JP5532575B2 - Adhesive sheet - Google Patents

Description

  The present invention relates to an adhesive sheet used for manufacturing a semiconductor device.

  In recent years, stacked MCP (Multi Chip Package) in which chips are stacked in multiple stages has become widespread and is mounted as a memory package for mobile phones and portable audio devices. High density and high integration of packages are being promoted. Along with this, there are demands for multi-stage chips and thinner packages, and wire-embedded packages are attracting attention as package forms that can satisfy these requirements.

  One of the most important characteristics as a mounting board on which various electronic components such as stacked MCP (Multi Chip Package) are mounted is reliability, but the chip can be formed without generating a gap on the adhesive surface. Whether it can be implemented is one factor that affects connection reliability. In particular, when a chip is stacked on a substrate having unevenness caused by wiring, the embedding property of these unevenness is important. There has been proposed an adhesive sheet that is compatible with such a process and can bury unevenness caused by wiring at the time of pressure bonding (see, for example, Patent Document 1).

  On the other hand, in recent years, in order to achieve miniaturization and thinning of semiconductor devices, thinning of substrates and wafers has been progressing. In thinning, warping of an element resulting from a difference in thermal expansion coefficient between the element and a substrate on which an electronic component is mounted has been a problem. In particular, the warp generated in the first-stage chip mounted on the substrate affects the crimping state of the chip mounted on the chip, and problems such as induction of trap voids during crimping may occur. An adhesive composition and an adhesive member having heat resistance, moisture resistance, and reflow crack resistance that can be used when the difference in thermal expansion coefficient between a semiconductor element and a substrate is large have been proposed (for example, see Patent Document 2). .

International Publication No. 05/103180 Pamphlet JP 2002-220576 A

  In order to achieve package thinning, the substrate and wafer are being thinned, and not only as a final product, but also warping of elements in the manufacturing process becomes a problem. In the adhesive member described in Patent Document 2, it is difficult to bury the unevenness caused by the wiring only by pressure mounting. On the other hand, in the adhesive sheet described in Patent Document 1, irregularities caused by wiring can be embedded only by crimp mounting. However, the adhesion area after mounting increases, and the warpage in the manufacturing process of the element tends to increase.

  The present invention has been made in view of the above-described problems of the prior art, can bury unevenness caused by wiring only by crimp mounting, has high heat resistance and high moisture resistance, and has a semiconductor element manufacturing process. An object of the present invention is to provide an adhesive sheet that can reduce the warpage of the element inside.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the melt viscosity before curing and the shear storage modulus after heating at 120 ° C. for 1 hour are due to the embedding property of the unevenness and the warp of the element in the manufacturing process. I found it related. That is, by specifying the components constituting the adhesive sheet, the melt viscosity at 80 ° C. before curing is 500-28000 Pa · s, and the shear storage modulus after heating at 120 ° C. for 1 hour is 1 Mpa or less. The sheet was found to be excellent in the embedding property of the unevenness and can reduce the warpage of the element in the manufacturing process, and completed the present invention.
That is, the present invention is as follows.

(1) The melt viscosity at 80 ° C. before curing is 500 to 28000 Pa · s, the shear storage elastic modulus at 120 ° C. after heating at 120 ° C. for 1 hour is 1 MPa or less, and an uneven organic substrate An adhesive sheet in which the unevenness is embedded under pressure bonding conditions of 120 ° C./0.1 MPa / 1 s.

（式（Ｉａ）中、Ｒ_１、Ｒ_２は直鎖、分岐もしくは環状のアルキル基、アラルキル基、アルケニル基、水酸基、アリール基又はハロゲン原子を示し、ｋ、ｍは０〜４の整数を示し、Ｒ_３、Ｒ_４は水素原子、直鎖、分岐もしくは環状のアルキル基、アラルキル基、アルケニル基、水酸基、アリール基又はハロゲン原子を示す。）

（式（Ｉｂ）中、Ｒ_１、Ｒ_２は直鎖、分岐もしくは環状のアルキル基、アラルキル基、アルケニル基、水酸基、アリール基又はハロゲン原子を示し、ｋ、ｍは０〜４の整数をす。）

（式（II）中、Ｒ_５は直鎖、分岐もしくは環状のアルキル基、アラルキル基、アルケニル基、水酸基、アリール基又はハロゲン原子を示し、ｎは０〜３の整数を示す。ただし、末端は０〜４の整数を示す。繰り返し単位の数を示すｐは０〜５０の範囲の整数を示す。）

（式（III）中、繰り返し単位の数を示すｑは０〜５０の範囲の整数を示す。） (2) The following (a) and the following (b) 15-30 parts by mass, (c) 30-100 parts by mass, and (d) 0.05-0.20 parts by mass with respect to 100 parts by mass (a). Part of the adhesive sheet for a semiconductor having a melt viscosity at 80 ° C. before curing of 500 to 28000 Pa · s and an adhesive strength to the organic substrate of 2 MPa or more, after heating at 120 ° C. for 1 hour An adhesive sheet having a shear storage modulus at 120 ° C. of 1 MPa or less.
(A) a thermosetting resin comprising an epoxy resin represented by the following formula (Ia) or (Ib) and a compound represented by the following formula (II) or (III):
(B) an acrylic resin having a weight average molecular weight containing a crosslinkable functional group of 100,000 to 800,000 and Tg of −50 to 50 ° C .;
(C) an inorganic filler having an average particle size of 1.0 μm or less,
(D) Curing accelerator

(In formula (Ia), R ₁ and R ₂ represent a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group, or a halogen atom, and k and m represent an integer of 0 to 4. R ₃ and R ₄ represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group, or a halogen atom.

(In formula (Ib), R ₁ and R ₂ represent a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group, or a halogen atom, and k and m represent an integer of 0 to 4. .)

(In the formula (II), R ₅ represents a linear, branched or cyclic alkyl group, aralkyl group, alkenyl group, hydroxyl group, aryl group or halogen atom, and n represents an integer of 0 to 3. And represents an integer of 0 to 4. p indicating the number of repeating units represents an integer in the range of 0 to 50.)

(In formula (III), q representing the number of repeating units represents an integer in the range of 0 to 50.)

(3) The adhesive sheet according to (1) or (2), wherein the softening point of the compound represented by the formula (II) or (III) is 70 ° C. or lower.

(4) The adhesive sheet according to any one of (1) to (3), wherein the adhesive strength at 265 ° C. with the glass-epoxy substrate is 2 MPa or more.
(5) The inorganic filler has an average particle diameter of 0.5 μm or more and is 99% by mass distributed in 0.1 to 4.0 μm, according to any one of the above (1) to (4). Adhesive sheet.

