a mixture (blend) of two or more as required.

  The laminating temperature of the film adhesive of the present invention is preferably lower than the heat resistance or softening temperature of the protective tape of the wafer, that is, the back-grinding tape, or lower than the heat resistance or softening temperature of the dicing tape. From the viewpoint of suppressing warpage, the temperature is preferably from 10 to 100 ° C, more preferably from 20 to 80 ° C. In order to achieve the above laminating temperature, the Tg of the polyimide resin is preferably from 20 to 100C, more preferably from 30 to 80C. When the Tg exceeds 100 ° C., the possibility that the laminating temperature exceeds 100 ° C. increases, which is not preferable.

  The weight average molecular weight of the polyimide resin is preferably controlled within the range of 10,000 to 200,000, more preferably 20,000 to 100,000, and most preferably 30,000 to 80,000. When the weight average molecular weight is less than 10,000, the film-forming property is deteriorated, and when it exceeds 200,000, the fluidity at the time of heating is deteriorated, and the possibility that the lamination temperature exceeds 100 ° C. becomes high, and neither is preferable. . By setting the Tg and the weight average molecular weight of the polyimide within the above ranges, not only can the lamination temperature be kept low, but also the heating temperature (die bonding temperature) when the semiconductor element is bonded and fixed to the semiconductor element mounting support member. ) Can be reduced, and the effect of suppressing the warpage of the chip can be obtained. The Tg is a Tg measured using a DSC (DSC-7, manufactured by PerkinElmer) under the conditions of a sample amount of 10 mg, a heating rate of 5 ° C./min, and a measurement atmosphere of air. . In addition, the above-mentioned weight average molecular weight is a weight average molecular weight when measured in terms of polystyrene using high performance liquid chromatography (C-R4A manufactured by Shimadzu Corporation).

(B) Epoxy resin The epoxy resin (B) used in the present invention is (B1) 10 to 90% by weight of the total epoxy resin, and (B2) the liquid epoxy resin is 10 to 90% by weight of the total epoxy resin. % By weight.

  In the present invention, the content of the epoxy resin (B) may be 10 to 90% by weight of the epoxy resin having three or more functional groups and 10 to 90% by weight of the liquid epoxy resin as a whole.

  That is, (I) a bifunctional liquid epoxy resin, (II) a bifunctional solid epoxy resin, (III) a trifunctional or higher functional liquid epoxy resin, and (IV) a trifunctional or higher solid epoxy resin can be used in combination. In such a case, the total of (I) and (III) (that is, the total of the liquid epoxy resin) is 10 to 90% by weight, and the total of (III) and (IV) (that is, the total of the trifunctional or higher functional epoxy resin). Is adjusted to be 10 to 90% by weight, whereby the effect of the present invention can be obtained.

（式中、Ｑ^１０、Ｑ^１１及びＱ^１２は各々独立に水素又は炭素数１〜５のアルキレン基又は置換基を有してもよいフェニレン基を示し、ｒは１〜２０の整数を示す）で表されるノボラック型エポキシ樹脂の他、３官能型（又は４官能型）のグリシジルエーテル、３官能型（又は４官能型）のグリシジルアミン等が挙げられ、上記一般式（VII）で表されるノボラック型エポキシ樹脂としては、クレゾールノボラック樹脂のグリシジルエーテル、フェノールノボラック樹脂のグリシジルエーテル等が挙げられる。中でも、硬化物の架橋密度が高く、フィルムの熱時の接着強度を高くすることができる点で、上記一般式（VII）で表されるノボラック型エポキシ樹脂が好ましい。これらは単独で又は二種類以上を組み合わせて使用することができる。上記エポキシ樹脂は全エポキシ樹脂の１０〜９０重量％、好ましくは１０〜８０重量％、より好ましくは１０〜７０重量％、さらに好ましくは１０〜６０重量％である。１０重量％未満では硬化物の架橋密度を有効に上げることができず、９０重量％を超えると硬化前の熱時の流動性が十分に得られず、いずれも好ましくない。 The (B1) trifunctional or higher functional epoxy resin is not particularly limited as long as it contains at least three or more epoxy groups in the molecule. Examples of such an epoxy resin include the following general formula (VII)

(Wherein Q ¹⁰ , Q ¹¹ and Q ¹² each independently represent hydrogen or an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and r represents an integer of 1 to 20) In addition to the novolak type epoxy resin represented by the formula, there may be mentioned trifunctional (or tetrafunctional) glycidyl ether, trifunctional (or tetrafunctional) glycidylamine, and the like. Examples of the novolak type epoxy resin include glycidyl ether of cresol novolak resin and glycidyl ether of phenol novolak resin. Above all, a novolak-type epoxy resin represented by the general formula (VII) is preferable because the crosslinked density of the cured product is high and the adhesive strength of the film when heated can be increased. These can be used alone or in combination of two or more. The epoxy resin accounts for 10 to 90% by weight of the total epoxy resin, preferably 10 to 80% by weight, more preferably 10 to 70% by weight, and further preferably 10 to 60% by weight. If it is less than 10% by weight, the crosslink density of the cured product cannot be increased effectively, and if it exceeds 90% by weight, sufficient fluidity during heating before curing cannot be obtained, and both are not preferred.

  The liquid epoxy resin (B2) has two or more epoxy groups in a molecule and is a liquid epoxy resin at 10 to 30 ° C., and the liquid includes a state of a viscous liquid.

（式中、Ｑ^１３及びＱ^１６は各々独立に炭素数１〜５のアルキレン基又は置換基を有してもよいフェニレン基又はフェノキシ基を示し、Ｑ^１４及びＱ^１５は各々独立に炭素数１〜５のアルキル基又は水素を示し、ｔは１〜１０の整数を示す）で表されるビスフェノール型エポキシ樹脂が挙げられる。 Examples of such an epoxy resin include glycidyl ether of bisphenol A type (or AD type, S type and F type), glycidyl ether of water-added bisphenol A type, glycidyl ether of phenol novolak resin, and glycidyl ether of cresol novolak resin. Glycidyl ether of bisphenol A novolak resin, glycidyl ether of naphthalene resin, glycidyl ether of trifunctional (or tetrafunctional), glycidyl ether of dicyclopentadiene phenol resin, glycidyl ester of dimer acid, trifunctional (or tetrafunctional) Glycidylamine), glycidylamine of naphthalene resin, etc., and the following general formula (VIII)

(In the formula, Q ¹³ and Q ¹⁶ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group or a phenoxy group which may have a substituent, and Q ¹⁴ and Q ¹⁵ each independently represent 1 carbon atom. To 5 represents an alkyl group or hydrogen, and t represents an integer of 1 to 10).

  Examples of the epoxy resin represented by the above general formula (VIII) include glycidyl ether of ethylene oxide adduct bisphenol A type and propylene oxide adduct bisphenol A type glycidyl ether. Use to select a liquid.

  When selecting a bifunctional epoxy resin having two epoxy groups in the molecule, it is preferable to select a resin having a number average molecular weight in the range of 400 to 1500. Thereby, at the time of assembling and heating the package, it is possible to effectively reduce outgas which causes contamination of the chip surface or the device. The bisphenol-type epoxy resin represented by the general formula (VIII) is preferable in terms of ensuring good fluidity of the film when heated, imparting low-temperature laminating properties, and reducing the outgassing described above.

  These epoxy resins can be used alone or in combination of two or more. The epoxy resin accounts for 10 to 90% by weight of the total epoxy resin, preferably 20 to 90% by weight, more preferably 30 to 90% by weight, and still more preferably 40 to 90% by weight. If the amount is less than 10% by weight, sufficient fluidity during heating before curing cannot be obtained. If the amount exceeds 90% by weight, when a bifunctional epoxy resin is selected, the crosslink density of the cured product cannot be effectively increased, Neither is preferred.

