JP2012241162A - Adhesive composition, adhesive sheet and material for protection of semiconductor device, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition capable of providing a cured product excellent in film forming property and adhesiveness to a circuit board, and excellent in insulation reliability (migration resistance) and connection reliability under elevated temperature and moisture conditions.SOLUTION: The adhesive composition includes (A) a polymer including an aromatic polysilane block and a polysiloxane block with a weight-average molecular weight of 3,000-500,000 in terms of polystyrene determined with GPC using an elution solvent of tetrahydrofuran, (B) a thermosetting resin, and (C) a compound having flux activity. An adhesive sheet having an adhesive layer formed by using the adhesive composition and a material for protection of semiconductor device, and a semiconductor device equipped with the cured product of the adhesive composition are also provided.

Description

  The present invention relates to an adhesive composition, and more particularly, to an adhesive composition that can be suitably used for manufacturing a semiconductor device using a flip chip mounting method. Furthermore, the present invention relates to an adhesive sheet having an adhesive layer formed using the adhesive composition, a material for protecting a semiconductor device, and a semiconductor device provided with a cured product of the adhesive composition.

  In recent years, with the miniaturization and high performance of electronic devices, the demand for higher density and higher integration of semiconductor devices has increased, and the increase in capacity and density of IC packages has been progressing. Until now, wire bonding methods using fine metal wires have been widely applied to connect a semiconductor chip and a substrate. However, in order to meet the demand for higher density and higher integration of semiconductor devices, a flip chip mounting method in which conductive protrusions called bumps are formed on a semiconductor chip and the substrate electrode and the bumps of the semiconductor chip are directly connected is the mainstream. It is becoming. In general, in the flip chip mounting method, a gap between a semiconductor chip and a circuit board is sealed with an underfill agent for the purpose of reinforcing connection parts and improving the reliability of a semiconductor device. As a method of sealing with an underfill agent, a capillary underfill method is generally employed. The capillary underfill method is a method in which an underfill agent is applied to one side or a plurality of surfaces of a chip, and the underfill agent is poured into a gap between a circuit board and the chip by using a capillary phenomenon (Patent Document 1). .

In the capillary underfill method, steps (a) to (g) shown in FIG. 8 are required. Each step will be described below.
Step (a): Step of applying flux (reference numeral 21) to the circuit board (reference numeral 20) Step (b): A semiconductor chip (reference numeral 22) on which bumps (reference numeral 22a) are formed is formed on the circuit board (reference numeral 20). Step of mounting (c): Step of bonding the semiconductor chip (reference numeral 22) and the circuit board (reference numeral 20) via the flux (reference numeral 21) (bonding part: reference numeral 23)
Step (d): Step of cleaning the flux (reference numeral 21) Step (e): Step of applying an underfill agent (reference numeral 24) to one side or a plurality of surfaces of the semiconductor chip (reference numeral 22) (f): Capillary phenomenon Step (g) of using an underfill agent (reference numeral 24) to flow into the gap between the circuit board (reference numeral 20) and the semiconductor chip (reference numeral 22): curing the filled underfill agent (reference numeral 24) and resin Sealing process

  As described above and shown in FIG. 8, the capillary underfill method has a complicated process and requires treatment of the cleaning waste liquid. Further, since the capillary phenomenon is used in the step (f), the filling time becomes long, which may cause a problem in the productivity of the semiconductor device.

  As a method for solving these problems, a film for a semiconductor having an adhesive layer composed of a resin composition containing a resin capable of crosslinking reaction, a compound having flux activity, and a film-forming resin is used as a function of a semiconductor chip. A method of sticking to a surface and using it is disclosed (Patent Document 2). In the method described in Patent Document 2, since the semiconductor film functions as a flux and a resin sealant, the semiconductor chip can be bonded to the circuit board without using the flux. Therefore, the steps (a), (d), (e), and (f) are not required, and the productivity of the semiconductor device is improved.

JP 2007-217708 A JP 2009-239138 A

  However, since the method described in Patent Document 2 uses an acrylic resin, particularly an acrylic resin containing acrylonitrile, as a film-forming resin, there is a serious problem that it is inferior in insulation reliability (migration resistance) under high temperature and high humidity conditions. is there. Therefore, the method disclosed in Patent Document 2 cannot sufficiently achieve the objectives such as reinforcing the connection portion between the semiconductor chip and the circuit board and improving the reliability of the semiconductor device. Therefore, there is a strong demand for the development of an adhesive composition that can provide a semiconductor device that has excellent adhesion to a substrate and that is cured to provide excellent connection reliability and insulation reliability.

  The present invention provides an adhesive composition that is excellent in film formability and adhesion to a substrate, and that can provide a cured product having excellent insulation reliability (migration resistance) and connection reliability under high temperature and high humidity conditions. The purpose is to provide.

  As a result of intensive studies to achieve the above problems, the present inventors have a repeating unit represented by the following formulas (1-1), (1-2) and (1-3), An adhesive composition containing a polymer having a measured polystyrene equivalent weight average molecular weight of 3,000 to 500,000 forms an adhesive layer with excellent flexibility, and even under high temperature and high humidity conditions The present inventors have found that a cured product that does not cause migration and has excellent insulation reliability is provided, and has led to the present invention.

式中、ｒ、ｓ及びｔは正の整数であり、式（１−１）、式（１−２）及び式（１−３）で表される繰返し単位を構成する各単位の末端ケイ素原子が各同じ単位あるいは異なる単位のＸ^１、Ｘ^２またはＸ^３の末端炭素原子と結合しており、式中、Ｒ^１は、互いに独立に、炭素数１〜８の１価炭化水素基であり、Ｘ^１は、互いに独立に、下記式（２）で示される２価の基であり、

（式中、Ｚは、置換または非置換の、炭素数１〜１５の２価炭化水素基であり、ｐは０又は１である。Ｒ^２は、互いに独立に、炭素数１〜４のアルキル基又はアルコキシ基であり、ｑは０、１または２である）
Ｘ^２は、互いに独立に、下記式（３）で示される２価の基であり、

（式中、Ｒ^３は水素原子、炭素数１〜８の１価炭化水素基、またはグリシジル基である）
Ｘ^３は、互いに独立に、下記式（４）で示される２価の基であり、

（式中、Ｒ^４は、互いに独立に、炭素数１〜８の１価炭化水素基であり、ｎは０〜１００の整数である）
（Ｂ）熱硬化性樹脂
（Ｃ）フラックス活性を有する化合物 That is, the present invention provides an adhesive composition containing the following components (A), (B) and (C).
(A) It contains repeating units represented by the following formulas (1-1), (1-2) and (1-3), and has a polystyrene equivalent weight average molecular weight of 3, measured by GPC using tetrahydrofuran as an elution solvent. Polymer from 000 to 500,000

In the formula, r, s and t are positive integers, and the terminal silicon atom of each unit constituting the repeating unit represented by the formula (1-1), the formula (1-2) and the formula (1-3) Are bonded to the terminal carbon atom of X ¹ , X ² or X ³ of the same unit or different units, and in the formula, R ¹ is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. , X ¹ are each independently a divalent group represented by the following formula (2):

(In the formula, Z is a substituted or unsubstituted divalent hydrocarbon group having 1 to 15 carbon atoms, and p is 0 or 1. R ² is independently alkyl having 1 to 4 carbon atoms. Group or alkoxy group, q is 0, 1 or 2)
X ² is, independently of each other, a divalent group represented by the following formula (3),

(Wherein R ³ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms, or a glycidyl group)
X ³ is, independently of each other, a divalent group represented by the following formula (4),

(In the formula, R ⁴ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, and n is an integer of 0 to 100).
(B) Thermosetting resin (C) Compound having flux activity

  Furthermore, the present invention provides an adhesive sheet having an adhesive layer formed using the adhesive composition, a semiconductor device protecting material having the adhesive layer, and a semiconductor provided with a cured product of the adhesive composition. Providing equipment.

  The adhesive composition of this invention can form the adhesive layer excellent in the softness | flexibility by containing the polymer which has the said repeating unit. Moreover, the adhesive composition containing the polymer having the repeating unit does not cause a migration problem under a high temperature and high humidity condition, and can provide a cured product having excellent insulation reliability. Therefore, the adhesive composition of the present invention can be suitably used as an adhesive layer for an adhesive sheet and a semiconductor protecting material, and can provide a semiconductor device in which insulation reliability is guaranteed.

  Moreover, since the adhesive composition of this invention contains the compound which has flux activity, the adhesive bond layer which has the effect (flux activity) which removes a metal oxide film by heating etc. is formed. Thereby, a semiconductor device having excellent connection reliability can be provided. In addition, the adhesive layer functions as a flux when the semiconductor chip and the circuit board are bonded to each other, thereby applying a flux to the circuit board when the semiconductor chip is flip-chip mounted on the board (FIG. 8: Step (a)), flux cleaning step (FIG. 8: Step (d)), step of applying an underfill agent to one or more sides of the semiconductor chip (FIG. 8: Step (e)), and capillary action This eliminates the need for a step (FIG. 8: step (f)) of flowing an underfill agent into the gap between the circuit board and the chip, thereby improving the productivity of the semiconductor device.