(6) The equivalent ratio of the epoxy equivalent of the epoxy resin in the (a) thermosetting resin and the hydroxyl equivalent of the compound represented by formula (II) or (III) is 0.70 / 0.30-0. The adhesive sheet according to any one of (1) to (5), which is 30 / 0.70.

  ADVANTAGE OF THE INVENTION According to this invention, the unevenness | corrugation on an organic substrate can be completely embedded only by crimp mounting, and the adhesive sheet which can reduce the curvature of the semiconductor element in a manufacturing process can be provided.

  The adhesive sheet of the present invention has a melt viscosity of 500 to 28000 Pa · s at 80 ° C. before curing, a shear storage elastic modulus at 120 ° C. of 1 MPa or less after heating at 120 ° C. for 1 hour, The unevenness of an organic substrate is embedded under a pressure bonding condition of 120 ° C./0.1 MPa / 1 s.

Moreover, the following structures may be sufficient as the adhesive sheet of this invention.
(B) 15-30 parts by mass, (c) 30-100 parts by mass, and (d) 0.05-0.20 parts by mass with respect to 100 parts by mass of (a) below An adhesive sheet for a semiconductor having a melt viscosity of 500 to 28000 Pa · s at 80 ° C. before curing and an adhesive strength to an organic substrate of 2 MPa or more at 120 ° C. after heating at 120 ° C. for 1 hour. The adhesive sheet has a shear storage elastic modulus of 1 MPa or less.
(A) a thermosetting resin comprising an epoxy resin represented by the following formula (Ia) or (Ib) and a compound represented by the following formula (II) or (III):
(B) an acrylic resin having a weight average molecular weight containing a crosslinkable functional group of 100,000 to 800,000 and Tg of −50 to 50 ° C .;
(C) an inorganic filler having an average particle size of 1.0 μm or less,
(D) A curing accelerator.

（式（Ｉａ）中、Ｒ_１、Ｒ_２は直鎖、分岐もしくは環状のアルキル基、アラルキル基、アルケニル基、水酸基、アリール基又はハロゲン原子を示し、ｋ、ｍは０〜４の整数を示し、Ｒ_３、Ｒ_４は水素原子、直鎖、分岐もしくは環状のアルキル基、アラルキル基、アルケニル基、水酸基、アリール基又はハロゲン原子を示す。）

(In formula (Ia), R ₁ and R ₂ represent a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group, or a halogen atom, and k and m represent an integer of 0 to 4. R ₃ and R ₄ represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group, or a halogen atom.

（式（Ｉｂ）中、Ｒ_１、Ｒ_２は直鎖、分岐もしくは環状のアルキル基、アラルキル基、アルケニル基、水酸基、アリール基又はハロゲン原子を示し、ｋ、ｍは０〜４の整数をす。）

(In formula (Ib), R ₁ and R ₂ represent a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group, or a halogen atom, and k and m represent an integer of 0 to 4. .)

（式（II）中、Ｒ_５は直鎖、分岐もしくは環状のアルキル基、アラルキル基、アルケニル基、水酸基、アリール基又はハロゲン原子を示し、ｎは０〜３の整数を示す。ただし、末端は０〜４の整数を示す。繰り返し単位の数を示すｐは０〜５０の範囲の整数を示す。）

(In the formula (II), R ₅ represents a linear, branched or cyclic alkyl group, aralkyl group, alkenyl group, hydroxyl group, aryl group or halogen atom, and n represents an integer of 0 to 3. And represents an integer of 0 to 4. p indicating the number of repeating units represents an integer in the range of 0 to 50.)

（式（III）中、繰り返し単位の数を示すｑは０〜５０の範囲の整数を示す。）

(In formula (III), q representing the number of repeating units represents an integer in the range of 0 to 50.)

<Adhesive sheet material>
Hereinafter, materials used in the present invention will be described.

(A) Thermosetting resin (a) The thermosetting component used in the thermosetting resin used in the adhesive sheet of the present invention is an epoxy having heat resistance and moisture resistance required for mounting a semiconductor element. A mixture of a resin and a compound represented by the above formula (II) or formula (III) is preferred.
The epoxy resin constituting the thermosetting resin (a) in the present invention is preferably an epoxy resin represented by the following (Ia) or (Ib), but is cured to become an epoxy curable resin exhibiting an adhesive action. If it is a thing, there will be no restriction | limiting in particular.

（式（Ｉａ）中、Ｒ_１、Ｒ_２は直鎖、分岐もしくは環状のアルキル基、アラルキル基、アルケニル基、水酸基、アリール基又はハロゲン原子を示し、ｋ、ｍは０〜４の整数を示し、Ｒ_３、Ｒ_４は水素原子、直鎖、分岐もしくは環状のアルキル基、アラルキル基、アルケニル基、水酸基、アリール基又はハロゲン原子を示す。）

(In formula (Ia), R ₁ and R ₂ represent a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group, or a halogen atom, and k and m represent an integer of 0 to 4. R ₃ and R ₄ represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group, or a halogen atom.

（式（Ｉｂ）中、Ｒ_１、Ｒ_２は直鎖、分岐もしくは環状のアルキル基、アラルキル基、アルケニル基、水酸基、アリール基又はハロゲン原子を示し、ｋ、ｍは０〜４の整数をす。）

(In formula (Ib), R ₁ and R ₂ represent a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group, or a halogen atom, and k and m represent an integer of 0 to 4. .)

Specific examples include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and bisxylenol type epoxy resins.
Examples of the epoxy resin preferably used in the present invention include YSLV-80XY (bisxylenol type epoxy resin) and YDF-8170C (bisphenol F type epoxy resin) manufactured by Tohto Kasei Co., Ltd.

  The epoxy resin in the present invention is preferably an epoxy resin represented by the above formula (Ia) or (Ib), but is not particularly limited as long as it is cured and has an adhesive action. From the viewpoint of reducing warping of the element in the semiconductor element manufacturing process, an epoxy resin that is not polyfunctional is preferable, and a bifunctional epoxy resin is more preferable from the viewpoint of embedding at the time of pressure bonding. Specifically, bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin, novolak type epoxy resins such as phenol novolac type epoxy resin and cresol novolac type epoxy resin, etc. are used. You can also. Moreover, what is generally known, such as a polyfunctional epoxy resin, a glycidylamine type epoxy resin, a heterocyclic ring-containing epoxy resin, or an alicyclic epoxy resin, can be applied.