  In the present invention, the content of the epoxy resin (B) is such that the epoxy resin having three or more functions is 10 to 90% by weight of the total epoxy resin and the liquid epoxy resin is 10 to 90% by weight of the total epoxy resin. Good. That is, (I) a bifunctional liquid epoxy resin, (II) a bifunctional solid epoxy resin, (III) a trifunctional or higher functional liquid epoxy resin, and (IV) a trifunctional or higher solid epoxy resin can be used in combination. In such a case, the effect of the present invention is adjusted by adjusting the total of (I) and (III) to be 10 to 90% by weight and the total of (III) and (IV) to be 10 to 90% by weight. Obtainable.

(C) Epoxy resin curing agent The epoxy resin curing agent (C) is not particularly limited, and includes, for example, a phenolic compound, an aliphatic amine, an alicyclic amine, an aromatic polyamine, a polyamide, an aliphatic acid anhydride, Alicyclic acid anhydride, aromatic acid anhydride, dicyandiamide, organic acid dihydrazide, boron trifluoride amine complex, imidazoles, tertiary amines and the like, among which phenol compounds are preferable, and at least Phenolic compounds having two phenolic hydroxyl groups are more preferred.

  Examples of the phenolic compound having at least two phenolic hydroxyl groups in the molecule include a phenol novolak resin, a cresol novolak resin, a t-butylphenol novolak resin, a dicyclopentagencresol novolak resin, and a dicyclopentadienephenol novolak resin. And xylylene-modified phenol novolak resin, naphthol novolak resin, trisphenol novolak resin, tetrakisphenol novolak resin, bisphenol A novolak resin, poly-p-vinylphenol resin, and phenol aralkyl resin. Among them, those having a number average molecular weight in the range of 400 to 1500 are preferable. Thereby, at the time of assembling and heating the package, it is possible to effectively reduce outgas which causes contamination of the chip surface or the device. Above all, naphthol novolak resin or trisphenol novolak resin is preferable in that it can effectively reduce outgas that causes contamination of the chip surface or the device or odor during package assembly heating.

The naphthol novolak resin is a naphthol compound represented by the following general formula (XI) or the following general formula (XII) and having three or more aromatic rings in a molecule.

In the above formulas (XI) and (XII), R ^{1 to} R ²⁰ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a hydroxyl group, and n represents an integer of 1 to 10. . X is a divalent organic group, for example, the following groups.

More specifically, such a naphthol compound is exemplified by condensation with a xylylene-modified naphthol novolak represented by the following general formulas (XIII) and (XIV) or p-cresol represented by (XV). And naphthol novolak.

Here, the number of repetitions n in the general formulas (XIII) and (XIV) is preferably 1 to 10.

The trisphenol-based compound is a trisphenol novolak resin having three hydroxyphenyl groups in a molecule, and is preferably represented by the following general formula (XVI).

However, in the formula (XVI), R ^{1 to} R ¹⁰ each independently represent a group selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, a phenyl group, and a hydroxyl group. D represents a tetravalent organic group, and examples of such a tetravalent organic group are shown below.

  Specific examples of such a trisphenol-based compound include, for example, 4,4 ′, 4 ″ -methylidene trisphenol, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) −1-methylethyl] phenyl] ethylidene] bisphenol, 4,4 ′, 4 ″ -ethylidinetris [2-methylphenol], 4,4 ′, 4 ″ -ethylidinetrisphenol, 4,4 ′-[( 2-hydroxyphenyl) methylene] bis [2-methylphenol], 4,4 '-[(4-hydroxyphenyl) methylene] bis [2-methylphenol], 4,4'-[(2-hydroxyphenyl) methylene ] Bis [2,3-dimethylphenol], 4,4 '-[(4-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4'-[(3-H Roxyphenyl) methylene] bis [2,3-dimethylphenol], 2,2 ′-[(2-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 2,2 ′-[(4-hydroxyphenyl ) Methylene] bis [3,5-dimethylphenol], 2,2 ′-[(2-hydroxyphenyl) methylene] bis [2,3,5-trimethylphenol], 4,4 ′-[(2-hydroxyphenyl ) Methylene] bis [2,3,6-trimethylphenol], 4,4 ′-[(3-hydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4,4 ′-[(4- (Hydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4,4 ′-[(2-hydroxyphenyl) methylene] bis [2-cyclohexyl- -Methylphenol], 4,4 '-[(3-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4'-[(4-hydroxyphenyl) methylene] bis [2-cyclohexyl -5-methylphenol], 4,4 '-[(3,4-dihydroxyphenyl) methylene] bis [2-methylphenol], 4,4'-[(3,4-dihydroxyphenyl) methylene] bis [2 , 6-dimethylphenol], 4,4 '-[(3,4-dihydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4- [bis (3-cyclohexyl-4-hydroxy-6- Methylphenyl) methyl] -1,2-benzenediol, 4,4 ′-[(2-hydroxyphenyl) methylene] bis [3-methylphenol ], 4,4 ', 4 "-(3-methyl-1-propanyl-3-ylidene) trisphenol, 4,4'-[(2-hydroxyphenyl) methylene] bis [2-methylethylphenol], 4 , 4 '-[(3-hydroxyphenyl) methylene] bis [2-methylethylphenol], 4,4'-[(4-hydroxyphenyl) methylene] bis [2-methylethylphenol], 2,2'- [(3-hydroxyphenyl) methylene] bis [3,5,6-trimethylphenol], 2,2 ′-[(4-hydroxyphenyl) methylene] bis [3,5,6-trimethylphenol], 4,4 '-[(2-hydroxyphenyl) methylene] bis [2-cyclohexylphenol] and 4,4'-[(3-hydroxyphenyl) methylene] bis [2-cyclo Silphenol], 4,4 '-[1- [4- [1- (4-hydroxy-3,5-dimethylphenyl) -1-methylethyl] phenyl] ethylidene] bis [2,6-dimethylphenol], 4,4 ', 4 "-methylidine tris [2-cyclohexyl-5-methylphenol], 4,4'-[1- [4- [1- (3-cyclohexyl-4-hydroxyphenyl) -1-methyl] Ethyl] phenyl] ethylidene] bis [2-cyclohexylphenol], 2,2 ′-[(3,4-dihydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(3,4 -Dihydroxyphenyl) methylene] bis [2- (methylethyl) phenol], 2,2 '-[(3,4-dihydroxyphenyl) methylene] bis [3,5,6-trimethyl Phenol], 4,4 '-[(3,4-dihydroxyphenyl) methylene] bis [2-cyclohexylphenol], α, α', α "-tris (4-hydroxyphenyl) -1,3,5-tri Isopropylbenzene, and the like.

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

  The equivalent ratio of the epoxy equivalents of the above (B1) and (B2) and the OH equivalent of the phenolic compound as the epoxy resin curing agent (C) is 0.95 to 1.05: 0.95 to 1.05. I do. If the ratio is outside the above range, unreacted monomers may remain, or the crosslinked density of the cured product may not increase, which is not preferable.

  Further, based on 100 parts by weight of the polyimide resin (A), 5 to 30 parts by weight of the epoxy resin (B1) having three or more functions and 10 to 50 parts by weight of the liquid epoxy resin (B2) are contained. However, it is preferable because good reliability as a package, such as low outgassing property at the time of assembling and heating, low reflow resistance and moisture resistance reliability, can be secured at the same time.

  The addition amount of the curing accelerator is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the epoxy resin. If the amount is less than 0.01 part by weight, the curability tends to be poor, and if it exceeds 20 parts by weight, the storage stability tends to decrease.

(D) Filler The (D) filler used in the present invention is not particularly limited, and examples thereof include metal fillers such as silver powder, gold powder, copper powder, and nickel powder; alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, and carbonate. Inorganic fillers such as magnesium, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, crystalline silica, amorphous silica, boron nitride, titania, glass, iron oxide, and ceramic; carbon, Organic fillers such as rubber-based fillers and the like can be mentioned, and the shape of the filler is not particularly limited.