FIG. 1 shows an embodiment in which an adhesive sheet having an adhesive layer formed using the adhesive composition of the present invention is pressure-bonded onto a semiconductor wafer. FIG. 2 shows a mode in which a semiconductor wafer is mounted on a protective tape for semiconductor processing via an adhesive sheet having an adhesive layer formed using the adhesive composition of the present invention. FIG. 3 shows an aspect of grinding a semiconductor wafer. FIG. 4 shows an aspect of dicing a semiconductor wafer. FIG. 5 shows a mode of picking up a cut semiconductor chip. FIG. 6 shows a mode in which the picked-up semiconductor chip is positioned and mounted on the base substrate. FIG. 7 shows a state in which the semiconductor chip and the base substrate are joined by soldering. FIG. 8 is a flowchart showing a flip chip mounting process in the capillary underfill method. FIG. 9 is an embodiment of a test in which the adhesive strength of the adhesive layer to the substrate was measured.

(A) Polymer containing silphenylene structure and siloxane structure In the present invention, the component (A) functions as a film-forming resin. (A) component of this invention contains the repeating unit represented by the said Formula (1-1), Formula (1-2), and Formula (1-3), The polystyrene measured by GPC using tetrahydrofuran as an elution solvent A polymer having a converted weight average molecular weight of 3,000 to 500,000, preferably 5,000 to 200,000. In the above formula (1-1), formula (1-2) and formula (1-3), r, s and t are the formula (1-1), formula (1-2) and formula (1-3). The number of repetitions of each unit constituting the repeating unit represented by r, s and t are positive integers, and the polymer may have a weight average molecular weight of 3,000 to 500,000, preferably 5,000 to 200,000, preferably 0.05. ≦ r / (r + s + t) ≦ 0.8, 0.1 ≦ s / (r + s + t) ≦ 0.7, and an integer satisfying 0.05 ≦ t / (r + s + t) ≦ 0.8, more preferably 0 0.1 ≦ r / (r + s + t) ≦ 0.6, 0.2 ≦ s / (r + s + t) ≦ 0.5, and 0.1 ≦ t / (r + s + t) ≦ 0.7. Each unit constituting the repeating unit represented by the above formula (1-1), formula (1-2), and formula (1-3) is the same unit or different unit X ^{1 in} each unit. , X ² or X ³ bonded to the terminal carbon atom. Each unit may be bonded at random or may be bonded as a block polymer.

In the above formula, R ¹ is each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, methyl group, ethyl group, propyl group, hexyl group, cyclohexyl group, and phenyl group. Etc. Among these, a methyl group and a phenyl group are preferable because of easy availability of raw materials.

In the above formula (2), R ² is each independently an alkyl group or alkoxy group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, methyl, ethyl group, propyl group, tert-butyl group, methoxy group. And an ethoxy group. q is 0, 1 or 2, preferably 0.

In the above formula (2), Z is a substituted or unsubstituted divalent hydrocarbon group having 1 to 15 carbon atoms, and a part or all of the hydrogen atoms bonded to the carbon atom are fluorine atom, chlorine It may be substituted with a halogen atom such as an atom or a bromine atom. Preferably, Z is a divalent group selected from any of the groups shown below. p is 0 or 1.

In the above formula (3), R ³ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 3 carbon atoms, or a glycidyl group. Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, and a cyclohexyl group.

In the above formula (4), R ⁴ is each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, methyl group, ethyl group, propyl group, hexyl group, cyclohexyl group, And a phenyl group. Of these, a methyl group and a phenyl group are preferable because of easy availability of raw materials. n is an integer of 0 to 100, preferably an integer of 0 to 60.

式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｚ、ｎ、ｐ、ｑ、ｒ、ｓ及びｔは上述の通りであり、繰返しを構成する各単位の末端ケイ素原子が各同じ単位あるいは異なる単位の末端炭素原子と結合しており、重合体の末端は脂肪族不飽和基またはケイ素原子に結合した水素原子である。 The polymer containing the repeating unit represented by the above formula (1-1), formula (1-2) and formula (1-3) can be represented by the following formula.

In the formula, R ¹ , R ² , R ³ , R ⁴ , Z, n, p, q, r, s and t are as described above, and the terminal silicon atom of each unit constituting the repetition is the same unit or It is bonded to a terminal carbon atom of a different unit, and the polymer terminal is a hydrogen atom bonded to an aliphatic unsaturated group or a silicon atom.

The present invention further includes a repeating unit represented by the above formula (1-1), formula (1-2) and formula (1-3), a unit represented by the following formula (5), and the following formula (6). And a polymer having at least one of units represented by the following formula (7).

Each unit constituting the repeating unit represented by the above formula (1-1), formula (1-2), and formula (1-3), the unit represented by formula (5), and the formula (6) In the unit and the unit represented by the formula (7), the terminal silicon atom of each unit is bonded to the terminal carbon atom of each same unit or different unit. Each unit may be bonded at random or may be bonded as a block polymer. In the formula (5), X is independently a group represented by the above X ¹ , X ² or X ³ , and m is an integer of 0 to 100, preferably an integer of 1 to 60. In the above formula (6) and formula (7), e, f, g, h, i and j are integers of 0 to 100, preferably 0 to 30. However, e + f + g ≧ 3, e = f = 0 is not satisfied, and h = i = 0 is not satisfied. In the above formula (5), formula (6) and formula (7), R ¹ is as described above.

The polymer of the present invention contains 5 mol% or more and 80 mol% of the group represented by X ¹ (that is, the above formula (2)) with respect to the total mol of the groups represented by X ¹ , X ² and X ^3. Or less, preferably 10 mol% or more and 60 mol% or less, a group represented by X ² (that is, the above formula (3)) is 10 mol% or more and 70 mol% or less, preferably 20 mol% or more and 50 mol% or less, The group represented by X ³ (that is, the above formula (4)) is contained in an amount of 5 mol% to 80 mol%, preferably 10 mol% to 70 mol%.

  The polymer of this invention can have 1 type in a unit represented by the said Formula (5), Formula (6), and Formula (7), or 2 or more types. The number of repeating units may be any number such that the polymer has a polystyrene-equivalent weight average molecular weight measured by GPC of 3,000 to 500,000, preferably 5,000 to 200,000. Preferably, the total number of repeating units (that is, r + s + t) of the repeating units represented by the above formulas (1-1), (1-2), and (1-3) is a (a is a positive integer). When the repeating number of the unit represented by the formula (5) is b, the repeating number of the unit represented by the formula (6) is c, and the repeating number of the unit represented by the formula (7) is d (b , C and d are integers), the number of a relative to the sum of a, b, c and d is 0.05 ≦ a / (a + b + c + d) ≦ 0.99, preferably 0.2 ≦ a / (a + b + c + d) ≦ 0. The number should be 98. When the polymer has a unit represented by the above formula (5), the number of repeating units is 0.01 ≦ b / (a + b + c + d) ≦ 0.95, preferably 0.05 ≦ b / (a + b + c + d) ≦. A number that is 0.8 is good. When the polymer has a unit represented by the above formula (6), the number of repeating units is 0.01 ≦ c / (a + b + c + d) ≦ 0.8, preferably 0.05 ≦ c / (a + b + c + d) ≦. A number that is 0.5 is good. When the polymer has a unit represented by the above formula (7), the number of repeating units is 0.01 ≦ d / (a + b + c + d) ≦ 0.8, preferably 0.01 ≦ d / (a + b + c + d) ≦. A number that is 0.5 is good.

式中、Ｒ^１、Ｘ、ｅ、ｆ、ｇ、ｈ、ｉ、及びｊは上述の通りであり、各単位の末端炭素原子は、上述した各単位の末端ケイ素原子と結合する。 The polymer of the present invention may further contain the following units in addition to the units described above.

In the formula, R ¹ , X, e, f, g, h, i, and j are as described above, and the terminal carbon atom of each unit is bonded to the terminal silicon atom of each unit described above.

式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｚ、ｎ、ｍ、ｐ、ｑ、ｒ、ｓ、ｔ及びｂは上述の通りであり、繰返しを構成する各単位の末端ケイ素原子が各同じ単位あるいは異なる単位の末端炭素原子と結合しており、重合体の末端は脂肪族不飽和基またはケイ素原子に結合した水素原子である。 The polymer having the repeating unit represented by the formula (1-1), the formula (1-2) and the formula (1-3) and the unit represented by the formula (5) is represented by the following formula, for example. Can do.

In the formula, R ¹ , R ² , R ³ , R ⁴ , Z, n, m, p, q, r, s, t and b are as described above, and the terminal silicon atom of each unit constituting the repeat is It is bonded to the terminal carbon atom of each same unit or different unit, and the terminal of the polymer is a hydrogen atom bonded to an aliphatic unsaturated group or a silicon atom.