From the viewpoint of high flexibility of the adhesive sheet in the B-stage state, the weight average molecular weight of the epoxy resin is preferably 1000 or less, and more preferably 500 or less. Examples of the epoxy resin having a weight average molecular weight of 500 or less that is excellent in flexibility include bifunctional epoxy resins.
Here, the “B stage state” refers to a state immediately after forming a sheet and before curing. Although details will be described later, the B-stage film is also targeted for the measurement of the melt viscosity.

  As the compound constituting the thermosetting resin (a) in the present invention, compounds represented by the following (II) or (III) (in the present invention, hereinafter collectively referred to as “phenol resins”) are preferably exemplified. It is done. This is a curable resin that cures and exhibits an adhesive action.

（式（II）中、Ｒ_５は直鎖、分岐もしくは環状のアルキル基、アラルキル基、アルケニル基、水酸基、アリール基又はハロゲン原子を示し、ｎは０〜３の整数を示す。ただし、末端は０〜４の整数を示す。繰り返し単位の数を示すｐは０〜５０の範囲の整数を示す。）

(In the formula (II), R ₅ represents a linear, branched or cyclic alkyl group, aralkyl group, alkenyl group, hydroxyl group, aryl group or halogen atom, and n represents an integer of 0 to 3. And represents an integer of 0 to 4. p indicating the number of repeating units represents an integer in the range of 0 to 50.)

  In the above formula (II), a phenol resin in which n is 0 and p is 2 to 5 is preferably used.

（式（III）中、繰り返し単位の数を示すｑは０〜５０の範囲の整数を示す。）

(In formula (III), q representing the number of repeating units represents an integer in the range of 0 to 50.)

  In the above formula (III), a phenol resin having q of 2 to 5 is preferably used.

  The phenol resins represented by the above general formulas (II) and (III) used in the present invention have a softening point of 70 ° C. or less and a hydroxyl group equivalent of 160 or more in consideration of the shear storage modulus after thermal history. Preferably there is. Also, from the viewpoint of heat resistance and moisture resistance, the water absorption after introduction into a constant temperature and humidity chamber of 85 ° C. and 85% RH for 48 hours is 2% by mass or less and measured at 350 ° C. measured with a thermogravimetric analyzer (TGA). A heating mass reduction rate (temperature increase rate: 5 ° C./min, atmosphere: nitrogen) of less than 5% by mass can be more preferably used.

  When the softening point of the phenol resin in the present invention exceeds 70 ° C., the embedding property of the unevenness tends to deteriorate.

  More preferably, the phenolic resin in the present invention has a hydroxyl group equivalent of 165 to 400. When the hydroxyl group equivalent is 165 or less, warping tends to increase, and when it exceeds 400, curing in the semiconductor element manufacturing process is slow, which may cause problems such as foaming.

  As a phenol resin having a softening point of 70 ° C. or less and a hydroxyl group equivalent of 165 to 400, typical examples of the phenol resin represented by the above general formula (II) include Millex XLC-series and XL series manufactured by Mitsui Chemicals, Inc. There is. Typical examples of the phenol resin represented by the general formula (III) include SN100 series and SN400 manufactured by Toto Kasei Co., Ltd.

(A) The amount of the epoxy resin and the phenol resin in the thermosetting resin is preferably 0.70 / 0.30 to 0.30 / 0.70 in terms of the equivalent ratio of epoxy equivalent and hydroxyl equivalent, 0.65 / 0.35 to 0.35 / 0.65 is more preferable, 0.60 / 0.40 to 0.40 / 0.60 is further preferable, and 0.60 / 0. It is particularly preferably 40 to 0.50 / 0.50. If the blending ratio exceeds the above range, the produced adhesive sheet may be inferior in curability, or the viscosity of the B-stage sheet may be high and fluidity may be inferior.
Moreover, (a) In 100 mass parts of thermosetting resins, it is preferable that an epoxy resin is 25 mass parts or more, and a phenol resin is 35-55 mass parts. By setting it as this compounding quantity, the embedding property of the unevenness | corrugation at the time of pressure bonding and reduction of curvature can be made compatible.

(B) High molecular weight component The (b) acrylic resin in the present invention is not particularly limited as long as the weight average molecular weight containing a crosslinkable functional group is 100,000 to 800,000 and Tg is -50 to 50 ° C.
Examples of the crosslinkable functional group in the present invention include a carboxylic acid group, an amino group, a hydroxyl group or an epoxy group, and an isocyanate group.

  The acrylic resin in the present invention has a Tg (glass transition temperature) of −50 ° C. to 50 ° C. and a weight average molecular weight having a crosslinkable functional group of 100,000 to 800,000, for example, a crosslink such as glycidyl acrylate or glycidyl methacrylate. An epoxy group-containing (meth) acrylic resin obtained by polymerizing a functional functional monomer is preferred. As the epoxy group-containing (meth) acrylic resin, for example, an epoxy group-containing (meth) acrylic acid ester copolymer, an epoxy group-containing acrylic rubber or the like can be used, and an epoxy group-containing acrylic rubber is more preferable.

The acrylic rubber is a rubber mainly composed of an acrylate ester and mainly composed of a copolymer such as butyl acrylate and acrylonitrile, a copolymer such as ethyl acrylate and acrylonitrile, or the like.
The polymerization method for obtaining the acrylic resin in the present invention is not particularly limited, and pearl polymerization, solution polymerization and the like can be used.
In addition, a weight average molecular weight is a polystyrene conversion value using the calibration curve by a standard polystyrene by the gel permeation chromatography method (GPC).

  If the Tg of the acrylic resin exceeds 50 ° C., the flexibility of the sheet may be lowered. If the Tg is less than −50 ° C., the flexibility of the sheet is too high and the sheet is difficult to cut during wafer dicing. The dicing property may be deteriorated due to the generation of burrs.

  In addition, if the weight average molecular weight of the acrylic resin is less than 100,000, the film-forming property may be deteriorated and the adhesive strength and heat resistance of the sheet may be deteriorated. The fluidity of the sheet may decrease. More preferably, it is 200,000 to 800,000.

  Weight average molecular weight with Tg of -20 ° C to 40 ° C in terms of easy cutting of the adhesive sheet during wafer dicing, less resin waste, high adhesive strength and heat resistance, and high fluidity of the uncured sheet. Is preferably a high molecular weight component having a Tg of -10 ° C to 40 ° C and a molecular weight of 200,000 to 800,000.

  Examples of acrylic resins having a Tg of −50 ° C. to 50 ° C. and a weight-average molecular weight having a crosslinkable functional group of 100,000 to 800,000 include HTR-860P and 860-230k manufactured by Teikoku Chemical Industry Co., Ltd. be able to.