  The filler can be properly used depending on a desired function. For example, metal fillers are added for the purpose of imparting conductivity, thermal conductivity, thixotropy, etc. to the adhesive composition; non-metallic inorganic fillers provide thermal conductivity, low thermal expansion, low hygroscopicity, etc. to the adhesive film. The organic filler is added for the purpose of imparting toughness or the like to the adhesive film. These metal fillers, inorganic fillers or organic fillers can be used alone or in combination of two or more. Among them, a metal filler, an inorganic filler, or an insulating filler is preferable in terms of being capable of imparting conductivity, heat conductivity, low moisture absorption properties, and insulating properties, which are required for an adhesive material for a semiconductor package. Among the conductive fillers, boron nitride is more preferable because it has good dispersibility in a resin varnish and can provide high adhesive strength when heated.

  The filler has an average particle diameter of 10 μm or less, a maximum particle diameter of 25 μm or less, and preferably an average particle diameter of 5 μm or less and a maximum particle diameter of 20 μm or less. If the average particle size exceeds 10 μm and the maximum particle size exceeds 25 μm, the effect of improving fracture toughness cannot be obtained. The lower limit is not particularly limited, but both are usually 0.1 μm.

  The filler needs to satisfy both an average particle diameter of 10 μm or less and a maximum particle diameter of 25 μm or less. When a filler having a maximum particle diameter of 25 μm or less but an average particle diameter of more than 10 μm is used, high adhesive strength cannot be obtained. When a filler having an average particle diameter of 10 μm or less but a maximum particle diameter of more than 25 μm is used, the particle diameter distribution is widened and the adhesive strength tends to vary. When the adhesive composition of the present invention is processed into a thin film and used, the surface is roughened and the adhesive strength is reduced.

  Examples of the method for measuring the average particle diameter and the maximum particle diameter of the filler include a method of measuring the particle diameter of about 200 fillers using a scanning electron microscope (SEM).

  As a measurement method using an SEM, for example, a sample is prepared in which a semiconductor element and a semiconductor supporting substrate are bonded using an adhesive composition and then cured by heating (preferably at 150 to 200 ° C. for 1 to 10 hours). Then, a method of cutting a central portion of the sample and observing a cross section of the sample with an SEM may be used.

  When the filler used is a metal filler or an inorganic filler, a method of heating the adhesive composition in an oven at 600 ° C. for 2 hours to decompose and volatilize the resin component, and observe and measure the remaining filler by SEM. Can also be taken. When the filler itself is observed by SEM, a double-sided adhesive tape is stuck on a sample stage for SEM observation, the filler is sprinkled on the adhesive surface, and then a sample obtained by vapor deposition by ion sputtering is used. At this time, it is assumed that the existence probability of the filler is 80% or more of all the fillers.

  The amount of the filler (D) to be used is determined according to the properties or functions to be imparted, and (A) a thermoplastic resin, (B) an epoxy resin, (C) a resin component containing an epoxy resin curing agent, and (D) 1) 1 to 50% by volume, preferably 2 to 40% by volume, more preferably 5 to 30% by volume, based on the total amount of the filler. If it is less than 2% by volume, the effect of imparting the properties or functions by adding the filler cannot be obtained, and if it exceeds 50% by volume, the adhesiveness decreases, and both are not preferred. By increasing the amount of filler, a high elastic modulus can be achieved, and dicing properties (cutability with a dicer blade), wire bonding properties (ultrasonic efficiency), and adhesive strength during heating can be effectively improved, but the amount is increased more than necessary. Then, the low-temperature sticking property and the interfacial adhesion to the adherend, which are the features of the present invention, are impaired, and the reliability including reflow resistance is lowered, which is not preferable. The optimum filler content is determined to balance the required properties.

  The film adhesive of the present invention may further contain optional components described below in addition to the above components.

  Various coupling agents can be added to the film adhesive of the present invention in order to improve interfacial bonding between different materials.

(Production method)
The film adhesive of the present invention comprises (A) a thermoplastic resin, (B) an epoxy resin, and if necessary, (C) an epoxy resin curing agent, (D) a filler, and other components mixed in an organic solvent. After kneading to prepare a varnish (varnish for coating a film adhesive), a varnish layer is formed on a substrate film, and the substrate is removed after heating and drying. The above mixing and kneading can be carried out by appropriately combining ordinary dispersing machines such as a stirrer, a grinder, a three-roll mill and a ball mill. The heating and drying conditions are not particularly limited as long as the used solvent is sufficiently volatilized, but the heating and drying are usually performed by heating at 60 to 200 ° C. for 0.1 to 90 minutes.

  Here, in order to control the flow amount in the B-stage state within the range of 200 to 1500 μm, it is desirable to reduce the residual solvent as much as possible, and to the extent that the sticking property is not impaired, Alternatively, it is desirable to advance the crosslinking reaction between the polyimide resin and the epoxy resin to some extent. From this viewpoint, it is preferable that the film preparation includes a drying step at 120 to 160 ° C. for 10 to 60 minutes.

  The organic solvent used for the preparation of the varnish in the production of the film adhesive, that is, the varnish solvent is not particularly limited as long as it can uniformly dissolve, knead or disperse the material. For example, dimethylformamide, dimethylacetamide, N- Methyl pyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane, cyclohexanone, ethyl acetate, etc., but the crosslinking reaction between the polyimide resin and the epoxy resin The nitrogen-containing compound is preferable from the viewpoint of effectively proceeding with. Examples of such a solvent include the above-mentioned dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like. Among them, N-methylpyrrolidone is preferable because of its excellent solubility of the polyimide resin.

  The substrate film used in the production of the film adhesive is not particularly limited as long as it can withstand the above-mentioned heating and drying conditions.For example, a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a poly Examples include an etherimide film, a polyether naphthalate film, and a methylpentene film. Two or more of these base films may be used in combination to form a multilayer film, or the surface of the base material may be treated with a silicone-based or silica-based release agent. At this time, a film-like adhesive with a substrate may be used as a film support without removing the substrate.

  Next, the present invention will be described in more detail with reference to some preferred embodiments.

(First aspect)
The film adhesive as one embodiment of the present invention has a tan δ peak temperature of 20 to 65 ° C. and a flow rate of 200 to 1500 μm. The above-mentioned tan δ peak temperature means that a film heat-cured under the conditions of 180 ° C. for 5 hours is measured using a rheometrics viscoelastic analyzer RSA-2 with a film size of 35 mm × 10 mm, a temperature rising rate of 5 ° C./min, a frequency of 1 Hz, and a measurement. Temperature is a tan δ peak temperature measured at a temperature of −100 to 300 ° C. If the tan δ peak temperature of the film is less than 20 ° C., the probability that the flow amount exceeds 1500 μm increases, and if the tan δ peak temperature exceeds 65 ° C., the possibility that the lamination temperature exceeds 100 ° C. increases, Not preferred. In addition, the flow amount is 10 mm × 10 mm × 40 μm thick (the film thickness was adjusted with an error of ± 5 μm. The description of the film thickness error is omitted because it is the same as above). A 10 mm × 10 mm × 50 μm thick Iupirex film is superimposed on the film (uncured film) and sandwiched between two slide glasses (made by Matsunami, 76 mm × 26 mm × 1.0-1.2 mm thick). This is the maximum value when the amount of protrusion from the above-mentioned Iupirex film after applying a load of 100 kgf / cm ² on a hot plate at 180 ° C. and applying heat and pressure for 120 seconds is observed with an optical microscope. If the flow amount at this time is less than 100 μm, it is not possible to sufficiently bury the irregularities on the wiring-attached substrate due to heat and pressure during transfer molding, and if it exceeds 1500 μm, the heat during die bonding or wire bonding It flows due to the history, and it becomes easy to entrap bubbles remaining between the irregularities with respect to the irregularities on the substrate, and even if heat and pressure are applied in the transfer molding process, the bubbles are not completely removed and become voids. Any of them is not preferable because it remains in the film layer and the voids serve as a starting point and easily foam during moisture absorption reflow.

(Second aspect)
The film adhesive as one embodiment of the present invention has a 90 ° peeling force at 25 ° C. against the silicon wafer at 25 ° C. of 5 N / m or more when laminated at 80 ° C. on the back surface of the silicon wafer (back-grind treated surface). There is a feature.