式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｚ、ｎ、ｐ、ｑ、ｅ、ｆ、ｇ、ｒ、ｓ、ｔ及びｃは上述の通りであり、繰返しを構成する各単位の末端ケイ素原子が各同じ単位あるいは異なる単位の末端炭素原子と結合しており、重合体の末端は脂肪族不飽和基またはケイ素原子に結合した水素原子である。 The polymer having the repeating unit represented by the above formula (1-1), formula (1-2) and formula (1-3) and the unit represented by formula (6) is represented by the following formula, for example. I can do things.

In the formula, R ¹ , R ² , R ³ , R ⁴ , Z, n, p, q, e, f, g, r, s, t and c are as described above, and each unit constituting the repetition A terminal silicon atom is bonded to a terminal carbon atom of the same unit or a different unit, and the terminal of the polymer is a hydrogen atom bonded to an aliphatic unsaturated group or a silicon atom.

式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｚ、ｎ、ｐ、ｑ、ｈ、ｉ、ｊ、ｒ、ｓ、ｔ及びｄは上述の通りであり、繰返しを構成する各単位の末端ケイ素原子が各同じ単位あるいは異なる単位の末端炭素原子と結合しており、重合体の末端は脂肪族不飽和基またはケイ素原子に結合した水素原子である。 The polymer having the repeating unit represented by the above formula (1-1), formula (1-2) and formula (1-3) and the unit represented by formula (7) is represented by the following formula, for example. I can do things.

In the formula, R ¹ , R ² , R ³ , R ⁴ , Z, n, p, q, h, i, j, r, s, t and d are as described above, and each unit constituting the repetition A terminal silicon atom is bonded to a terminal carbon atom of the same unit or a different unit, and the terminal of the polymer is a hydrogen atom bonded to an aliphatic unsaturated group or a silicon atom.

（式中、Ｚ、Ｒ^２、ｐ及びｑは上述の通りである）

（式中、Ｒ^３は上述の通りである）

（式中、Ｒ^４及びｎは上述の通りである） The polymer having a repeating unit represented by the above formula (1-1), formula (1-2) and formula (1-3) includes a compound represented by the following formula (8) and the following formula (9). And a compound represented by the following formula (10) and a compound represented by the following formula (11) can be produced by a method including a step of addition polymerization in the presence of a metal catalyst. .

(Wherein Z, R ² , p and q are as described above)

(Wherein R ³ is as described above)

(Wherein R ⁴ and n are as described above)

Examples of the compound represented by the above formula (11) include the following.

（式中、Ｒ^１、ｍ、ｅ、ｆ、ｇ、ｈ、ｉ及びｊは上述の通りである） Moreover, the repeating unit represented by the formula (1-1), formula (1-2) and formula (1-3), the unit represented by the formula (5), and the formula (6). And a polymer having at least one of the units represented by the formula (7) includes a compound represented by the formula (8), a compound represented by the formula (9), and the above formula. The compound represented by (10), the compound represented by the above formula (11), the compound represented by the following formula (12), the compound represented by the following formula (13), and the following formula (14) And at least one of the compounds represented by formula (1) can be produced by a method including a step of addition polymerization in the presence of a metal catalyst.

(Wherein R ¹ , m, e, f, g, h, i and j are as described above)

Examples of the compound represented by the above formula (13) include the following.

Examples of the compound represented by the above formula (14) include the following.

Examples of the metal catalyst include platinum group metals such as platinum (including platinum black), rhodium and palladium; H ₂ PtCl ₄ · xH ₂ O, H ₂ PtCl ₆ · xH ₂ O, NaHPtCl ₆ · xH ₂ O, KHPtCl ₆ · xH ₂ O, Na ₂ PtCl ₆ · xH ₂ O, K ₂ PtCl ₄ · xH ₂ O, PtCl ₄ · xH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ · xH ₂ O (wherein x is 0 to 0) Platinum chloride, chloroplatinic acid and chloroplatinic acid salts, such as an integer of 6, preferably 0 or 6, and alcohol-modified chloroplatinic acid (for example, those described in US Pat. No. 3,220,972); Complexes of chloroplatinic acid and olefins (eg, US Pat. No. 3,159,601, US Pat. No. 3,159,662, and US Pat. No. 3,775,452). Described above); a platinum group metal such as platinum black or palladium supported on a carrier such as alumina, silica, carbon; rhodium-olefin complex; chlorotris (triphenylphosphine) rhodium (so-called Wilkinson catalyst); and chloride A complex of platinum, chloroplatinic acid or chloroplatinate and a vinyl group-containing siloxane (particularly a vinyl group-containing cyclic siloxane) can be used.

The amount of the catalyst used may be a catalytic amount, and is 0.0001 to 0.1% by mass, preferably 0.001 to 0.01% by mass, based on the total amount of raw material compounds subjected to the reaction, as a platinum group metal. It is preferable. The addition reaction can be carried out without a solvent, but a solvent may be used as necessary. As the solvent, for example, hydrocarbon solvents such as toluene and xylene are preferable. The reaction temperature may be a temperature at which the catalyst is not deactivated and the polymerization can be completed in a short time, and is preferably 40 to 150 ° C, particularly preferably 60 to 120 ° C. What is necessary is just to select reaction time suitably with the kind and quantity of a polymer, for example, 0.5 to 100 hours, Especially 0.5 to 30 hours are preferable. When a solvent is used, it is subjected to vacuum distillation after completion of the reaction to distill off the solvent.

The reaction method is not particularly limited. For example, the reaction method is represented by the compound represented by the formula (8), the compound represented by the formula (9), the compound represented by the formula (10), and the formula (11). When the compound to be reacted is first mixed with the compounds represented by formula (9), formula (10) and formula (11) and heated, a metal catalyst is added to the mixture, and then the formula (9) It is good to add the compound represented by 8) dropwise over 0.1 to 5 hours. When the compound represented by the formula (12) is reacted, the compound represented by the formula (8) and the compound represented by the formula (12) are mixed separately or simultaneously as required, It is good to add dropwise over 0.1 to 5 hours.

When the compound represented by the formula (13) and the compound represented by the formula (14) are reacted, first, they are represented by the formula (8), the formula (9), the formula (10), and the formula (11). And the compound represented by the formula (12) if necessary for addition polymerization, stirring for 0.5 to 100 hours, particularly 0.5 to 30 hours, and then adding the formula ( The compound represented by 13) or the compound represented by formula (14) may be added dropwise over 0.1 to 5 hours and stirred for 1 to 10 hours, particularly 2 to 5 hours. When the compound represented by Formula (8)-(12) and the compound represented by Formula (13) or (14) are made to react simultaneously, there exists a possibility that a product may gelatinize.

  The compounding ratio of each compound is the sum of the number of moles of hydrosilyl groups possessed by the compounds represented by formula (8), formula (12), formula (13), and formula (14), and formula (9), The total number of moles of alkenyl groups in the compounds represented by formula (10), formula (11), formula (13), and formula (14) is such that the total number of moles of hydrosilyl groups relative to the total number of moles of alkenyl groups is It is good to mix | blend so that it may become 0.67-1.67, Preferably 0.83-1.25. The weight average molecular weight of the polymer can be controlled by using a monoallyl compound such as o-allylphenol, or a monohydrosilane or monohydrosiloxane such as triethylhydrosilane as a molecular weight modifier.

(B) A thermosetting resin (B) component contains in order to improve the adhesiveness and connection reliability of an adhesive composition. In the present invention, the thermosetting resin is not particularly limited, and examples thereof include an epoxy resin, a phenol resin, a melamine resin, a urethane resin, and a polyester resin. Among these, an epoxy resin is preferable. The epoxy resin can undergo a crosslinking reaction with the phenolic hydroxyl group contained in the polymer (A). Therefore, when the thermosetting resin is an epoxy resin, the thermosetting resin and the polymer (A) undergo a cross-linking reaction when the adhesive composition is cured. Connection reliability is improved.

  Epoxy resins include, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, or those hydrogenated thereto, phenol novolac type epoxy resins, cresol novolac type epoxy resins and the like glycidyl ether type epoxy resins, hexahydrophthalic acid, etc. Examples include glycidyl ester epoxy resins such as glycidyl ester and dimer acid glycidyl ester, glycidyl amine epoxy resins such as triglycidyl isocyanurate and tetraglycidyl diaminodiphenylmethane, and preferably bisphenol A type epoxy resins and bisphenol F type epoxy resins. And phenol novolac type epoxy resins and cresol novolac type epoxy resins. Examples of these commercially available products include jER1001 (manufactured by Mitsubishi Chemical), Epicron 830S (manufactured by DIC), jER517 (manufactured by Mitsubishi Chemical), and EOCN103S (manufactured by Nippon Kayaku).

  Moreover, a phenol resin can also be used as a thermosetting resin. Examples of the phenol resin include resol type phenol resins and / or novolacs prepared from alkylphenols such as phenol, bisphenol A, pt-butylphenol, octylphenol, and p-cumylphenol, p-phenylphenol, cresol, and the like as raw materials. Type phenolic resin. A thermosetting resin may be used individually by 1 type, or may use 2 or more types together.