  The compounding quantity in the adhesive sheet composition of (b) acrylic resin in this invention shall be 15-30 mass parts with respect to 100 mass parts of said (a) thermosetting resin. If this blending amount is less than 15 parts by mass, curing in the semiconductor element manufacturing process tends to be slow, and there is a tendency to cause problems such as foaming. If it exceeds 30 parts by mass, the unevenness embedding at the time of crimping tends to deteriorate. is there.

(C) Inorganic filler In the adhesive sheet of the present invention, improvement of the dicing property of the adhesive sheet in the B-stage state, improvement of handling property of the adhesive sheet, improvement of thermal conductivity, adjustment of melt viscosity, imparting thixotropic properties, It is preferable to blend an inorganic filler for the purpose of improving the adhesive strength.
The inorganic filler (c) in the present invention is not particularly limited. For example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, Aluminum nitride, aluminum borate whisker, boron nitride, crystalline silica, amorphous silica and the like can be used, and these can be used alone or in combination of two or more. In order to improve thermal conductivity, it is preferable that aluminum oxide, aluminum nitride, boron nitride, crystalline silica, amorphous silica or the like is contained. For the purpose of adjusting melt viscosity and imparting thixotropic properties, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, crystalline silica, It is preferable that amorphous silica or the like is contained.

  In this invention, it is the high fluidity | liquidity of the sheet | seat of a B stage state that 30-100 mass parts is contained with respect to 100 mass parts of said (a) thermosetting resin in (c) inorganic filler in an adhesive sheet composition. And preferred for the development of meltability during the curing process.

  When an excessive amount of inorganic filler is contained, the fluidity of the B-stage sheet may be lowered. Inorganic fillers having different average particle diameters can be mixed and used, but as a main component occupying a ratio of 90% or more, the average particle diameter is 0.5 μm or more to 0.1 to 4.0 μm. An inorganic filler in which 99% is distributed is preferable, and an inorganic filler in which 99% is distributed in an average particle diameter of 0.5 μm or more and 0.1 to 1.0 μm is more preferable. By using such an inorganic filler, it is possible to control the fluidity before curing and to exhibit good embedding properties.

  When an inorganic filler having an average particle size of 0.1 μm or less is used as a main inorganic filler component, the fluidity of the uncured sheet may be lowered due to an increase in specific surface area and an increase in the number of contained particles, and the average particle size is When an inorganic filler of 1.0 μm or more is used as a main inorganic filler component, it may cause a decrease in adhesive force due to a decrease in contained particles and a deterioration in film film formability.

  As an inorganic filler having a different average particle diameter to be added to the main inorganic filler, there is no particular limitation as long as it does not exceed the film thickness of the adhesive sheet to be produced, but a low elastic modulus for reducing the warpage of the element, From the viewpoint of improving adhesive strength, an inorganic filler having an average particle size of 0.1 μm or less is preferable.

(D) Curing accelerator A curing accelerator is contained in the adhesive sheet of the present invention. Highly reactive curing accelerators can cause excessive curing of the adhesive sheet during the semiconductor device manufacturing process, resulting in excessive warping. On the other hand, when a low-reactivity accelerator is used, the adhesive sheet is not completely cured in the heat history in the semiconductor element manufacturing process, and is mounted in the product as it is uncured. There is a risk of inducing semiconductor device failures.
From the above, imidazole compounds are preferred as the curing accelerator. Specific examples include 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, etc., and these may be used alone or in combination of two or more. You can also

  In the present invention, the adhesive sheet composition contains (d) a curing accelerator in an amount of 0.05 to 0.20 parts by mass with respect to 100 parts by mass of the (a) thermosetting resin. It is preferable for the development of high fluidity of the sheet and meltability during the curing process.

(E) Other components of adhesive sheet The adhesive sheet of the present invention may contain additives, coupling agents, and the like in addition to the above components.
Examples of the additive include an ion scavenger for improving insulation reliability during moisture absorption. As the ion scavenger, there is no particular limitation, and a compound known as a copper damage preventive agent to prevent copper from ionizing and dissolving, for example, a triazine thiol compound, a bisphenol-based reducing agent, etc. can be used. Inorganic ion adsorbents such as zirconium-based and antimony bismuth-based magnesium aluminum compounds can also be used.
Examples of the coupling agent for improving the interfacial bond between different materials include silane-based, titanium-based, and aluminum-based, and the silane-based coupling agent is most preferable. As these, generally known ones can be used.

<Method for producing adhesive sheet>
The adhesive sheet of the present invention is obtained by mixing and kneading the above (a) thermosetting resin, (b) acrylic resin, (c) inorganic filler, (d) curing accelerator and other components in an organic solvent. Can be obtained by forming the adhesive layer with the varnish on the base film, heating and drying, and then removing the base. The above mixing and kneading can be carried out by appropriately combining dispersers such as ordinary stirrers, crackers, three rolls, and ball mills. The heating and drying conditions are not particularly limited as long as the solvent used is sufficiently volatilized, but it is usually performed by heating at 60 to 200 ° C. for 0.1 to 90 minutes.

  There is no restriction | limiting in particular as said base film, For example, there exist a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyether naphthalate film, a methylpentene film etc.

  The organic solvent used for adjusting the varnish in the production of the adhesive sheet of the present invention is not limited as long as the material can be uniformly dissolved, kneaded or dispersed, and a conventionally known one can be used. Examples of such an organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, dimethylformamide, dimethylacetamide, N methylpyrrolidone, toluene, xylene, and the like. It is preferable to use methyl ethyl ketone, cyclohexanone, etc. in terms of fast drying speed and low price.

  The film thickness of the adhesive sheet of the present invention is preferably 5 to 250 μm in order to be able to fill the irregularities such as the wiring circuit of the substrate. If the thickness is less than 5 μm, the stress relaxation effect and adhesiveness tend to be poor. If the thickness is more than 250 μm, it is not economical and the demand for miniaturization of the semiconductor device cannot be met. In addition, 20-100 micrometers is more preferable at the point which has high adhesiveness and can make a semiconductor device thin, More preferably, it is 20-60 micrometers.

<Physical properties of adhesive sheet>
The adhesive sheet (adhesive layer) of the present invention has a melt viscosity of 500 to 28000 Pa · S at 80 ° C. before curing (B stage state). When the melt viscosity is less than 500 Pa · S, foaming of the adhesive sheet in the semiconductor element manufacturing process tends to be remarkable, whereas when it is greater than 28000 Pa · S, the unevenness during compression bonding tends to deteriorate. A more preferable melt viscosity is 1000 to 10,000 Pa · S.