  Here, the 90 ° peeling force will be described with reference to the schematic diagrams of FIGS.

  1 and 2 are schematic views of a laminating method in which the film adhesive 1 of the present invention is laminated on a silicon wafer 3 using an apparatus having a roll 2 and a support 4. The 90 ° peeling force refers to a laminate having a roll temperature of the apparatus of 80 ° C. and a feeding speed of 0.5 m / min, and laminating a 40-μm thick film-like adhesive on the back surface of a 5-inch, 400-μm thick silicon wafer. The peeling force when the film adhesive (1 cm width) is peeled off in the direction of 90 ° at 100 mm / min by the method shown in FIG.

  The 90 ° peel force is preferably 5 N / m or more, more preferably 8 N / m or more, further preferably 10 N / m or more, and even more preferably 20 N / m or more. If the peeling force is less than 5 N / m, there is a high possibility that chip fly will occur during dicing.

  In the above lamination conditions, the lamination pressure is preferably determined from the thickness and size of the semiconductor wafer as the adherend. Specifically, when the thickness of the wafer is 10 to 600 μm, the linear pressure is preferably 0.5 to 20 kgf / cm, and when the thickness of the wafer is 10 to 200 μm, the linear pressure is preferably 0.5 to 5 kgf / cm. . The size of the wafer is generally about 4 to 10 inches, but is not particularly limited thereto. With the above lamination conditions, the balance between prevention of wafer cracking during lamination and securing of adhesion can be maintained.

(Third aspect)
The film adhesive as one embodiment of the present invention is a 5 mm × 5 mm × 0.55 mm thick glass chip having a thickness of 5 mm × 5 mm × 0.55 mm × 10 mm on an organic substrate having a thickness of 0.1 mm and a solder resist layer having a thickness of 15 μm on the surface. After die bonding under the condition of Tg (here, tan δ peak temperature) + 100 ° C. × 500 gf / chip × 3 sec with a film-like adhesive having a thickness of 40 μm, the film was heated and pressed under the condition of 180 ° C. × 5 kgf / chip × 90 sec. After heat curing the film adhesive at 180 ° C. for 5 hours, the film adhesive is subjected to a moisture absorption treatment at 85 ° C. and 85% relative humidity (hereinafter also referred to as “RH”) for 15 hours, and then placed on a hot plate at 260 ° C. for 30 seconds. When heated, no foaming is observed.

  The film-like adhesive as one embodiment of the present invention has the above-mentioned feature that the generation of foaming is not recognized, and furthermore, adds a 3.2 mm × 3.2 mm × 0.4 mm thick silicon chip to the organic substrate. After die-bonding with a film adhesive having a thickness of 0.2 mm × 3.2 mm × 40 μm under the conditions of Tg (tan δ peak temperature in this case) + 100 ° C. × 500 gf / chip × 3 sec, 180 ° C. × 5 kgf / chip × 90 sec. The film adhesive was heated and cured at 180 ° C. for 5 hours, then subjected to a moisture absorption treatment at 85 ° C. and 60% RH for 168 hours, and then heated on a hot plate at 260 ° C. for 30 seconds. Has a shear adhesive strength of 5 N / chip or more.

  The presence or absence of the occurrence of the foaming is determined by visually observing with an optical microscope (× 20). The above-mentioned shear adhesive strength is measured using a BT2400 manufactured by Dage under the conditions of a measuring speed of 500 μm / sec and a measuring gap of 50 μm.

(Fourth aspect)
The film adhesive according to one embodiment of the present invention is used for a film die bonding material containing at least a thermoplastic resin and a thermosetting resin, and the volatile adhesive remaining in the film adhesive is V (% By weight), the water absorption after heating and curing is M (% by weight), the flow amount is F (μm), and the storage elastic modulus at 260 ° C. after heating and curing is E (MPa). ~ (4):
(1) V ≦ 10.65 × E,
(2) M ≦ 0.22 × E,
(3) V ≦ −0.0043F + 11.35,
(4) M ≦ −0.0002F + 0.6
Characterized by satisfying at least one condition of

  In this case, it is preferable that the conditions (3) and (4) are simultaneously satisfied, more preferably the conditions (2) to (4) are satisfied, and all the conditions (1) to (4) are satisfied. It is more preferable to satisfy the following.

  The above-mentioned residual volatile content V is determined from the film after preparation, V = (film weight before heating−film weight after heating in an oven at 260 ° C. for 2 hours) / film weight before heating. The water absorption M after the above heat curing is as follows: M = (weight of film after immersion in ion exchanged water for 24 hours−weight of film before water absorption) / film before water absorption for a film heat cured at 180 ° C. for 5 hours. Calculate from the weight of The weight of the film before water absorption is the weight after drying in a vacuum dryer at 120 ° C. for 3 hours. The above-mentioned flow amount F is a value measured under the above-described conditions. The storage elastic modulus E at 260 ° C. after heat curing is as follows: For a film heat-cured at 180 ° C. for 5 hours, using a viscoelastic analyzer RSA-2 manufactured by Rheometrics, the film size is 35 mm × 10 mm, and the rate of temperature rise is 5 ° C. / Min, a frequency of 1 Hz, and a storage elastic modulus at 260 ° C. when measured at a measurement temperature of −50 to 300 ° C. If any of the above-mentioned residual volatile components V, water absorption M, flow amount F, and storage modulus E (MPa) are out of the ranges of the above formulas, the low-temperature laminating property and good reflow resistance in the present invention are obtained. It is difficult to secure the properties at the same time.

(Fifth aspect)
Further, as one embodiment of the present invention, there is provided an adhesive sheet in which a base material layer, an adhesive layer, and the film-like adhesive layer of the present invention are formed in this order. This adhesive sheet is an integrated adhesive sheet including at least a film adhesive and a dicing film for the purpose of simplifying a semiconductor device manufacturing process. That is, it is an adhesive sheet having characteristics required for both the dicing film and the die bonding film.

  Thus, the adhesive layer serving as a dicing film is provided on the base material layer, and the film adhesive layer of the present invention serving as a die bonding film is further provided on the adhesive layer. By laminating them, they function as a dicing film during dicing and as a die bonding film during die bonding. Therefore, the integrated adhesive sheet is laminated on the back surface of the semiconductor wafer while heating the film adhesive layer of the integrated adhesive sheet on the back surface of the semiconductor wafer, diced, and picked up as a semiconductor element with a film adhesive. Can be used.

The pressure-sensitive adhesive layer may be either a pressure-sensitive type or a radiation-curable type, but the radiation-curable type has a higher adhesive strength at the time of dicing, and is irradiated with ultraviolet rays (UV) before picking up. This is preferable in that the adhesive strength becomes low and the adhesive strength is easily controlled. The radiation-curable adhesive layer has sufficient adhesive strength so that the semiconductor element does not scatter during dicing, and has a low adhesive strength that does not damage the semiconductor element in the subsequent semiconductor element pickup step. If so, a conventionally known material can be used without any particular limitation. At this time, at the stage of lamination at 80 ° C. on the silicon wafer, the 90 ° peeling force of the film adhesive at 25 ° C. on the silicon wafer is A, and the radiation after UV irradiation under the condition of the exposure amount of 500 mJ / cm ² is A Assuming that the 90 ° peel force at 25 ° C. of the curable pressure-sensitive adhesive layer with respect to the film adhesive is B, the value of AB is preferably 1 N / m or more, more preferably 5 N / m or more. Preferably, it is even more preferably 10 N / m or more. The 90 ° peel force at 25 ° C. of the film adhesive on the silicon wafer is as described above. Further, the 90 ° peeling force at 25 ° C. of the radiation-curable adhesive layer at 25 ° C. with respect to the film-like adhesive after UV irradiation under the condition of an exposure amount of 500 mJ / cm ² is the back surface of the silicon wafer (back-grind treated surface). After laminating at 80 ° C. (the laminating method is described above), the above dicing tape was laminated at room temperature, and then subjected to UV irradiation at a light exposure of 500 mJ / cm ² at 25 ° C. with respect to the film adhesive of the dicing tape. Is the peeling force when the 90 ° peeling force (1 cm width, FIG. 4) is peeled off in the 90 ° direction. If the above value (AB) is less than 1 N / m, each element tends to be damaged at the time of pickup, or at the interface between the silicon chip and the film-like adhesive agent at the time of pickup, it cannot be picked up effectively. Therefore, it is not preferable.