  Although the compounding quantity of a thermosetting resin is not specifically limited, It is good that it is 5-500 mass parts with respect to 100 mass parts of (A) component, Preferably it is 10-410 mass parts. When the blending amount of the thermosetting resin is within the above range, the adhesiveness when the adhesive composition or the adhesive layer is pressure-bonded to the substrate is improved. Moreover, since the hardened | cured material of this adhesive composition turns into a hardened | cured material excellent in connection reliability, it is preferable.

  The adhesive composition of the present invention preferably further contains an epoxy resin curing agent and / or an epoxy resin curing accelerator in addition to the epoxy resin. By containing an epoxy resin curing agent and / or an epoxy resin curing accelerator, the curing reaction can be appropriately and uniformly advanced. The compounding amount of the epoxy resin curing agent is 3 to 200 parts by mass, preferably 5 to 160 parts by mass with respect to 100 parts by mass of the component (A), and the compounding amount of the epoxy resin curing accelerator is (A). 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the component.

  The epoxy resin curing agent is not particularly limited as long as it is usually used, but an aromatic curing agent and an alicyclic curing agent are more preferable from the viewpoint of heat resistance. Examples of the epoxy resin curing agent include amine-based curing agents, acid anhydride-based curing agents, boron trifluoride amine complex salts, and phenol resins. Examples of amine curing agents include aliphatic amine curing agents such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine, alicyclic amine curing agents such as isophoronediamine, and aromatic amines such as diaminodiphenylmethane and phenylenediamine. Examples thereof include a system curing agent and dicyandiamide. Of these, aromatic amine curing agents are preferred. Examples of the acid anhydride curing agent include phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, and the like. The said epoxy resin hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

  Examples of the epoxy resin curing accelerator include 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and ethyl isocyanate compounds of these compounds, 2-phenylimidazole, 2-phenyl-4-methylimidazole. Imidazole compounds such as 2-phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole, 1,8-diazabicyclo (5.4.0) undecene-7 (DBU), DBU compounds such as 1,5-diazabicyclo (4.3.0) nonene-5 (DBN), DBU organic acid salt, DBU phenol resin salt, DBU derivative tetraphenylborate salt, triphenylphosphine, tributylphosphine , Tris (p-methylphenyl) pho Fins, tris (p-methoxyphenyl) phosphine, tris (p-ethoxyphenyl) phosphine, triorganophosphines such as triphenylphosphine / triphenylborate, tetraphenylphosphine / tetraphenylborate, quaternary phosphonium salts, triethyleneammonium -Tertiary amines such as triphenylborate, and tetraphenylborates thereof. The said epoxy resin hardening accelerator may be used individually by 1 type, or may use 2 or more types together.

(C) Compound having flux activity (C) The compound having flux activity is not particularly limited as long as it has the effect of reducing and removing the metal oxide film by heating or the like (flux activity). For example, activated rosin, Examples thereof include organic acids having a carboxyl group, amines, phenols, alcohols and azines.

  In particular, the compound having flux activity according to the present invention is preferably a compound having a carboxy group or a phenolic hydroxyl group in the molecule. The compound having flux activity may be liquid or solid. If the compound having a flux activity is a compound having a carboxy group or a phenolic hydroxyl group in the molecule, it exists on the functional surface when soldering the functional surface of the semiconductor chip to which the adhesive composition is bonded. This is preferable because the effect of removing the metal oxide film of the bump by heating or the like becomes particularly high.

  Examples of the compound having a carboxyl group include an aliphatic acid anhydride, an alicyclic acid anhydride, an aromatic acid anhydride, an aliphatic carboxylic acid, and an aromatic carboxylic acid. Examples of the compound having a phenolic hydroxyl group include phenols.

  Examples of the aliphatic acid anhydride include succinic anhydride, polyadipic acid anhydride, polyazeline acid anhydride, and polysebacic acid anhydride.

  Examples of alicyclic acid anhydrides include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, and methylcyclohexene dicarboxylic acid. An acid anhydride etc. are mentioned.

  Examples of the aromatic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, and glycerol tris trimellitate.

  Examples of the aliphatic carboxylic acid include glutaric acid, adipic acid, pimelic acid, sebacic acid and the like. Other aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, methacrylic acid, Examples include crotonic acid, oleic acid, fumaric acid, maleic acid, oxalic acid, malonic acid, and oxalic acid.

  Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, merophanic acid, platnic acid, pyromellitic acid, merit acid, triylic acid, xylic acid, Hemellitic acid, mesitylene acid, prenylic acid, toluic acid, cinnamic acid, salicylic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, gentisic acid (2,5-dihydroxybenzoic acid), 2,6- Dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid (3,4,5-trihydroxybenzoic acid), 1,4-dihydroxy-2-naphthoic acid, and 3,5-dihydroxy-2-naphthoic acid Naphthoic acid derivatives such as diphenolic acid and the like.

  Examples of the compound having a phenolic hydroxyl group include phenol, o-cresol, 2,6-xylenol, p-cresol, m-cresol, o-ethylphenol, 2,4-xylenol, 2,5 xylenol, m-ethylphenol. 2,3-xylenol, meditol, 3,5-xylenol, p-tertiarybutylphenol, catechol, p-tertiaryamylphenol, resorcinol, p-octylphenol, p-phenylphenol, bisphenol A, bisphenol F, bisphenol AF, Examples thereof include monomers containing a phenolic hydroxyl group such as biphenol, diallyl bisphenol F, diallyl bisphenol A, trisphenol, and tetrakisphenol and phenolphthalein.

  Moreover, it is preferable that the compound which has (C) flux activity can carry out a crosslinking reaction with (A) component or (B) component. By reacting with the component (A) and the component (B), a compound having a flux activity can be three-dimensionally incorporated into the crosslinked structure. In particular, a resin curing agent having flux activity is preferable. Examples of the curing agent having flux activity include compounds having at least two phenolic hydroxyl groups in one molecule and a carboxyl group directly bonded to at least one aromatic group. Specifically, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, gentisic acid (2,5-dihydroxybenzoic acid), 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, gallic acid Benzoic acid derivatives such as acid (3,4,5-trihydroxybenzoic acid); 1,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid, 3,7-dihydroxy-2-naphthoic acid Naphthoic acid derivatives such as acids; phenolphthalein; and diphenolic acid.

  By incorporating the compound having the flux activity into the crosslinked structure three-dimensionally, it is possible to suppress the residue of the compound having the flux activity from being precipitated from the three-dimensional crosslinked structure of the cured product. Thereby, the growth of dendrite derived from the residue of the compound can be suppressed, and the insulation reliability (migration resistance) of the cured product can be further improved.

  (C) Although the compounding quantity of the compound which has flux activity is not specifically limited, It is 1-20 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, Preferably, it is 2-15 mass parts. There should be. (C) If the content of the compound having flux activity is less than the above lower limit value, the effect of flux activity is not sufficiently obtained, and if it exceeds the above upper limit value, the compound having flux activity precipitates from the crosslinked structure after the flip chip mounting process. May cause dendrite to grow. When the compounding amount of the compound having the flux activity is within the above range, the oxide film on the metal surface can be sufficiently removed, so that good bonding with high strength can be obtained at the time of solder bonding.

Other components In addition to the components (A) to (C), other components may be added to the adhesive composition of the present invention as long as the properties of the adhesive composition of the present invention are not impaired. Examples of other components include inorganic fillers and silane coupling agents.

Inorganic Filler The adhesive composition of the present invention can contain an inorganic filler in order to obtain properties such as heat resistance, dimensional stability, and moisture resistance. Examples of inorganic fillers include silicates such as talc, calcined clay, unfired clay, mica, glass, etc., oxidation of powders such as titanium oxide, alumina, fused silica (fused spherical silica, fused crushed silica), crystalline silica, etc. Products, carbonates such as calcium carbonate, magnesium carbonate and hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite, boron Examples thereof include borates such as zinc oxide, barium metaborate, aluminum borate, calcium borate, and sodium borate, and nitrides such as aluminum nitride, boron nitride, and silicon nitride. These inorganic fillers may be mixed singly or in combination of two or more. Among these, silica powder such as fused silica and crystalline silica is preferable, and fused spherical silica is particularly preferable.

  By containing the inorganic filler, it is possible to improve the heat resistance, moisture resistance, strength, etc. after curing the adhesive composition of the present invention, and it is formed using the adhesive composition of the present invention. In the adhesive sheet formed by laminating the adhesive layer and the protective layer, the peelability of the adhesive layer with respect to the protective layer can be improved. In addition, although the shape of an inorganic filler is not specifically limited, It is preferable that it is a perfect sphere, Thereby, an adhesive layer without anisotropy can be formed.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more and 0.5 μm or less, and particularly preferably 0.01 μm or more and 0.3 μm or less. If the average particle diameter of the inorganic filler is less than the above lower limit value, the inorganic filler tends to aggregate and the strength decreases, which is not preferable. If the value exceeds the upper limit, the transparency of the adhesive layer is lowered, it is difficult to recognize the alignment mark on the surface of the semiconductor chip, and the alignment of the semiconductor chip and the substrate is difficult, which is not preferable.