  Further, the melt viscosity at 80 ° C. before curing of the adhesive sheet (adhesive layer) can be measured by a parallel plate plastometer method. Specifically, a measurement sample (B-stage sheet) is produced as follows. First, an adhesive sheet varnish is applied to a support film or the like, and three B-stage sheets having a film thickness of 40 μm are produced. From these, the support film is peeled and removed, and then three adhesive layers are bonded together at 60 ° C. to obtain a sheet having a thickness of 120 μm. Next, the sheet is punched in the thickness direction to obtain a disk-shaped measurement sample for melt viscosity having a diameter of 6 mm and a thickness of 120 μm. A disk-shaped measurement sample for melt viscosity is sandwiched between 150 μm thick glass slides in the thickness direction, and using a pressure bonding (compression) machine set to 80 ° C. during pressure compression), 3 kgf for 3 seconds. Crimp (compress) in the thickness direction. The melt viscosity is calculated from the change in the contact area between the measurement sample for melt viscosity and the slide glass at that time.

The “B stage state” is a state immediately after the sheet is formed, but the melt viscosity of the adhesive sheet of the present invention is from immediately after sheet formation (B stage state) to immediately before curing, before curing. It is considered that there is almost no change in characteristics through any process.
In order to set the melt viscosity at 80 ° C. to 500 to 28000 Pa · S, it can be controlled by appropriately using the material of the adhesive sheet described above and appropriately adjusting the drying conditions when forming a B-stage sheet (measurement sample). It is.

  The adhesive sheet (adhesive layer) of the present invention has a shear storage elastic modulus of 1 MPa or less at 120 ° C. after being heated at 120 ° C. for 1 hour. If the shear storage modulus is greater than 1 MPa, the warp of the semiconductor element tends to increase. More preferably, it is 0.8 MPa or less. The adjustment of the shear storage modulus can be realized by selecting the phenol resin as the thermosetting resin (a) which is an adhesive sheet component. Specifically, the crosslink density may be low.

The shear storage modulus may be measured by preparing a measurement sample as follows.
The adhesive sheet varnish is applied to a support film or the like, and four B-stage sheets having a film thickness of 40 μm are prepared. Next, the support film is peeled off from three of the four B-stage sheets, and four sheets are bonded at 60 ° C. to obtain a sheet having a thickness of 160 μm. The sheet is punched out into a circular shape with a diameter of 25 mm in the thickness direction to produce a measurement sample for shear storage modulus. A circular aluminum plate jig having a diameter of 25 mm is set on ARES (manufactured by Rheometric Scientific), and the support film is peeled off from the punched measurement sample for shear storage modulus and set here. Thereafter, the shear storage modulus is measured every 8 seconds while applying 10% strain at 120 ° C., and the measured value after 1 hour is recorded.
In order to set the shear storage modulus at 120 ° C. after heating at 120 ° C. for 1 hour to 1 MPa or less, the above-mentioned adhesive sheet material is used as appropriate, and the drying conditions for forming a B-stage sheet (measurement sample) Can be controlled by appropriately preparing.

  In the adhesive sheet of the present invention, the unevenness of an uneven organic substrate can be embedded under pressure bonding conditions of 120 ° C./0.1 MPa / 1 s. Usually, when the crimping performance is good, the warpage of the element in the semiconductor manufacturing process is likely to occur. However, the adhesive sheet of the present invention satisfies the melt viscosity at 80 ° C. and the shear storage elastic modulus at 120 ° C. It is excellent and the warpage of the element in the semiconductor manufacturing configuration can be reduced.

  In the present invention, the melt viscosity and the shear storage modulus are values when each measurement sample prepared as described above is measured under the above measurement conditions. When the sheet prepared and measured by these methods falls within the range of a melt viscosity of 500 to 28000 Pa · S and a shear storage modulus of 1 MPa or less, all are within the scope of the present invention.

  The adhesive (adhesive layer) sheet of the present invention has an adhesive force to the organic substrate of 2 MPa or more. When the adhesive strength is less than 2 MPa, heat resistance and moisture resistance tend to deteriorate. The adhesive strength can be adjusted, for example, by increasing the amount of the inorganic filler.

The adhesive strength (hereinafter also referred to as “die shear strength”) may be measured as follows. First, the adhesive sheet varnish is applied to a support film or the like to produce a B-stage sheet having a thickness of 40 μm. Next, the adhesive sheet is peeled from the support film, and the adhesive layer is attached to a semiconductor wafer having a thickness of 400 μm at 60 ° C. Next, they are diced into 3.2 mm squares to obtain chips. On the surface of a glass-epoxy substrate (manufactured by Hitachi Chemical Co., Ltd., trade name: E-697FG) coated with a resist (manufactured by Taiyo Ink, trade name: AUS308) on the adhesive layer side of the singulated chip, 100 ° C. A measurement sample for adhesive strength is obtained by thermocompression bonding under conditions of 100 gf / cm ² for 1 second. Thereafter, the adhesive layer of the obtained adhesive force sample is cured by step cure in the order of 100 ° C. for 1 hour, 110 ° C. for 1 hour, 120 ° C. for 1 hour, and 170 ° C. for 1 hour. Further, the measurement sample after curing of the adhesive layer is allowed to stand for 168 hours under the conditions of 85 ° C. and 60 RH%. Immediately after standing, the die shear strength is measured at 265 ° C. and a shear rate of 50 μm / s, and this is taken as the adhesive strength.

  The adhesive sheet (adhesive layer) of the present invention has a storage elastic modulus of 200 to 6000 MPa as measured by dynamic viscoelasticity at 25 ° C. before curing of the adhesive sheet (adhesive layer) (B stage state). It is preferable at an excellent point. 200 to 2000 MPa is more preferable in terms of excellent dicing properties and excellent adhesion to the wafer. Further, if the storage elastic modulus measured by dynamic viscoelasticity measurement at 80 ° C. before curing of the adhesive sheet (adhesive layer) is 10 MPa or less, it can be laminated on the wafer at 80 ° C. In particular, it is more preferably 5 MPa or less from the viewpoint of high adhesion to the wafer.

In the present invention, the storage elastic modulus by dynamic viscoelasticity measurement at 170 ° C. after curing of the adhesive sheet (adhesive layer) (C stage state) is 5 to 1000 MPa in order to obtain good wire bonding properties. preferable.
In addition, the storage elastic modulus is measured by using a dynamic viscoelasticity measuring device (for example, DVE-V4 manufactured by Rheology Co., Ltd.), applying a tensile load to the adhesive sheet (adhesive layer), and increasing the frequency to 10 Hz. It implements in the temperature dependence measurement mode which measures from -50 degreeC to 300 degreeC with a speed | rate 5-10 degreeC / min. The storage elastic modulus in the B-stage state is measured by preparing a measurement sample in the same manner as for the melt viscosity measurement. The adhesive sheet in the C-stage state is produced by heating at 120 ° C. for 1 hour and at 170 ° C. for 3 hours.