The above 90 ° peeling force is determined by laminating the silicon wafer on the back surface (back-grind treated surface) at 80 ° C. (the laminating method is as described above), laminating the above dicing tape at room temperature, and then exposing at a dose of 500 mJ / cm ^2. The peeling force when the 90 ° peeling force (1 cm width, FIG. 4) of the dicing tape at 25 ° C. (1 cm width, FIG. 4) with respect to the film adhesive after UV irradiation under the condition of (1) was peeled in the 90 ° direction. The "peel peeling force" will be described in more detail later in the Examples section.

The 90 ° peeling force at 25 ° C. of the radiation-curable pressure-sensitive adhesive layer at 25 ° C. on the film-like adhesive after UV irradiation under the conditions of the above-mentioned exposure amount of 500 mJ / cm ^{2 was} measured by the method shown in FIG. (1 cm width) This refers to the peeling force when the film adhesive (1: film adhesive, 3: silicon wafer, 4: support) is peeled off in the direction of 90 ° at 100 mm / min.

  The radiation-curable pressure-sensitive adhesive layer is not particularly limited as long as it has the above characteristics, and a conventionally known one can be used.

  Specifically, a layer containing a pressure-sensitive adhesive and a radiation-polymerizable oligomer can be used as the radiation-curable adhesive layer.

  In this case, the pressure-sensitive adhesive constituting the radiation-curable pressure-sensitive adhesive layer is preferably an acrylic pressure-sensitive adhesive. More specifically, for example, a (meth) acrylate copolymer containing (meth) acrylate or a derivative thereof as a main constituent monomer unit, a mixture of these copolymers, and the like can be given. In addition, in this specification, when it describes like (meth) acrylic ester, it shows both a methacrylic ester and an acrylic ester.

  Examples of the (meth) acrylate copolymer include at least one or more alkyl (meth) acrylate monomers selected from alkyl (meth) acrylates having 1 to 15 carbon atoms in the alkyl group. (A) from the group consisting of glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, vinyl acetate, styrene and vinyl chloride Copolymer of at least one polar monomer having no acid group (b) and at least one comonomer having at least one acid group selected from the group consisting of acrylic acid, methacrylic acid and maleic acid (c) Coalescence and the like.

  The copolymerization ratio of the (meth) acrylic acid alkyl ester monomer (a), the polar monomer (b) having no acid group, and the comonomer (c) having an acid group is represented by a / b / c by weight. = 35-99 / 1-60 / 0-5. Further, the comonomer (c) having an acid group may not be used, and in such a case, it is preferable to mix in the range of a / b = 70 to 95/5 to 30.

  When the polar monomer (b) having no acid group as a comonomer is copolymerized in an amount exceeding 60% by weight, the radiation-curable pressure-sensitive adhesive layer 3 becomes a completely compatible system, and the elastic modulus after radiation curing exceeds 10 MPa. As a result, there is a tendency that sufficient expandability and pickup property cannot be obtained. On the other hand, when the polar monomer (b) having no acid group is copolymerized in less than 1% by weight, the radiation-curable pressure-sensitive adhesive layer 3 becomes a non-uniform dispersion system, and good pressure-sensitive adhesive properties tend not to be obtained. .

  When (meth) acrylic acid is used as a comonomer having an acid group, the copolymerization amount of (meth) acrylic acid is preferably 5% by weight or less. When (meth) acrylic acid is copolymerized in excess of 5% by weight as a comonomer having an acid group, the radiation-curable pressure-sensitive adhesive layer 3 becomes a completely compatible system and tends to have insufficient expandability and pickup property. is there.

The weight average molecular weight of the (meth) acrylate copolymer obtained by copolymerizing these monomers is preferably 2.0 × 10 ^{5 to} 10.0 × 10 ⁵ , and 4.0 × 10 ^{5. 5 to} 8.0 × 10 ⁵ is more preferable.

  The molecular weight of the radiation-polymerizable oligomer constituting the radiation-curable pressure-sensitive adhesive layer is not particularly limited, but is usually about 3,000 to 30,000, and preferably about 5,000 to 10,000.

  The radiation polymerizable oligomer is preferably uniformly dispersed in the radiation-curable pressure-sensitive adhesive layer. The dispersed particle size is preferably from 1 to 30 μm, more preferably from 1 to 10 μm. The dispersed particle size is a value determined by observing the radiation-curable pressure-sensitive adhesive layer 3 with a microscope at a magnification of 600 and actually measuring the particle size of the oligomer dispersed on a scale in the microscope. In addition, the state in which the particles are uniformly dispersed (uniform dispersion) refers to a state in which the distance between adjacent particles is 0.1 to 10 μm.

  Examples of the radiation-polymerizable oligomer include compounds having at least one carbon-carbon double bond in a molecule thereof, such as urethane acrylate oligomers, epoxy-modified urethane acrylate oligomers, and epoxy acrylate oligomers. Urethane acrylate oligomers are preferred because various compounds can be selected according to the purpose.

  The urethane acrylate oligomer includes, for example, a polyol compound such as a polyester type or polyether, and 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate. For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate may be used as the terminal isocyanate urethane prepolymer obtained by reacting with a polyvalent isocyanate compound such as isocyanate, diphenylmethane, and 4,4-diisocyanate. Acrylate or methacrylate having a hydroxyl group such as, 2-hydroxypropyl methacrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, etc. It can be obtained by reacting and.

  The molecular weight of the urethane acrylate oligomer is not particularly limited, but is preferably from 3,000 to 30,000, more preferably from 3,000 to 10,000, and most preferably from 4,000 to 8,000.

  In the adhesive sheet of the present invention, the mixing ratio of the pressure-sensitive adhesive and the radiation-polymerizable oligomer in the radiation-curable pressure-sensitive adhesive layer is such that the radiation-polymerizable oligomer is used in an amount of 20 to 200 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive. And more preferably 50 to 150 parts by weight.

  With the above mixing ratio, a large initial adhesive force is obtained between the radiation-curable pressure-sensitive adhesive layer and the die-bonding adhesive layer, and the adhesive force is significantly reduced after irradiation, so that the wafer chip can be easily formed. And the adhesive layer for die bonding can be picked up from the pressure-sensitive adhesive sheet. In addition, since a certain degree of elasticity is maintained, it is easy to obtain a desired chip interval in the expanding step, and the chip can be stably picked up without any deviation of the chip body. If necessary, other components may be added in addition to the above components.

(Applications and usage)
The film-like adhesive of the present invention includes semiconductor elements such as ICs and LSIs, lead frames such as 42 alloy lead frames and copper lead frames; plastic films such as polyimide resins and epoxy resins; A material impregnated and cured with a plastic such as an epoxy resin; used as an adhesive material for die bonding for bonding a semiconductor mounting support member such as ceramics such as alumina. Among them, it is suitably used as an adhesive material for die bonding for bonding to an organic substrate having an organic resist layer.

  Further, in Stacked-PKG having a structure in which a plurality of semiconductor elements are stacked, it is suitably used as an adhesive material for bonding semiconductor elements to each other.

  The application of the film adhesive of the present invention will be specifically described with reference to the drawings for a semiconductor device provided with the film adhesive of the present invention. In recent years, semiconductor devices having various structures have been proposed, and the application of the film adhesive of the present invention is not limited to the semiconductor devices having the structures described below.

  FIG. 5 shows a semiconductor device having a general structure. In FIG. 5, a semiconductor element 10a is bonded to a semiconductor element support member 12 via a film adhesive 11a of the present invention, and a connection terminal (not shown) of the semiconductor element 10a is connected to an external connection terminal (not shown) via a wire 13. (Not shown), and is sealed with a sealing material 14.