  Although content of an inorganic filler is not specifically limited, It is preferable to set it as 5 to 60 mass% with respect to the total mass of the adhesive composition of this invention, Preferably it is 10 to 50 mass%. If the content of the inorganic filler exceeds the above upper limit value, the transparency and tackiness of the adhesive layer are lowered, which is not preferable.

Silane Coupling Agent The adhesive composition of the present invention may contain a silane coupling agent. By including the silane coupling agent, the adhesiveness of the adhesive layer to the adherend can be further enhanced. Examples of the silane coupling agent include an epoxy silane coupling agent and an aromatic-containing aminosilane coupling agent. These may be used alone or in combination of two or more. Although content of a silane coupling agent is not specifically limited, It is preferable to set it as 0.01 to 5 mass% of the total mass of the adhesive composition of this invention.

  Moreover, the adhesive composition of this invention may contain components other than the above. For example, in order to improve the compatibility between the polymer (A) and the thermosetting resin (B), or to improve various properties such as storage stability or workability of the adhesive composition, various additives are appropriately used. It may be added. For example, an internal mold release agent such as fatty acid ester, glyceric acid ester, zinc stearate, calcium stearate, or the like, a phenol-based, phosphorus-based, or sulfur-based antioxidant can be added within a range that does not impair the effects of the present invention. . Other optional components may be added to the adhesive composition of the present invention without a solvent, or may be added after dissolving or dispersing in an organic solvent and preparing a solution or dispersion. The solvent can use the organic solvent demonstrated below as a solvent for preparing the dispersion liquid of an adhesive composition.

Preparation of Adhesive Composition The adhesive composition of the present invention comprises a polymer (A), a thermosetting resin (B), a compound having a flux activity (C), and other optional components as required, and if necessary. The organic solvent is prepared by stirring, dissolving, mixing and dispersing simultaneously or separately with heat treatment if necessary. Although the apparatus used for these operations is not particularly limited, a lykai machine equipped with a stirring and heating apparatus, a three roll, a ball mill, a planetary mixer, and the like can be used. Moreover, you may combine these apparatuses suitably. The organic solvent should just be an organic solvent demonstrated below as a solvent for preparing the dispersion liquid of adhesive composition.

  The adhesive composition of the present invention has a viscosity at 25 ° C. of 10 to 3000 mPa · s, preferably 100 to 2000 mPa · s. The viscosity can be measured using a rotary viscometer.

  When forming an adhesive layer using the adhesive composition of the present invention, it is preferable to use the adhesive composition as a solution in which the adhesive composition is dispersed in an organic solvent. Examples of the organic solvent include N, N-dimethylacetamide, methyl ethyl ketone, N, N-dimethylformamide, cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, toluene, methanol, ethanol, isopropanol, acetone, propylene glycol monomethyl ether, Examples include propylene glycol monomethyl ether acetate, and preferably methyl ethyl ketone, cyclopentanone, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. These organic solvents may be used alone or in combination of two or more. The organic solvent is blended so that the solid component concentration is 30 to 70% by mass, preferably 40 to 65% by mass.

Production of Adhesive Sheet The present invention provides an adhesive sheet having an adhesive layer formed using the adhesive composition. Examples of the adhesive sheet include an adhesive sheet obtained by laminating an adhesive layer formed from the adhesive composition of the present invention and a protective layer (mold release substrate) covering the adhesive layer. . An example of the manufacturing method of the adhesive sheet of this invention is shown below.

  A solution obtained by dispersing the adhesive composition in an organic solvent is applied onto a protective layer (release substrate) using a reverse roll coater, a comma coater or the like. A protective layer (release substrate) coated with the dispersion of the adhesive composition is passed through an in-line dryer, and the organic solvent is removed and dried at 80 to 160 ° C. for 2 to 20 minutes to form an adhesive layer. The adhesive sheet has an adhesive layer. Moreover, it is good also as an adhesive sheet by pressure-bonding and laminating | stacking another protective layer (release base material) on the said adhesive bond layer using a roll laminator as needed. The thickness of the adhesive layer formed on the adhesive sheet is preferably 5 to 150 μm, particularly 10 to 100 μm.

  The protective layer (release substrate) used for the production of the adhesive sheet is not particularly limited as long as it can be peeled off from the adhesive layer without impairing the form of the adhesive layer. For example, a plastic film such as a polyethylene (PE) film, a polypropylene (PP) film, a polymethylpentene (TPX) film, a polyester film subjected to a release treatment, or the like can be used.

Use of Adhesive Sheet An adhesive sheet having an adhesive layer formed by using the adhesive composition of the present invention is, for example, a flip for directly connecting bumps provided on a semiconductor wafer and electrodes provided on a substrate. Can be used for chip mounting. It can also be used to connect semiconductor elements having through electrodes.

  An example of the aspect which mounts a semiconductor wafer using the adhesive sheet which has an adhesive bond layer formed using the adhesive composition of this invention is shown in FIGS. Each step will be described below.

(Step 1: FIG. 1)
A semiconductor wafer in which bumps (FIG. 1: omitted, FIG. 6: reference numeral 11) are formed in advance on an adhesive sheet (reference numeral 2 ′) formed by laminating a protective layer (reference numeral 1) and an adhesive layer (reference numeral 2). Bonded to the functional surface (bump forming surface) of (reference numeral 3) by thermocompression bonding or the like. The thermocompression bonding is usually performed at a temperature of 80 to 130 ° C., a pressure of 0.01 to 1 MPa, and a time of 5 to 300 seconds. Alternatively, the bonding is performed by bonding the adhesive sheet under vacuum at 50 to 1300 Pa, and then returning to atmospheric pressure.

(Process 2: FIG. 2)
The protective layer (symbol 1) surface of the adhesive sheet (symbol 2 ′) bonded to the semiconductor wafer (symbol 3) is pasted on a semiconductor processing protective tape (symbol 4), and the wafer ring (symbol 5) is used. to support. The protective tape for semiconductor processing can use what is generally marketed by the name of a back grinding tape, a dicing tape, etc., and should just select it suitably according to a use. The semiconductor processing protective tape (reference numeral 4) and the adhesive layer (reference numeral 2) can be directly bonded without using the protective layer (reference numeral 1). The process of sticking the pressure-sensitive adhesive sheet on the tape is usually a temperature of 20 to 40 ° C., a linear pressure of 5 to 50 N / cm, and a pressure bonding time of 5 to 60 seconds. You may perform this process using an adhesive tape. Moreover, it can bond by pressure-bonding by 50-1300Pa under a vacuum, and returning to atmospheric pressure after that.

(Process 3: FIG. 3)
Next, the semiconductor processing protection tape (reference numeral 4) is fixed to a grinding (polishing) stage (not shown), and the semiconductor wafer (reference numeral 3) is ground (polished) by a grind wheel (reference numeral 6). A grinding (polishing) apparatus having a grind wheel is not particularly limited, and a commercially available apparatus may be used. Here, the thickness of the semiconductor wafer after grinding (polishing) (FIG. 4: reference numeral 7) is not particularly limited, but is preferably about 30 to 600 μm.

(Process 4: FIG. 4)
The ground semiconductor wafer (reference numeral 7) is placed on the dicer table (reference numeral 9) so that the surface of the semiconductor processing protective tape (reference numeral 4) and the dicer table (reference numeral 9) are in contact with each other. The semiconductor wafer (reference numeral 7) is cut together with a protective layer (reference numeral 1) and an adhesive layer (reference numeral 2) using a dicing saw (not shown) having a dicing blade (reference numeral 8). The spindle rotation speed and cutting speed at the time of dicing may be appropriately selected. Usually, the spindle rotation speed is 25,000 to 45,000 rpm, and the cutting speed is 10 to 50 mm / sec.

(Process 5: FIG. 5)
A protective tape for semiconductor processing (reference numeral 4) is extended by an expanding device, and a certain gap is formed between each of the semiconductor chips (reference numeral 12) separated into pieces together with the adhesive sheet (reference numeral 2 '). The adhesive layer (reference numeral 2) and the protective layer (reference numeral 1) are peeled off, and a semiconductor chip (reference numeral 12) provided with the adhesive layer is picked up.

(Step 6: FIG. 6)
Position the bump (reference numeral 11) provided on the functional surface of the cut semiconductor chip (reference numeral 12) and the electrode (reference numeral 13) on the base substrate (reference numeral 10) using a flip chip bonder (not shown). In addition, the semiconductor chip (reference numeral 12) is mounted on the base substrate (reference numeral 10).

(Step 7: FIG. 7)
The bump (reference numeral 11) provided on the functional surface of the cut semiconductor chip (reference numeral 12) and the electrode (reference numeral 13) on the base substrate (reference numeral 10) are joined by thermocompression bonding. The thermocompression bonding is usually performed at a temperature of 100 to 280 ° C., a load of 1 to 500 N, and a time of 1 to 30 seconds. Thereafter, the adhesive composition is cured by heating, and the gap between the semiconductor chip (reference numeral 12) and the base substrate (reference numeral 10) is sealed. Curing of the adhesive composition is usually performed at 160 to 240 ° C., particularly 180 to 220 ° C., 0.5 to 6 hours, particularly 1 to 4 hours.