<Aspect of adhesive sheet>
The adhesive sheet of the present invention may be used by itself, but as an embodiment, it can also be used as a dicing / die bonding integrated adhesive sheet in which the adhesive sheet of the present invention is laminated on a conventionally known dicing tape. . In this case, the efficiency of the operation can be improved in that the laminating process on the wafer is performed only once.

  Examples of the dicing tape used together with the adhesive sheet of the present invention include plastic films such as polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, and polyimide film. Further, surface treatment such as primer coating, UV treatment, corona discharge treatment, polishing treatment and etching treatment may be performed as necessary. The dicing tape preferably has adhesiveness, and the above-mentioned plastic film provided with adhesiveness may be used, or an adhesive layer may be provided on one side of the above-mentioned plastic film. This is because the resin composition for the pressure-sensitive adhesive layer having an appropriate tack strength obtained by adjusting the ratio of the liquid component and the Tg of the high molecular weight component in the resin composition for the pressure-sensitive adhesive layer as is generally done. It can be formed by applying an object to the above-mentioned plastic film and drying.

When the adhesive sheet of the present invention is used as a dicing / die bonding integrated adhesive sheet for manufacturing a semiconductor device, it has an adhesive force that prevents the semiconductor element from scattering during dicing, and then needs to be peeled off from the dicing tape during pickup. It is. For example, if the adhesive sheet is too sticky, picking up may be difficult. Therefore, it is preferable to appropriately adjust the tack strength of the adhesive sheet. As the method, by increasing the melt viscosity at room temperature of the adhesive sheet, the adhesive strength and tack strength are also increased, and if the melt viscosity is decreased, the adhesive strength and tack strength tend to decrease. Good.
For example, in the case of increasing the melt viscosity, for example, there are methods of containing a plasticizer and a tackifier. Conversely, when the melt viscosity is lowered, the content of the compound may be reduced. Examples of the plasticizer include monofunctional acrylic monomers, monofunctional epoxy resins, liquid epoxy resins, acrylic resins, and epoxy-based so-called diluents.

  As a method of laminating the adhesive sheet of the present invention on the above-mentioned dicing tape, in addition to printing, there is a method of pressing an adhesive sheet prepared in advance on a dicing tape, hot roll laminating, but it can be continuously produced, A hot roll laminating method is preferable in terms of efficiency.

  The film thickness of the dicing tape is not particularly limited, and is appropriately determined based on the knowledge of those skilled in the art depending on the thickness of the adhesive sheet and the application of the dicing tape-integrated adhesive sheet. The film is usually 60 to 150 μm, preferably 70 to 130 μm in terms of good handleability of the film.

  The adhesive sheet of the present invention is preferably used for production of a semiconductor device, more preferably a wafer, an adhesive sheet (adhesive layer) and a dicing tape bonded at 0 ° C. to 80 ° C., and then a wafer with a rotary blade or laser, After cutting the adhesive sheet (adhesive layer) and the dicing tape, peeling the cut chip from the dicing tape to obtain a chip with an adhesive layer, the chip with the adhesive layer is loaded on a substrate having irregularities, preferably an organic base material It is used for manufacturing a semiconductor device including a step of bonding at 0.001 to 1 MPa and filling irregularities. The load is preferably 0.01 to 0.5 MPa, and more preferably 0.02 to 0.3 MPa. When the load is less than 0.001 MPa, there are many unfilled sites, and as a result, the heat resistance tends to decrease.

  On the other hand, when the crimping load exceeds 1 MPa, the chip tends to be damaged. Further, when the chip with the adhesive layer is bonded to a substrate having irregularities, preferably an organic base material, it is desirable to heat the adherend or the chip with the adhesive layer, or both, and the heating temperature is 60 to 180. Although it is preferable that it is ° C, it is more preferable that it is 80-160 ° C. When the temperature is less than 60 ° C., the embedding property of the unevenness tends to decrease, and when the temperature exceeds 180 ° C., the substrate tends to be deformed and warpage tends to increase. Examples of the heating method include a method of bringing the substrate into contact with a heated hot plate, irradiating infrared rays or microwaves, and blowing hot air.

  In the present invention, as the wafer, in addition to single crystal silicon, polycrystalline silicon, various ceramics, compound semiconductors such as gallium arsenide, and the like are used.

  When the adhesive sheet is used alone, after adhering the adhesive sheet (adhesive layer) to the wafer, the dicing tape may then be attached to the adhesive sheet (adhesive layer) surface. Moreover, a semiconductor device can also be manufactured by using the adhesive sheet (adhesive layer) of this invention and the dicing die bonding integrated adhesive sheet provided with a dicing tape.

  The temperature at which the adhesive sheet is attached to the wafer, that is, the laminating temperature, is 0 to 90 ° C, preferably 15 to 80 ° C, and more preferably 40 to 80 ° C. When the temperature exceeds 90 ° C., a change in thickness due to excessive melting of the adhesive sheet may become remarkable.

  When the dicing tape or the dicing / die bonding integrated adhesive sheet is attached, it is preferably performed at the above temperature.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these at all.
(Examples 1-2 and Comparative Examples 1-3)
Adhesive sheet varnishes for forming the adhesive compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were prepared with the compositions shown in Tables 1 and 2 (blending units; parts by weight).
Specifically, cyclohexanone was added to the composition composed of various epoxy resins, phenol resins and inorganic fillers shown in Tables 1 and 2 and mixed with stirring to obtain a uniform composition. An acrylic resin (acrylic rubber) was added thereto and stirred, and then a coupling agent and a curing accelerator were added and stirred until uniform to obtain a varnish for an adhesive sheet. Thereafter, the mixture was filtered through a 500 mesh filter and vacuum degassed. The adhesive sheet varnish thus produced was applied on a polyethylene terephthalate film (PET) having a thickness of 38 μm and subjected to a release treatment. This was subjected to two-stage heat drying at 90 ° C. (5 minutes) followed by 140 ° C. (5 minutes) to form a B-stage coating film having a film thickness of 40 μm, thereby producing adhesive films each having a carrier film.