  FIG. 6 shows an example of a semiconductor device having a structure in which semiconductor elements are bonded to each other. In FIG. 6, the first-stage semiconductor element 10a is adhered to the semiconductor-element supporting member 12 via the film-like adhesive 11a of the present invention, and the film-like adhesive 11b of the present invention is further applied on the first-stage semiconductor element 10a. The second-stage semiconductor element 10b is bonded through the intermediary. A connection terminal (not shown) of the first-stage semiconductor element 10a and the second-stage semiconductor element 10b is electrically connected to an external connection terminal (not shown) via a wire 13 and a sealing material (not shown). )). Thus, the film adhesive of the present invention can be suitably used for a semiconductor device having a structure in which a plurality of semiconductor elements are stacked.

  In the semiconductor device (semiconductor package) having the above structure, the film-like adhesive of the present invention is sandwiched between the semiconductor element and the support member, and the two members are bonded by heating and pressure bonding. It can be obtained by passing through a step such as a sealing step using a sealing material. The heating temperature in the thermocompression bonding step is usually 40 to 250 ° C. for 0.1 to 300 seconds.

  The film adhesive of the present invention is preferably a single-layer film adhesive composed of only the adhesive layer 15 as shown in FIG. The structure which provided the adhesive layer 15 may be sufficient. Incidentally, a cover film may be provided on the adhesive layer as appropriate in order to prevent damage and contamination of the adhesive layer. That is, as shown in FIG. 9, a film adhesive having a structure in which the adhesive layer 18 is provided on the base film 17 and the cover film 19 is further provided may be used.

  The film-like adhesive of the present invention has excellent low-temperature laminating properties and pick-up properties after dicing as an adhesive material for electronic components such as semiconductor elements and supporting members such as lead frames and insulating supporting substrates, and has good thermal adhesion. It has excellent reliability against force and heat history of high-temperature soldering at the time of mounting, and can be suitably used as a die-bonding material of a lead-free semiconductor package. A semiconductor device having a structure in which a semiconductor element and a supporting member are bonded to each other using the adhesive composition or the film adhesive of the present invention is excellent in reliability.

  Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited to these.

(Examples 1-3, Comparative Examples 1-4)
Using the following polyimides A to E as thermoplastic resins, film coating varnishes were prepared as shown in the composition tables in Tables 1 and 2.

<Polyimide A>
In a 300 ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, 2.71 g (0.045 mol) of 1,12-diaminododecane and polyetherdiamine (manufactured by BASF, polyetherdiamine 2000 (molecular weight: 1923)) 5. 77 g (0.01 mol), 3.35 g (0.045 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (manufactured by Shin-Etsu Chemical, LP-7100) and 113 g of N-methyl-2-pyrrolidone And stirred. After dissolution of the diamine, 4,4 ′-(4,4′-isopropylidene diphenoxy) bis (phthalic dianhydride) recrystallized and purified using acetic anhydride while cooling the flask in an ice bath. 62 g (0.1 mol) were added in small portions. After reacting at room temperature for 8 hours, 75.5 g of xylene was added, and the mixture was heated at 180 ° C. while blowing nitrogen gas to azeotropically remove xylene with water to obtain a polyimide solution (Tg: 53 ° C., weight average molecular weight). : 58000).

<Polyimide B>
In a 300 ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, 13.67 g (0.10 mol) of 2,2-bis (4-aminophenoxyphenyl) propane and 124 g of N-methyl-2-pyrrolidone were charged and stirred. did. After dissolution of the diamine, 17.40 g (0.10 mol) of decamethylene bistrimellitate dianhydride was added little by little while the flask was cooled in an ice bath. After reacting at room temperature for 8 hours, 83 g of xylene was added, and the mixture was heated at 180 ° C. while blowing nitrogen gas to azeotropically remove xylene with water to obtain a polyimide solution (Tg: 120 ° C., weight average molecular weight: 121000). ).

<Polyimide C>
In a 300 ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, 6.83 g (0.05 mol) of 2,2-bis (4-aminophenoxyphenyl) propane, 4,9-dioxadecane-1,12-diamine 3 .40 g (0.05 mol) and 110.5 g of N-methyl-2-pyrrolidone were charged and stirred. After dissolution of the diamine, 17.40 g (0.10 mol) of decamethylene bistrimellitate dianhydride was added little by little while the flask was cooled in an ice bath. After reacting at room temperature for 8 hours, 74 g of xylene was added, and the mixture was heated at 180 ° C. while blowing nitrogen gas to azeotropically remove xylene with water to obtain a polyimide solution (Tg: 73 ° C., weight average molecular weight: 84300). ).

<Polyimide D>
In a 300 ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, 2.73 g (0.02 mol) of 2,2-bis (4-aminophenoxyphenyl) propane, polysiloxane diamine (KF-8010 manufactured by Shin-Etsu Silicone, molecular weight) : 90024.00 g (0.08 mol) and 176.5 g of N-methyl-2-pyrrolidone were stirred in. After dissolution of the diamine, the flask was cooled in an ice bath while decamethylene bistrimellitate dianhydride was added. After reacting at room temperature for 8 hours, 117.7 g of xylene was added, and the mixture was heated at 180 ° C. while blowing nitrogen gas to remove azeotropically with water. A polyimide solution was obtained (Tg: 40 ° C., weight average molecular weight: 19700).

<Polyimide E>
In a 300 ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, 5.41 g (0.045 mol) of 1,12-diaminododecane and 11.54 g of ether diamine (manufactured by BASF, ether diamine 2000 (molecular weight: 1923)) were added. 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, 31.23 g (0.1 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic dianhydride) was added while cooling the flask in an ice bath. Were added. After reacting at room temperature for 8 hours, 112.7 g of xylene was added, and the mixture was heated at 180 ° C. while blowing nitrogen gas to azeotropically remove xylene with water to obtain a polyimide solution (Tg: 25 ° C., weight average molecular weight). : 35000).

  In Table 1, various symbols mean the following.

ESCN-195: Sumitomo Chemical, cresol novolak type solid epoxy resin (epoxy equivalent: 200, molecular weight: 778),
BEO-60E: Shin-Nippon Rikagaku, ethylene oxide 6 mol adduct bisphenol A liquid epoxy resin (epoxy equivalent: 373, molecular weight: 746),
XB-4122: Asahi Chiba, alkylene oxide adduct bisphenol A liquid epoxy resin (epoxy equivalent: 336, molecular weight: 672),
N-730: Dainippon Ink and Chemicals, phenol novolak type liquid epoxy resin (epoxy equivalent: 175, molecular weight: 600 to 800),
EXA830CRP: Dainippon Chemical, bisphenol F type liquid epoxy resin (epoxy equivalent: 160, molecular weight: 320),
H-1: Meiwa Kasei, phenol novolak (OH equivalent: 106, molecular weight: 653),
NH-7000: Nippon Kayaku, naphthol novolak (OH equivalent: 175, molecular weight: 420),
TrisP-PA: Honshu Chemical, Trisphenol novolak (OH equivalent: 141, molecular weight: 424),
XL-225, Mitsui Toatsu Chemicals, xylylene-modified phenol novolak (OH equivalent: 175, molecular weight: 976),
TPPK: Tokyo Chemical Industry, Tetraphenylphosphonium tetraphenylborate,
2PZ-CN: Shikoku Chemical Industry, 1-cyanoethyl-2-phenylimidazole,
NMP: Kanto Chemical, N-methyl-2-pyrrolidone,
HP-P1: Mizushima alloy iron, boron nitride (average particle diameter: 1.0 μm, maximum particle diameter: 5.1 μm),
E-03: Tokai mineral, silica (average particle diameter: 4.0 μm, maximum particle diameter: 11.4 μm),
SE-1: Tokuyama, silica (average particle diameter: 0.8 μm, maximum particle diameter: 3.1 μm),

  This varnish is applied to a base material (peeling agent-treated PET) to a thickness of 40 μm, heated in an oven at 80 ° C. for 30 minutes, then at 150 ° C. for 30 minutes, and then peeled from the base material at room temperature to obtain a film. Adhesive adhesive was obtained. All of the films were self-supporting films, except that tackiness was observed at room temperature only in Comparative Example 4.