  As described above, by using the adhesive layer formed using the adhesive composition of the present invention, the steps (a), (d), (e) and (e) in the capillary underfill method (FIG. 8) and It becomes possible to omit the step (f). Moreover, the adhesive bond layer formed using the adhesive composition of this invention has the outstanding adhesiveness with respect to a base substrate at the time of pressure bonding. The cured adhesive layer is excellent in connection reliability and insulation reliability.

Semiconductor device protecting material The present invention also provides a semiconductor device protecting material having an adhesive layer formed using an adhesive composition. Examples of usage as a material for protecting a semiconductor device include a protective sheet in which an adhesive layer formed using the adhesive composition of the present invention and a protective tape for semiconductor processing are laminated. The surface of the semiconductor device can be protected by sticking the adhesive layer surface of the protective sheet to the surface to be protected of the semiconductor device, peeling off the protective tape, and then curing the adhesive layer surface to form a protective film. Since the cured product of the adhesive composition of the present invention is excellent in connection reliability and insulation reliability, it can suitably function as a protective film for semiconductor devices and electronic parts such as diodes, transistors, ICs, and LSIs. Examples of usage as a protective film include junction coating films, passivation films, and buffer coat films on the surface of semiconductor elements such as diodes, transistors, ICs, and LSIs; α-ray shielding films such as LSIs; interlayer insulating films for multilayer wiring; Circuit board conformal coating; ion implantation mask; solar cell surface protective film.

As the semiconductor device described above, as the method for manufacturing the semiconductor device of the present invention, a semiconductor chip is mounted on the base substrate via an adhesive layer formed using the adhesive composition of the present invention, then, A method for curing the adhesive composition is exemplified. As another aspect, a semiconductor device protecting material having an adhesive layer formed using the adhesive composition of the present invention is attached to a protective surface of a semiconductor device (adhered object), and then an adhesive is used. The method of hardening | curing a composition and forming a protective film is mentioned. The adhesive composition of the present invention provides a cured product that is excellent in film formability and adhesion to a substrate, and excellent in connection reliability and insulation reliability (migration resistance) under high temperature and high humidity conditions. Therefore, it can be suitably used for application to higher density and higher integration of semiconductor devices.

  EXAMPLES Hereinafter, although an Example is shown and this invention is further demonstrated, this invention is not restrict | limited to the following Example.

[Synthesis Examples 1 to 5]
In the synthesis examples, the weight average molecular weight of each polymer was determined by using a GPC column TSKgel Super HZM-H (manufactured by Tosoh Corporation) under the analysis conditions of a flow rate of 0.6 ml / min, an elution solvent tetrahydrofuran, and a column temperature of 40 ° C. It was measured by gel permeation chromatography (GPC) using dispersed polystyrene as a standard. Further, ¹ H-NMR analysis of each polymer was performed using JNM-LA300WB (manufactured by JEOL) and deuterated chloroform as a measurement solvent.

The compounds used in Synthesis Examples 1 to 5 are shown below.

[Synthesis Example 1]
In a 3 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device and a reflux condenser, 86.1 g (0.2 mol) of the compound represented by the above formula (S-1) and the above formula (S-3) After adding 93.0 g (0.5 mol) of the compound shown and 66.9 g (0.3 mol) of the compound represented by the above formula (S-5), 1300 g of toluene was added and heated to 70 ° C. . Thereafter, 1.0 g of toluene chloroplatinate solution (platinum concentration: 0.5 wt%) was added, and 194.4 g (1.0 mol) of the compound represented by the above formula (S-6) was added dropwise over 1 hour ( Total number of moles of hydrosilyl group / total number of moles of alkenyl group = 1/1). After completion of the dropwise addition, the mixture was heated to 100 ° C. and aged for 6 hours, and the structure of the product obtained by evaporating toluene from the reaction solution under reduced pressure was analyzed using ¹ H-NMR. It was a polymer. Moreover, the weight average molecular weight of polystyrene conversion measured by GPC of this polymer was 42,000.

（式中、ｒ／（ｒ＋ｓ＋ｔ）＝０．２、ｓ／（ｒ＋ｓ＋ｔ）＝０．３、及びｔ／（ｒ＋ｓ＋ｔ）＝０．５であり、各単位の末端ケイ素原子が各同じ単位あるいは異なる単位の末端炭素原子と結合しており、重合体の片末端はアルケニル基であり、もう一方の末端はケイ素原子に結合している水素原子である）

(Wherein, r / (r + s + t) = 0.2, s / (r + s + t) = 0.3, and t / (r + s + t) = 0.5, and the terminal silicon atom of each unit is the same unit or a different unit. And one end of the polymer is an alkenyl group, and the other end is a hydrogen atom bonded to a silicon atom)

[Synthesis Example 2]
In a 3 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device and a reflux condenser, 71.8 g (0.167 mol) of the compound represented by the above formula (S-1) and represented by the above formula (S-4) are shown. 333.3 g (0.074 mol) of the above compound and 14.9 g (0.067 mol) of the compound represented by the above formula (S-5) were added, and then 1150 g of toluene was added and heated to 70 ° C. Thereafter, 1.0 g of toluene chloroplatinate solution (platinum concentration 0.5 wt%) was added, and 64.8 g (0.333 mol) of the compound represented by the above formula (S-6) was dropped over 30 minutes ( Total number of moles of hydrosilyl group / total number of moles of alkenyl group = 1.08 / 1). After completion of dropping, the mixture was heated to 100 ° C. and aged for 6 hours, and then the structure of the product obtained by distilling toluene off from the reaction solution under reduced pressure was analyzed using ¹ H-NMR. It was a polymer. The weight average molecular weight in terms of polystyrene measured by GPC was 55,000.

（式中、ｒ／（ｒ＋ｓ＋ｔ）＝０．５、ｓ／（ｒ＋ｓ＋ｔ）＝０．２、及びｔ／（ｒ＋ｓ＋ｔ）＝０．３であり、各単位の末端ケイ素原子が各同じ単位あるいは異なる単位の末端炭素原子と結合しており、重合体の片末端はアルケニル基であり、もう一方の末端はケイ素原子に結合している水素原子である）

(Wherein, r / (r + s + t) = 0.5, s / (r + s + t) = 0.2, and t / (r + s + t) = 0.3, and the terminal silicon atom of each unit is the same unit or a different unit. And one end of the polymer is an alkenyl group, and the other end is a hydrogen atom bonded to a silicon atom)

[Synthesis Example 3]
In a 3 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device and a reflux condenser, 61.8 g (0.2 mol) of the compound represented by the above formula (S-2), and represented by the above formula (S-3). After adding 93.0 g (0.5 mol) of the compound and 66.9 g (0.3 mol) of the compound represented by the above formula (S-5), 1000 g of toluene was added, and the mixture was heated to 70 ° C. Thereafter, 1.0 g of a chloroplatinic acid toluene solution (platinum concentration: 0.5 wt%) was added, and 179.0 g (0.92 mol) of the compound represented by the above formula (S-6) and the above formula (S-7) Was added dropwise over 1 hour (total number of moles of hydrosilyl group / total number of moles of alkenyl group = 1/1). After completion of dropping, the mixture was heated to 100 ° C. and aged for 6 hours, and then the structure of the product obtained by distilling toluene off from the reaction solution under reduced pressure was analyzed using ¹ H-NMR. It was a polymer. The weight average molecular weight in terms of polystyrene measured by GPC was 52,000.

（式中、ｒ／（ｒ＋ｓ＋ｔ＋ｂ）＝０．２、ｓ／（ｒ＋ｓ＋ｔ＋ｂ）＝０．３、ｔ／（ｒ＋ｓ＋ｔ＋ｂ）＝０．４、及びｂ／（ｒ＋ｓ＋ｔ＋ｂ）＝０．１であり、各単位の末端ケイ素原子が各同じ単位あるいは異なる単位の末端炭素原子と結合しており、重合体の片末端はアルケニル基であり、もう一方の末端はケイ素原子に結合している水素原子である）

(Where r / (r + s + t + b) = 0.2, s / (r + s + t + b) = 0.3, t / (r + s + t + b) = 0.4, and b / (r + s + t + b) = 0.1, A terminal silicon atom is bonded to a terminal carbon atom of the same unit or a different unit, one end of the polymer is an alkenyl group, and the other end is a hydrogen atom bonded to the silicon atom)

[Synthesis Example 4]
In a 3 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device and a reflux condenser, 61.8 g (0.2 mol) of the compound represented by the above formula (S-2), and represented by the above formula (S-3). After adding 93.0 g (0.5 mol) of the compound and 66.9 g (0.3 mol) of the compound represented by the above formula (S-5), 1000 g of toluene was added, and the mixture was heated to 70 ° C. Thereafter, 1.0 g of a chloroplatinate toluene solution (platinum concentration: 0.5 wt%) was added, and 179.0 g (0.92 mol) of the compound represented by the above formula (S-6) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was heated to 100 ° C. and aged for 6 hours, and then 26.8 g (0.083 mol) of the compound represented by the above formula (S-8) was added dropwise over 1 hour (total of hydrosilyl groups). Number of moles / total number of moles of alkenyl group = 1/1). After completion of the dropwise addition, the mixture was aged at 100 ° C. for 2 hours, and the structure of the product obtained by evaporating toluene from the obtained reaction solution under reduced pressure was analyzed using ¹ H-NMR. It was a polymer. Moreover, the weight average molecular weight of polystyrene conversion measured by GPC was 66,000.