The materials in Table 1 and Table 2 are as follows.
YSLV-80XY (Bisxylenol type epoxy resin, manufactured by Toto Kasei Co., Ltd., epoxy equivalent 192, melting point 67 ° C.)
YDF-8170C (bisphenol F type epoxy resin, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 159, liquid at room temperature)
YDCN-700-10 (cresol novolac type epoxy resin, manufactured by Toto Kasei Co., Ltd., epoxy equivalent 210, softening point 75-85 ° C.)
Phenolite LF-4871 (phenol resin, manufactured by Dainippon Ink & Chemicals, hydroxyl equivalent: 118, softening point: 130 ° C.)
Millex XLC-LL (phenol resin, manufactured by Mitsui Chemicals, hydroxyl equivalent 175, softening point 77 ° C.)
Millex XLC-4L (phenol resin, manufactured by Mitsui Chemicals, hydroxyl equivalent 169, softening point 61-63 ° C.)
SN-170L (phenol resin, manufactured by Tohto Kasei Co., Ltd., hydroxyl equivalent 182; softening point 70 ° C.)
SC2050-HLG (silica filler dispersion, manufactured by Admatechs Co., Ltd., average particle size 0.500 μm, particle size distribution has a maximum particle size of 1.0 μm or less)
Aerosil R972 (silica, manufactured by Nippon Aerosil Co., Ltd., average particle size 0.016 μm, maximum particle size distribution is 1.0 μm or less)
HTR-860P (acrylic rubber, Teikoku Chemical Industry Co., Ltd., weight average molecular weight 800,000, Tg-7 ° C)
HTR-860P-230k (acrylic rubber, manufactured by Teikoku Chemical Industry Co., Ltd., weight average molecular weight 230,000, Tg-7 ° C.)
NUC A-1160 (γ-ureidopropyltriethoxysilane, manufactured by GE Toshiba Corporation)
NUC A-189 (γ-mercaptopropyltrimethoxysilane, manufactured by GE Toshiba Corporation)
Curezole 2PZ-CN (1-cyanoethyl-2-phenylimidazole, manufactured by Shikoku Kasei Co., Ltd.)

Below, using the adhesive sheet obtained above, the melt viscosity, adhesive strength, reflow resistance, shear storage elastic modulus, storage elastic modulus in the B stage state, storage elastic modulus in the C stage state, and the amount of warpage were evaluated. .
<Measurement of melt viscosity>
The melt viscosity of the adhesive sheet (adhesive layer) was measured by a parallel plate plastometer method. Three adhesive sheets obtained above were produced. From these, the support film was peeled and removed, and then three adhesive layers were bonded at 60 ° C. to obtain a sheet having a thickness of 120 μm. Subsequently, the sheet was punched in the thickness direction to obtain a disk-shaped measurement sample having a diameter of 6 mm and a thickness of 120 μm. A disk-shaped measurement sample is sandwiched between 150 μm thick glass slides in the thickness direction, and is used in a thickness direction at 3 kgf for 3 seconds using a pressure bonding (compression) machine set to 80 ° C. Crimped (compressed). The melt viscosity was calculated from the change in the contact area between the measurement sample and the slide glass at that time. The results are shown in Tables 3 and 4.

<Measurement of adhesive strength (die shear strength)>
The die shear strength of the adhesive sheet (adhesive layer) was measured by the following method. The adhesive sheet obtained above was peeled from the support film, and the adhesive layer was attached to a semiconductor wafer having a thickness of 400 μm at 60 ° C. Next, they were diced to 3.2 mm square to obtain chips. On the surface of a substrate (manufactured by Hitachi Chemical Co., Ltd., trade name: E-697FG) coated with a resist (trade name: AUS308, manufactured by Taiyo Ink Co., Ltd.) on the adhesive layer side of the separated chip, 100 ° C., 100 gf / cm ^{2. A} measurement sample was obtained by thermocompression bonding under conditions of 1 second. Thereafter, the adhesive layer of the obtained sample was cured by step cure in the order of 100 ° C. for 1 hour, 110 ° C. for 1 hour, 120 ° C. for 1 hour, and 170 ° C. for 1 hour. Further, the measurement sample after curing of the adhesive layer was allowed to stand for 168 hours under the conditions of 85 ° C. and 60 RH%. Immediately after standing, the die shear strength was measured at 265 ° C. and a shear rate of 50 μm / s, and this was taken as the adhesive strength. The results are shown in Tables 3 and 4.

<Evaluation of reflow resistance>
The reflow resistance of the adhesive sheet (adhesive layer) was evaluated by the following method. First, the adhesive layer of the adhesive sheet obtained above was attached to a semiconductor wafer having a thickness of 75 μm at 60 ° C. Next, they were diced into 7.5 mm squares to obtain chips. The adhesive layer of the chip | tip separated into pieces was crimped | bonded on the board | substrate surface which apply | coated the resist (The Taiyo Ink Co., Ltd. brand name: AUS308) on 120 degreeC, 0.05 Mpa and 1 second conditions, and the sample was obtained. Next, the obtained sample was heated at 120 ° C. for 60 minutes, and a thermal history equivalent to wire bonding (160 ° C., 5 minutes) was given to the sample using a hot plate. Subsequently, the sample was resin-sealed under conditions of 175 ° C. for 5 hours using a mold sealing material (manufactured by Hitachi Chemical Co., Ltd., trade name: CEL-9700HF) to obtain a package.
The obtained package was exposed to the environment defined by JEDEC (level 2, 85 ° C., 60 RH%, 168 hours) to absorb moisture. Subsequently, the package after moisture absorption was passed through an IR reflow furnace (260 ° C., maximum temperature 265 ° C.) three times. A case where no breakage of the package, a change in thickness, peeling of the interface, or the like was observed was evaluated as “A”, and a case where even one was observed was evaluated as “B”. The results are shown in Tables 3 and 4.

<Shear storage modulus after heat treatment at 120 ° C./1 hour>
The shear storage elastic modulus of the adhesive sheet (adhesive layer) was evaluated by the following method. Using the four adhesive sheets obtained above, the support film was peeled from three of the four B-stage adhesive sheets, and four sheets were bonded at 60 ° C. to obtain a sheet having a thickness of 160 μm. The sheet was punched into a circular shape with a diameter of 25 mm in the thickness direction to prepare a measurement sample. A circular aluminum plate jig with a diameter of 25 mm was set in ARES (manufactured by Rheometric Scientific), and the support film was peeled off from the punched measurement sample and set here. Thereafter, the shear storage modulus was measured every 8 seconds while applying 10% strain at 120 ° C., and the measured value after 1 hour was recorded. The results are shown in Tables 3 and 4.
In Comparative Example 2 and Comparative Example 3, the elastic modulus increased due to curing, and the 10% strain could not be endured, and the measurement sample was cracked before 1 hour and measurement was impossible. For this reason, Table 4 lists the maximum values during measurement.