Tables 3 and 4 show the results of evaluating the properties of the film adhesives of Examples 1 to 3 and Comparative Examples 1 to 4.

<Remaining volatiles>
A 50 mm × 50 mm × 40 μm thick film-shaped adhesive (uncured film) was used as a sample, the weight of the sample was set as M1, the sample was heated in an oven at 260 ° C. for 2 hours, weighed as M2, and [(M2-M1 ) / M1] × 100 = residual volatile content (wt%).

<Flow amount>
A 10 mm × 10 mm × 40 μm thick film adhesive (uncured film) was used as a sample, a 10 mm × 10 mm × 50 μm thick Iupirex film was superimposed on the sample, and two slide glasses (made by Matsunami) , 76 mm × 26 mm × 1.0 to 1.2 mm thick), and a load of 100 kgf / cm ² was applied on a hot plate at 180 ° C., and the amount of protrusion from the Iupirex film after being heated and pressed for 120 sec. The maximum value when observed with a graduated optical microscope was defined as the flow amount.

<Water absorption>
A 20 mm × 20 mm × 40 μm thick film adhesive (film cured by heating at 180 ° C. for 5 hours) was used as a sample, and the sample was dried in a vacuum dryer at 120 ° C. for 3 hours, allowed to cool in a desiccator, and dried. The weight is defined as M1, and the dried sample is immersed in ion-exchanged water at room temperature for 24 hours, taken out, wiped with a filter paper, weighed quickly, and defined as M2.

  The water absorption was calculated as [(M2−M1) / M1] × 100 = water absorption (wt%).

<260 ° C. storage modulus and tan δ peak temperature>
Using a rheometrics-made viscoelasticity analyzer RSA-2, the film adhesive was heat-cured under the conditions of 180 ° C. for 5 hours, and the film size was 35 mm × 10 mm × 40 μm thick, the temperature rising rate was 5 ° C./min, the frequency was 1 Hz, and the measurement temperature was The measurement was performed at -100 to 300 ° C, and the storage elastic modulus at 260 ° C and the tan δ peak temperature near Tg were estimated.

<Peel peel force>
Peeling force on wafer: Laminate a prepared film adhesive (uncured film) 1 having a thickness of 40 μm on the back surface of silicon wafer 3 using a device having roll 2 and support table 4 shown in FIG. did. At this time, the film adhesive 1 was laminated on the back surface of the silicon wafer 3 having a thickness of 5 inches and a thickness of 300 μm under the conditions of a roll temperature of the apparatus: 80 ° C., a linear pressure: 4 kgf / cm, and a feed speed: 0.5 m / min. . Thereafter, the peeling force when the film adhesive 1 (1 cm width) was peeled off in the direction of 90 ° by the method shown in FIG. 3 was taken as the peeling force for the wafer (measuring speed: 100 mm / min).

Peeling force of the radiation-curable pressure-sensitive adhesive layer on the film-like adhesive: UV-type radiation-curable pressure-sensitive adhesive layer on the other surface of the film-side adhesive with wafer 1 facing the wafer. Dicing tape 5 was laminated. The laminating conditions were the same as the laminating conditions for the film adhesive described above, except that the roll temperature of the apparatus was room temperature (25 ° C.). Thereafter, using a UV-330 HQP-2 type exposure machine manufactured by Oak Manufacturing Co., Ltd., under the conditions of a wavelength of 300 to 450 nm (lamp power: 3 kW, illuminance: 15 mW / cm ² ) and an exposure amount of 500 mJ / cm ² , FIG. The dicing tape was irradiated with radiation from the direction indicated by the middle arrow. Next, the peeling force when the dicing tape (1 cm width) was peeled off in the direction of 90 ° by the method shown in FIG. 4 was defined as the peeling force of the radiation-curable adhesive layer with respect to the film adhesive ( Measurement speed: 100 mm / min).

<Flying and pick-up during dicing>
Under the above conditions, a film-like adhesive was laminated on the back surface of the 5-inch, 400 μm-thick silicon wafer (lamination temperature: 80 ° C.), and then the above dicing tape was laminated under the same conditions as above, and then a dicer was used. Then, under the conditions of a dicing speed of 10 mm / sec and a rotation speed of 30,000 rpm, the presence or absence of chip fly when dicing to a size of 5 mm × 5 mm was observed. When the chip fly was 10% or less, no chip fly was taken. In addition, the jump of the chip cutting remaining portion at the wafer end was excluded from the evaluation.

  Next, for the sample without chip fly, after exposing the dicing tape side under the same conditions as above, good peeling property between the dicing tape and the film adhesive when picking up with tweezers for each chip, that is, The standard of the pick-up property is that 90% or more of the chips can be picked up.

<Foaming resistance>
A 5 mm × 5 mm × 0.55 mm thick glass chip is mounted on a 0.1 mm thick organic substrate having a 15 μm thick solder resist layer on the surface with a film adhesive of 5 mm × 5 mm × 40 μm thickness and the film Tg + 100 ° C. × After die bonding under the condition of 500 gf / chip × 3 sec, the film adhesive is heat-pressed under the condition of 180 ° C. × 5 kgf / chip × 90 sec, and heat-cured at 180 ° C. for 5 h. After the sample was heated on a hot plate at 260 ° C. for 30 seconds after being subjected to a moisture absorption treatment for 15 hours under the conditions described above, when the sample was visually observed with an optical microscope (× 20), foaming was 10% or less of the entire film. This was used as a standard for foam resistance.

<Shear strength>
A 3.2 mm × 3.2 mm × 0.4 mm thick silicon chip is mounted on the same organic substrate as above using a 3.2 mm × 3.2 mm × 40 μm thick film adhesive, and the tan δ peak temperature of the film + 100 ° C. × 500 gf / chip. After die bonding under the conditions of × 3 sec, the film adhesive is heat-pressed under the condition of 180 ° C. × 5 kgf / chip × 90 sec, and the film adhesive is heat-cured under the condition of 180 ° C. for 5 h, and then under the condition of 85 ° C. and 60% RH. After the moisture absorption treatment for 168 hours, the mixture was heated on a hot plate at 260 ° C. for 30 seconds, and then the shear adhesive strength was measured using a BT2400 made by Dage at a measuring speed of 500 μm / sec and a measuring gap of 50 μm.

<Reflow resistance>
A 6.5 mm × 6.5 mm × 280 μm thick silicon chip is mounted on a 0.1 mm thick organic substrate with copper wiring (wiring height: 12 μm) having a 15 μm thick solder resist layer on the surface. After performing die bonding with a film adhesive of × 6.5 mm × 40 μm thickness under the condition of tan δ peak temperature of the film + 100 ° C. × 500 gf / chip × 3 sec, heat history equivalent to wire bonding is applied at 170 ° C. for 3 min. Thereafter, transfer molding was performed (mold temperature: 180 ° C., cure time: 2 min), and the sealing material was heated and cured in an oven at 180 ° C. for 5 hours to obtain a semiconductor package (CSP 96 pin, sealing area: 10 mm). × 10 mm, thickness: 0.8 mm). After the package is subjected to a moisture absorption treatment of 30 ° C. and 60% RH for 192 h in a thermo-hygrostat, TAMURA IR reflow device (package surface peak temperature: 265 ° C., temperature profile: adjusted in accordance with JEDEC standard based on package surface temperature) Was repeatedly charged three times, and the presence or absence of peeling and destruction of the die bonding layer was examined using an ultrasonic inspection and imaging device HYE-FOUCUS manufactured by Hitachi, Ltd. Thereafter, the center of the package was cut, and the cut surface was polished. Then, the cross section of the package was observed using an Olympus metallographic microscope, and the presence or absence of peeling and destruction of the die bonding layer was examined. The absence of peeling and destruction was evaluated as an evaluation standard for reflow resistance.