（式中、ｒ／（ｒ＋ｓ＋ｔ＋ｃ）＝０．２、ｓ／（ｒ＋ｓ＋ｔ＋ｃ）＝０．３、ｔ／（ｒ＋ｓ＋ｔ＋ｃ）＝０．４、及びｃ／（ｒ＋ｓ＋ｔ＋ｃ）＝０．１であり、各単位の末端ケイ素原子が各同じ単位あるいは異なる単位の末端炭素原子と結合しており、重合体の片末端はアルケニル基であり、もう一方の末端はケイ素原子に結合している水素原子である）

(Where r / (r + s + t + c) = 0.2, s / (r + s + t + c) = 0.3, t / (r + s + t + c) = 0.4, and c / (r + s + t + c) = 0.1, A terminal silicon atom is bonded to a terminal carbon atom of the same unit or a different unit, one end of the polymer is an alkenyl group, and the other end is a hydrogen atom bonded to the silicon atom)

（式中、ｒ／（ｒ＋ｓ＋ｔ＋ｄ）＝０．３２、ｓ／（ｒ＋ｓ＋ｔ＋ｄ）＝０．２９、ｔ／（ｒ＋ｓ＋ｔ＋ｄ）＝０．３７、及びｄ／（ｒ＋ｓ＋ｔ＋ｄ）＝０．０１であり、各単位の末端ケイ素原子が各同じ単位あるいは異なる単位の末端炭素原子と結合しており、重合体の片末端はアルケニル基であり、もう一方の末端はケイ素原子に結合している水素原子である） [Synthesis Example 5]
In a 3 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device and a reflux condenser, 142.1 g (0.33 mol) of the compound represented by the above formula (S-1) and represented by the above formula (S-3) are shown. After adding 70.7 g (0.38 mol) of the above compound and 66.9 g (0.3 mol) of the compound represented by the above formula (S-5), 1500 g of toluene was added, and the mixture was heated to 70 ° C. Thereafter, 2.0 g of toluene chloroplatinate solution (platinum concentration: 0.5 wt%) was added, and 190.5 g (0.98 mol) of the compound represented by the above formula (S-6) was dropped over 1.5 hours. did. After completion of the dropwise addition, the mixture was heated to 100 ° C. and aged for 6 hours, and then 6.8 g (0.01 mol) of the compound represented by the above formula (S-9) was added dropwise over 0.1 hour (hydrosilyl group). Total number of moles / total number of moles of alkenyl group = 1 / 1.03). After completion of dropping, the mixture was aged at 100 ° C. for 2 hours to obtain a polymer solution. When the structure of the product obtained by distilling toluene off from this reaction solution under reduced pressure was analyzed using ¹ H-NMR, it was a polymer represented by the following formula. The weight average molecular weight in terms of polystyrene measured by GPC was 50,000.

(Where r / (r + s + t + d) = 0.32, s / (r + s + t + d) = 0.29, t / (r + s + t + d) = 0.37, and d / (r + s + t + d) = 0.01, A terminal silicon atom is bonded to a terminal carbon atom of the same unit or a different unit, one end of the polymer is an alkenyl group, and the other end is a hydrogen atom bonded to the silicon atom)

[Examples 1-8 and Comparative Examples 1-4]
Preparation of Adhesive Composition In the composition described in Table 1, (A) the polymer synthesized in Synthesis Examples 1 to 5, (B) thermosetting resin, (C) compound having flux activity, and other optional components Was formulated. Further, cyclopentanone in an amount so that the solid component concentration was 50% by mass was added, stirred using a ball mill, mixed and dissolved to prepare a dispersion of the adhesive composition. In addition, the unit of the numerical value which shows the compounding quantity in Table 1 is a "mass part". Comparative Example 1 is an adhesive composition containing no (B) thermosetting resin, Comparative Example 2 is an adhesive composition containing no compound having (C) flux activity, and Comparative Example 3 is (A). It is an adhesive composition that does not contain a polymer, and Comparative Example 4 is an adhesive composition that includes an epoxy resin, an acrylic resin, and a compound having flux activity, as described in JP-A-2009-239138. is there.

Each component used for preparation of an adhesive composition is shown below.
(B) Thermosetting resin / EOCN-103S (trade name) (manufactured by Nippon Kayaku, epoxy equivalent: 209 to 219)
JER1001 (trade name) (Mitsubishi Chemical, epoxy equivalent: 450-500)
NC6000 (trade name) (Nippon Kayaku, epoxy equivalent: 192-202)
Here, the epoxy equivalent and the OH equivalent refer to the equivalent of the epoxy group or OH group that each component molecule has.

Further, the following epoxy resin curing agent and epoxy resin curing accelerator were used.
・ Epoxy resin curing agent:
Rekajit HH (trade name) (manufactured by Nippon Nippon Chemical Co., Ltd., hexahydrophthalic anhydride)
Phenolite TD-2093 (trade name) (manufactured by DIC, OH equivalent: 104)
・ Epoxy resin curing accelerator:
Cureazole 2P4MHZ (trade name) (manufactured by Shikoku Chemicals, 2-phenyl-4-methyl-5-hydroxymethylimidazole)

(C) Flux-active compound , phenolphthalein (manufactured by Wako Pure Chemical Industries)
・ Sebacic acid (manufactured by Wako Pure Chemical Industries)

Other optional components and inorganic fillers: silica (manufactured by Admatechs, SE1050, average particle size of 0.25 μm)
Coupling agent: KBM-303 (manufactured by Shin-Etsu Chemical, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane)
Acrylic rubber: SG-708-6 (manufactured by Nagase ChemteX, butyl acrylate-ethyl acrylate-acrylonitrile-acrylic acid-2-hydroxyethyl copolymer, weight average molecular weight 700,000)

Preparation of adhesive sheet On the surface of a polyester film (protective layer, manufactured by Toyobo Co., Ltd.) that has been subjected to mold release treatment with an applicator, the dispersion liquid of the adhesive composition is applied so that the thickness after drying is 25 μm, Then, an adhesive layer was formed by drying in a blowing oven for 5 minutes to prepare an adhesive sheet having the adhesive layer. The properties of each adhesive sheet were evaluated according to the following evaluation methods. The results are shown in Table 1.

Evaluation 1: In each one of the flexible adhesive sheets of the adhesive layer, the adhesive sheet was folded in a 180 ° direction with the adhesive layer of the adhesive sheet on the outside and the polyester film surface on the inside. Flexibility was evaluated with a case where cracking occurred in the adhesive layer or a case where the adhesive layer was peeled off from the polyester film, and a case where cracking or peeling did not occur as ○. The results are shown in Table 1. ○ was determined to be acceptable.

Evaluation 2: Adhesive strength of adhesive layer Each adhesive sheet was subjected to vacuum film laminator (temperature: 110 ° C., pressure: 80 Pa, TEAM-100 (manufactured by Takatori Co., Ltd.) was used and bonded to a 6-inch semiconductor wafer (thickness 625 μm, manufactured by Shin-Etsu Semiconductor Co., Ltd.) (FIG. 1). Next, the polyester film surface of the adhesive sheet was attached to a dicing tape (manufactured by Denka) supported by wafer ring at a linear pressure of about 10 N / cm at room temperature (FIG. 2). The semiconductor wafer and the adhesive sheet were cut into a size of 2 mm × 2 mm square using a dicing saw equipped with a dicing blade (DAD685, manufactured by DISCO) (FIG. 4). The semiconductor chip separated from the adhesive layer and the polyester film and picked up was picked up to obtain a semiconductor chip provided with the adhesive layer (FIG. 5). The spindle rotation speed during dicing was 30,000 rpm, and the cutting speed was 50 mm / sec. Each of the separated semiconductor chips was bonded onto a 15 mm × 15 mm silicon wafer (base substrate) through an adhesive layer at a load of 150 ° C. and 50 mN. Then, it heated at 180 degreeC for 1 hour, the adhesive composition was hardened, and the test piece was obtained. Five test pieces were manufactured for each and subjected to the following adhesive strength measurement test.

  Using a bond tester (Dage series 4000-PXY: manufactured by Dage), the resistance force applied when the semiconductor chip (2 mm × 2 mm) is peeled from the base substrate (15 mm × 15 mm silicon wafer) is measured, and the adhesive layer The adhesive strength of was evaluated. The test conditions were a test speed of 200 μm / sec and a test height of 50 μm. An implementation diagram of the adhesive strength measurement test is shown in FIG. In FIG. 9, the moving direction of the measurement jig (reference numeral 30) of the bond tester is indicated by an arrow (reference numeral 31). The results are shown in Table 1. The numerical value shown in Table 1 is the average of the measured values in each of five specimens, and the higher the numerical value, the higher the adhesive strength of the adhesive sheet.