<Storage elastic modulus in C stage>
The storage elastic modulus in the C-stage state was measured using a dynamic viscoelasticity measuring device (for example, DVE-V4 manufactured by Rheology Co., Ltd.), and the adhesive sheet (adhesive layer) obtained above was 1 at 120 ° C. Temperature-dependent measurement, measuring from -50 ° C to 300 ° C at a frequency of 10 Hz and a temperature increase rate of 5-10 ° C / min by applying a tensile load to the cured sheet for 3 hours at 170 ° C for 3 hours. Implement in mode. The results are shown in Tables 3 and 4.

<Warpage amount>
The amount of warpage when the chip with the adhesive layer was mounted on the substrate was evaluated by the following method. First, the adhesive layer of the adhesive sheet obtained above was attached to a semiconductor wafer having a thickness of 75 μm at 60 ° C. Next, they were diced to 11.0 mm square to obtain chips. This was pressure-bonded and mounted on a substrate (E-679FG) having a thickness of 100 μm at 120 ° C./0.05 MPa / 1 s. It should be noted that the surface of the chip diagonal line was measured with a surface roughness meter as shown in FIG. 1, and the value obtained by subtracting the minimum value from the maximum value was treated as the amount of warpage. The amount of warpage after mounting was measured (warpage amount A), and the amount of warpage was measured in the same manner for the sample after heat treatment at 120 ° C./1 hour and further after heat treatment at 160 ° C. for 5 minutes. The warpage amount resulting from the curing of the adhesive layer was calculated by subtracting the warpage amount A after crimping and mounting from the warpage amount after each heat treatment. The results are shown in Tables 3 and 4.

  As is clear from the results shown in Tables 3 and 4, the adhesive sheets of the present invention (Example 1 and Example 2) were 120 ° C./1 hour later as compared with the adhesive sheets of Comparative Examples 1 to 3. It has been clarified that the shear storage modulus is low and the amount of warpage of the semiconductor element can be reduced.

  The adhesive sheet of the present invention can completely bury the irregularities on the substrate only by pressure mounting at 80 ° C. or higher, and is based on heat treatment before wire bonding 120 ° C./1 hour and heat treatment 160 ° C./5 minutes. It is possible to provide an adhesive sheet in which the warpage of the element derived from the curing of the adhesive sheet is 70 μm or less.

It is a schematic diagram which shows the measuring method of curvature amount.

Claims (5)

The following (a), the following (b) 15-30 parts by mass, (c) 30-100 parts by mass, and (d) 0.05-0.20 parts by mass with respect to 100 parts by mass (a). Including
The melt viscosity at 80 ° C. before curing is 500 to 28000 Pa · s, the shear storage elastic modulus at 120 ° C. after heating at 120 ° C. for 1 hour is 1 MPa or less, and the unevenness of the uneven organic substrate is Adhesive sheet embedded under pressure bonding conditions of 120 ° C./0.1 MPa / 1 s.
(A) an epoxy resin represented by the following formula (Ia) or (Ib), a compound represented by the following formula (II) or (III) having a softening point of 70 ° C. or less and a hydroxyl group equivalent of 160 or more, A thermosetting resin containing 100 parts by mass of the thermosetting resin, wherein the epoxy resin is 25 parts by mass or more, and the compound is 35 to 55 parts by mass,
(B) an acrylic resin having a weight average molecular weight containing a crosslinkable functional group of 100,000 to 800,000 and Tg of −50 to 50 ° C .;
(C) an inorganic filler having an average particle size of 1.0 μm or less,
(D) Curing accelerator

(In formula (Ia), R ₁ and R ₂ represent a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group, or a halogen atom, and k and m represent an integer of 0 to 4. R ₃ and R ₄ represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group, or a halogen atom.

(In the formula _{(Ib), R 1, R} 2 is a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group or a halogen atom, k, m may indicate an integer of 0 to 4 ()

(In the formula (II), R ₅ represents a linear, branched or cyclic alkyl group, aralkyl group, alkenyl group, hydroxyl group, aryl group or halogen atom, and n represents an integer of 0 to 3. And represents an integer of 0 to 4. p indicating the number of repeating units represents an integer in the range of 0 to 50.)

(In formula (III), q representing the number of repeating units represents an integer in the range of 0 to 50.) The following (a), the following (b) 15-30 parts by mass, (c) 30-100 parts by mass, and (d) 0.05-0.20 parts by mass with respect to 100 parts by mass (a). Including, an adhesive sheet for a semiconductor having a melt viscosity of 500 to 28000 Pa · s at 80 ° C. before curing and an adhesive strength to an organic substrate of 2 MPa or more, after heating at 120 ° C. for 1 hour An adhesive sheet having a shear storage elastic modulus of 1 MPa or less.
(A) an epoxy resin represented by the following formula (Ia) or (Ib), and a compound represented by the following formula (II) or (III) having a softening point of 70 ° C. or less and a hydroxyl group equivalent of 160 or more. A thermosetting resin containing, in 100 parts by mass of the thermosetting resin, the epoxy resin is 25 parts by mass or more, and the compound is 35 to 55 parts by mass,
(B) an acrylic resin having a weight average molecular weight containing a crosslinkable functional group of 100,000 to 800,000 and Tg of −50 to 50 ° C .;
(C) an inorganic filler having an average particle size of 1.0 μm or less,
(D) Curing accelerator

(In formula (Ia), R ₁ and R ₂ represent a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group, or a halogen atom, and k and m represent an integer of 0 to 4. R ₃ and R ₄ represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group, or a halogen atom.

(In the formula _{(Ib), R 1, R} 2 is a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group, a hydroxyl group, an aryl group or a halogen atom, k, m may indicate an integer of 0 to 4 ()

(In the formula (II), R ₅ represents a linear, branched or cyclic alkyl group, aralkyl group, alkenyl group, hydroxyl group, aryl group or halogen atom, and n represents an integer of 0 to 3. And represents an integer of 0 to 4. p indicating the number of repeating units represents an integer in the range of 0 to 50.)

(In formula (III), q representing the number of repeating units represents an integer in the range of 0 to 50.) The adhesive sheet according to claim 1 or 2 , wherein an adhesive force with a glass-epoxy substrate at 265 ° C is 2 MPa or more. The adhesive sheet according to any one of claims 1 to 3 , wherein the inorganic filler has an average particle size of 0.5 µm or more and is distributed by 99 mass% in a range of 0.1 to 4.0 µm. (A) The equivalent ratio of the epoxy equivalent of the epoxy resin in the thermosetting resin to the hydroxyl equivalent of the compound represented by the formula (II) or (III) is 0.70 / 0.30 to 0.30 / 0. The adhesive sheet according to any one of claims 1 to 4 , which is .70.

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