<Moisture resistance reliability>
The moisture resistance was evaluated by treating the package in an atmosphere (pressure cooker test: PCT treatment) at a temperature of 121 ° C., a humidity of 100% and 2.03 × 10 ⁵ Pa for 72 hours, and then observing peeling by the above method. went. When no peeling was observed, it was evaluated as ○, and when peeled, it was evaluated as x.

  From Tables 4 and 5, the film adhesive of the present invention can be laminated on the back surface of the wafer at a temperature lower than the softening temperature of the protective tape of the ultra-thin wafer or the dicing tape to be bonded, and the thermal stress such as warpage of the wafer It has been found that the semiconductor device can be manufactured with no chip flying during dicing, good pick-up properties, a simplified semiconductor device manufacturing process, and excellent heat resistance and moisture resistance reliability.

It is a figure showing an example of the lamination method concerning the present invention. It is a figure showing an example of the lamination method concerning the present invention. It is a figure showing an example about measurement of a 90 degree peeling force to a silicon wafer. It is a figure which shows an example regarding the measurement of 90 degree peeling force with respect to a dicing tape. FIG. 3 is a diagram illustrating an example of a semiconductor device having a general structure. FIG. 3 is a diagram illustrating an example of a semiconductor device having a structure in which semiconductor elements are bonded to each other. FIG. 3 is a cross-sectional view of a single-layer film-like adhesive composed of only an adhesive layer 15. FIG. 3 is a cross-sectional view of a film adhesive in which an adhesive layer 15 is provided on both surfaces of a base film 16. FIG. 2 is a cross-sectional view of a film adhesive including a base film 17, an adhesive layer 18, and a cover film 19.

Claims (24)

(A) a film-like adhesive containing a thermoplastic resin and (B) an epoxy resin,
The (B) epoxy resin is a film comprising (B1) a trifunctional or higher functional epoxy resin in an amount of 10 to 90% by weight of the total epoxy resin, and (B2) a liquid epoxy resin in an amount of 10 to 90% by weight of the total epoxy resin. Glue.   The film adhesive according to claim 1, wherein the tan δ peak temperature is 20 to 65 ° C and the flow amount is 200 to 1500 µm.   3. The film adhesive according to claim 1, further comprising (C) an epoxy resin curing agent.   The film adhesive according to any one of claims 1 to 3, further comprising (D) a filler.   The film adhesive according to claim 4, wherein the filler (D) is an insulating filler.   The film adhesive according to claim 4, wherein the filler (D) has an average particle diameter of 10 μm or less and a maximum particle diameter of 25 μm or less.   The thermoplastic resin (A) is selected from the group consisting of polyimide resins, polyetherimide resins, polyesterimide resins, polyamide resins, polyester resins, polysulfone resins, polyethersulfone resins, polyphenylene sulfide resins, polyetherketone resins, and phenoxy resins. The film adhesive according to any one of claims 1 to 6, which is at least one or more resins selected. The thermoplastic resin (A) comprises tetracarboxylic dianhydride and the following formula (I)

(Wherein, Q ¹ , Q ² and Q ³ each independently represent an alkylene group having 1 to 10 carbon atoms, and m represents an integer of 2 to 80)
Wherein the aliphatic ether diamine represented by the formula is 1 to 50 mol% of the total diamine, and the following general formula (II)

(Where n represents an integer of 5 to 20)
The aliphatic diamine represented by the formula is 20 to 80 mol% of the total diamine, and the following general formula (III)

(Wherein, Q ⁴ and Q ⁹ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and Q ⁵ , Q ⁶ , Q ⁷ , and Q ⁸ each independently represent Represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and p represents an integer of 1 to 5)
The film-like adhesive according to any one of claims 1 to 7, wherein the siloxane diamine represented by is a polyimide resin obtained by reacting with a diamine containing 20 to 80 mol% of all diamines. The thermoplastic resin (A) is represented by the following general formula (IV)

A polyimide resin obtained by reacting a tetracarboxylic dianhydride having a content of tetracarboxylic dianhydride of 40 mol% or more of all tetracarboxylic dianhydrides and a diamine with a diamine. The film adhesive according to any one of items 1 to 8, wherein   The film adhesive according to any one of claims 1 to 9, wherein the liquid epoxy resin (B2) is a bifunctional epoxy resin having a number average molecular weight of 400 to 1500. The bifunctional epoxy resin has the following general formula (VIII)

(In the formula, Q ¹³ and Q ¹⁶ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group or a phenoxy group which may have a substituent, and Q ¹⁴ and Q ¹⁵ each independently represent 1 carbon atom. The film-like adhesive according to claim 10, which is a bisphenol-type epoxy resin represented by the following formula (1): alkyl group or hydrogen of 5 to 5, and t is an integer of 1 to 10. The (B1) epoxy resin having three or more functional groups is represented by the following general formula (VII):

(Wherein Q ¹⁰ , Q ¹¹ and Q ¹² each independently represent hydrogen or an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and r represents an integer of 1 to 20) The film adhesive according to any one of claims 1 to 11, which is a novolak type epoxy resin represented by the following formula:   The film-form according to any one of claims 3 to 12, wherein the (C) epoxy resin curing agent is a phenolic compound having two or more hydroxyl groups in a molecule and having a number average molecular weight of 400 to 1500. adhesive.   The film adhesive according to any one of claims 3 to 12, wherein the (C) epoxy resin curing agent is a naphthol compound or a trisphenol compound having three or more aromatic rings in a molecule.   The film adhesive according to any one of claims 1 to 14, wherein the varnish solvent for applying the film adhesive is a nitrogen-containing compound.   The film adhesive according to any one of claims 1 to 15, wherein a 90 ° peel force at 25 ° C on the silicon wafer at 25 ° C is 5 N / m or more at the stage of lamination at 80 ° C. An organic substrate with a film adhesive obtained by die bonding a chip via the film adhesive on an organic substrate having an organic resist material provided on the surface thereof has the following requirements:
(1) After the above-mentioned organic substrate with a film-like adhesive is heated and cured, the film is subjected to a moisture absorption treatment at 85 ° C. and 85% relative humidity for 15 hours, and then foaming occurs when heated on a hot plate at 260 ° C. for 30 seconds. unacceptable;
(2) After heat-curing the above-mentioned organic substrate with a film-like adhesive, it was subjected to a moisture absorption treatment at 85 ° C. and a relative humidity of 60% for 168 hours. 5N / chip or more;
The film adhesive according to any one of claims 1 to 16, which satisfies at least one of the following. A film adhesive used for a die bonding film containing at least a thermoplastic resin and a thermosetting resin,
The residual volatile content of the film adhesive is V (% by weight), the water absorption after heat curing is M (% by weight), the flow amount is F (μm), and the storage elastic modulus at 260 ° C. after heat curing is E ( MPa), the following conditions (1) to (4):
(1) V ≦ 10.65 × E,
(2) M ≦ 0.22 × E,
(3) V ≦ −0.0043F + 11.35,
(4) M ≦ −0.0002F + 0.6,
A film adhesive satisfying at least one of the following.   The film adhesive according to any one of claims 1 to 18, which is a die bonding adhesive material for bonding a semiconductor element and a semiconductor mounting support member.   20. The film adhesive according to claim 19, wherein the semiconductor mounting support member is an organic substrate having an organic resist layer.   An adhesive sheet comprising a base material layer, an adhesive layer, and the film adhesive layer according to any one of claims 1 to 20, which are formed in this order.   The adhesive sheet according to claim 21, wherein the adhesive layer is a radiation-curable adhesive layer. At the stage of lamination at 80 ° C. on a silicon wafer, the radiation-curable mold after UV irradiation under the conditions of A, a 90 ° peeling force at 25 ° C. of the film adhesive on the silicon wafer at 25 ° C., and an exposure amount of 500 mJ / cm ^2. The adhesive sheet according to claim 22, wherein the value of AB is 1 N / m or more, where B is a 90 ° peeling force at 25 ° C of the adhesive layer with respect to the film adhesive layer. Via the film adhesive according to any one of claims 1 to 20,
(1) a semiconductor element and a support member for mounting a semiconductor; and (2) semiconductor elements,
A semiconductor device having a structure in which at least one of the above is bonded.

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