Evaluation 3: Connection reliability An adhesive sheet having an adhesive layer thickness of 50 μm was prepared in accordance with the above-described method for producing an adhesive sheet. The bump adhering surface of the semiconductor wafer (8 inches, thickness 725 μm) provided with the bumps and the adhesive layer surface of each adhesive sheet were bonded using a vacuum film laminator (temperature: 110 ° C., pressure: 80 Pa) (FIG. 1). ). Thereafter, the protective layer surface of the semiconductor wafer provided with the adhesive sheet is pasted onto a back grind tape (made by Denka) supported by wafer ring at a linear pressure of about 10 N / cm at room temperature (FIG. 2), and a grinding (polishing) apparatus (DAG810). The product was ground (polished) until the thickness of the semiconductor wafer reached 100 μm using DISCO (FIG. 3).

  Next, the semiconductor wafer is cut into a 10 mm × 10 mm square using a dicing saw equipped with a dicing blade (FIG. 4), the separated semiconductor chip is picked up (FIG. 5), and the semiconductor chip provided with an adhesive layer (80 μmφ, Sn-3Ag-0.5Cu bump, bump height 50 μm, pitch 150 μm, number of bumps 3,844) were obtained. The spindle rotation speed during dicing was 40,000 rpm, and the cutting speed was 30 mm / sec.

  The semiconductor chip having the adhesive layer is aligned on a bismaleimide triazine (BT) resin substrate (thickness 0.94 mm) coated with a solder resist (manufactured by Taiyo Ink, PSR4000 AUS703) using a flip chip bonder. After performing and mounting (FIG. 6), it was heat-pressed at 255 ° C. for 15 seconds to produce flip chip packages (10 each). Thereafter, the package was heated at 180 ° C. for 1 hour to cure the adhesive layer.

  The connection resistance of each of the 10 flip chip packages manufactured by the above method was measured to confirm initial conduction. Thereafter, the package was subjected to a heat cycle test (holding at −25 ° C. for 10 minutes and holding at 125 ° C. for 10 minutes for 1000 cycles) to confirm conduction after the heat cycle test. In all cases, the connection reliability was evaluated by ◯ indicating that conduction was achieved, Δ indicating that conduction was initially achieved but ceased to be achieved after the heat cycle test, and x indicating that conduction was not initially achieved. The results are shown in Table 1. ○ was determined to be acceptable.

Evaluation 4: Insulation reliability (migration resistance)
A comb-shaped circuit having a Cu thickness of 5 μm and a line width / space width = 20 μm / 20 μm is prepared on a glass substrate, and using a vacuum film laminator (temperature: 110 ° C., pressure: 80 Pa), a comb shape is formed on the adhesive layer surface of the adhesive sheet. It was pasted so as to cover the circuit (the terminal portion was masked with a masking tape). Next, the protective layer of the adhesive sheet was peeled off, and the adhesive layer was cured by heating at 180 ° C. for 1 hour, thereby producing insulation reliability evaluation samples (5 pieces each). For each test piece, a DC voltage of 10 V was applied to both poles of the circuit under conditions of a temperature of 85 ° C. and a relative humidity of 85%, and insulation reliability was measured using a migration tester (IMV, MIG-86). Evaluated. When a short circuit (reduction in resistance value) occurs between the conductors within 1,000 hours after voltage application, or when dendrite growth is observed, it is evaluated as “bad” and indicated by x. The case where the resistance value was maintained even after the passage of time and no dendrite was generated was evaluated as “good” and indicated by ◯. The results are shown in Table 1.

  The connection reliability of Examples 1 to 8 and Comparative Examples 3 and 4 was evaluated as “good” in all 10 packages. The connection reliability of Comparative Examples 1 and 2 was evaluated as x in all 10 packages. The insulation reliability of Examples 1 to 8 and Comparative Examples 1 to 3 was evaluated as “good” for all five test pieces. The insulation reliability of Comparative Example 4 was evaluated as x in all five test pieces.

  From Table 1, the adhesive composition containing no film-forming resin is inferior in flexibility of the adhesive layer (Comparative Example 3). The cured product of the adhesive composition described in JP-A-2009-239138 has good flexibility of the adhesive layer, but causes migration and is inferior in insulation reliability (Comparative Example 4). On the other hand, the adhesive layer formed using the adhesive composition of the present invention is excellent in the flexibility of the adhesive layer and excellent in the adhesive force when it is pressure-bonded to the substrate, and the adhesive composition The cured product was excellent in connection reliability and insulation reliability. Further, the semiconductor device protected by the adhesive layer of the present invention is a semiconductor device in which connection reliability and insulation reliability are guaranteed. Comparative Example 1 shows that an adhesive composition not containing a thermosetting resin has poor adhesive strength and poor connection reliability, and Comparative Example 2 shows an adhesive composition that does not contain a compound having flux activity. Indicates that connection reliability is inferior.

  The adhesive composition of the present invention provides a cured product that is excellent in film formability and adhesion to a substrate, and excellent in connection reliability and insulation reliability (migration resistance) under high temperature and high humidity conditions. can do. Therefore, it is expected that the adhesive composition of the present invention is suitably used for application to higher density and higher integration of semiconductor devices.

  DESCRIPTION OF SYMBOLS 1 ... Protective layer, 2 ... Adhesive layer, 2 '... Adhesive sheet, 3 ... Semiconductor wafer, 4 ... Protective tape for semiconductor processing, 5 ... Wafer ring, 6 ... Grind wheel, 7 ... Grinded (polished) semiconductor wafer , 8 ... Dicing blade, 9 ... Dicer table, 10 ... Base substrate, 11 ... Bump, 12 ... Divided semiconductor chip, 13 ... Electrode, 14 ... Junction between semiconductor chip and substrate, 20 ... Circuit board, 21 ... Flux, 22 ... Semiconductor chip, 22a ... Semiconductor chip bump, 23 ... Semiconductor chip and substrate joint, 24 ... Underfill agent, 24a ... Hardened material of underfill agent, 30 ... Measurement jig for bond tester, 31 ... Moving direction of measuring jig for bond tester

Claims (11)

Adhesive composition containing the following (A), (B) and (C) components (A) containing repeating units represented by the following formulas (1-1), (1-2) and (1-3) A polymer having a polystyrene-equivalent weight average molecular weight of 3,000 to 500,000 as measured by GPC using tetrahydrofuran as an elution solvent

In the formula, r, s and t are positive integers, and the terminal silicon atom of each unit constituting the repeating unit represented by the formula (1-1), the formula (1-2) and the formula (1-3) Are bonded to the terminal carbon atom of X ¹ , X ² or X ³ of the same unit or different units, and in the formula, R ¹ is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. , X ¹ are each independently a divalent group represented by the following formula (2):

(In the formula, Z is a substituted or unsubstituted divalent hydrocarbon group having 1 to 15 carbon atoms, and p is 0 or 1. R ² is independently alkyl having 1 to 4 carbon atoms. Group or alkoxy group, q is 0, 1 or 2)
X ² is, independently of each other, a divalent group represented by the following formula (3),

(Wherein R ³ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms, or a glycidyl group)
X ³ is, independently of each other, a divalent group represented by the following formula (4),

(In the formula, R ⁴ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, and n is an integer of 0 to 100).
(B) Thermosetting resin (C) Compound having flux activity. In the formula (2), Z is

The adhesive composition according to claim 1, which is a group selected from any one of the above. The component (A) further has at least one of a unit represented by the following formula (5), a unit represented by the following formula (6), and a unit represented by the following formula (7). The adhesive composition described in 1.

(In the formula, R ¹ is each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, m is an integer of 0 to 100, and e, f, g, h, i and j are 0 to 0. It is an integer of 100, provided that e + f + g ≧ 3, e = f = 0 and not h = i = 0 X is independently of each other a group represented by the above-mentioned X ¹ , X ² or X ³ Each unit constituting the repeating unit represented by the above formula (1-1), formula (1-2) and formula (1-3), and the above formula (5), formula (6) and formula The terminal silicon atom of the unit represented by (7) is bonded to the terminal carbon atom of the same unit or a different unit).   The amount of the component (B) is 5 to 500 parts by mass with respect to 100 parts by mass of the component (A), and the amount of the component (C) is 1 to 20 with respect to 100 parts by mass in total of the components (A) and (B). The adhesive composition according to any one of claims 1 to 3, wherein the adhesive composition is part by mass.   The adhesive composition according to any one of claims 1 to 4, wherein the thermosetting resin is an epoxy resin.   The adhesive composition according to claim 5, further comprising at least one of an epoxy resin curing agent and an epoxy resin curing accelerator.   The adhesive composition according to any one of claims 1 to 6, wherein the compound having flux activity has a carboxy group or a phenolic hydroxyl group.   The adhesive sheet which has an adhesive bond layer formed using the adhesive composition of any one of Claims 1-7.   The semiconductor device protection material which has an adhesive bond layer formed using the adhesive composition of any one of Claims 1-7.   A semiconductor device protected using the semiconductor device protecting material according to claim 9.   The semiconductor device provided with the hardened | cured material of the adhesive composition of any one of Claims 1-7.

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