JP6547220B2 - Adhesive for die bonding - Google Patents

Description

  The present invention relates to a die bonding adhesive containing a thermosetting resin.

  At the time of manufacturing a semiconductor package, a semiconductor chip having a film-like adhesive for die bonding attached to the back surface opposite to the circuit surface is die-bonded to a lead frame or substrate by this adhesive, and in some cases, this die After laminating the semiconductor chip on the circuit surface of the bonded semiconductor chip, the electrode part of the semiconductor chip is connected to the lead frame, the conductor on the substrate, etc. by metal wires, and wire bonding is performed to electrically connect these. . Finally, the entire stack is covered with a resin, pressurized and heated, and sealed to form a semiconductor package. At the time of this sealing, the curing of the film adhesive is completed.

  Among these manufacturing steps, when die bonding is performed, a void (hereinafter referred to as a “void”) is usually generated between the film adhesive and the substrate to which the adhesive is to be attached. By control, this void disappears by the above-mentioned pressurization and heating at the time of sealing with resin.

  However, for example, in the step of performing die bonding or wire bonding, if the heating time is long, voids will not disappear but remain between the film adhesive and the substrate even after sealing. This is because the curing of the film-like adhesive proceeds beyond the allowable range in the above process, and the film-like adhesive is already hard at the stage before sealing, and follows the adhesive surface of the substrate etc. It is presumed that the cause is a decrease in sex. The semiconductor package in which such a void remains has low reliability such as generation of a crack under wet heat conditions.

  On the other hand, it is an adhesive sheet used for manufacture of a semiconductor package by which an adhesive layer and an adhesive layer are laminated in this order on a substrate, and what is excellent in adhesion reliability of a semiconductor chip and an adhesive layer is disclosed (See Patent Document 1). The adhesive sheet is mainly composed of a high molecular weight resin component and a low molecular weight resin component having a weight average molecular weight of 3000 or less.

Unexamined-Japanese-Patent No. 2004-256695

  However, the semiconductor package obtained by using the adhesive sheet disclosed in Patent Document 1 has high reliability even when the heating time becomes long in the step of performing die bonding and wire bonding as described above. It is not clear whether or not.

  The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide an adhesive for die bonding capable of manufacturing a semiconductor package having high reliability even if the heating time in steps other than sealing becomes long. I assume.

In order to solve the above problems, the present invention contains an epoxy resin and a phenol resin as an epoxy-based thermosetting resin, and further contains a polymer component that does not correspond to the epoxy resin and the phenol resin, and the epoxy resin and the phenol resin Has a biphenylene group which may have a substituent, and the epoxy resin has two or more constitutional units including the biphenylene group and a group having an epoxy group as an essential constitutional unit in the main chain It is a polymer compound which it has, and the said polymer component provides an adhesive agent for die bonding characterized by including acrylic resin.
The adhesive for die bonding of the present invention preferably has a mass ratio of "content of the polymer component: content of the epoxy-based thermosetting resin" of 65: 35 to 99: 1.

  According to the present invention, there is provided an adhesive for die bonding capable of manufacturing a semiconductor package having high reliability even when the heating time in the process other than sealing becomes long.

<< Die bonding adhesive >>
The adhesive agent for die bonding according to the present invention (hereinafter sometimes abbreviated as "adhesive") contains an epoxy resin and a phenol resin as an epoxy-based thermosetting resin, and the epoxy resin and the phenol resin are substituted. It is characterized by having a biphenylene group which may have a group.
The adhesive is usually provided in the form of a film on a support sheet and used as a film adhesive. As the support sheet, a substrate or a substrate provided with a pressure-sensitive adhesive layer can be used, and in the case of using a support sheet provided with a pressure-sensitive adhesive layer, a film adhesive is formed on the pressure-sensitive adhesive layer. Set up. Then, a film adhesive is applied to the back surface of the semiconductor chip opposite to the circuit surface, and is used for die bonding to a lead frame or a substrate, and is sealed with resin after wire bonding to form a semiconductor package The curing is completed by heating.

  When the adhesive is used for producing a semiconductor package, the epoxy resin and the phenol resin used in combination as a thermosetting resin each have a biphenylene group which may have a substituent. Even if the heating time in processes other than sealing, such as the process of performing wire bonding, is prolonged, peeling between the adhesive and the bonding target such as a substrate is suppressed, and the generation of cracks is suppressed. Thus, by using the adhesive, a highly reliable semiconductor package can be obtained.

  As described above, the reason why the peeling is suppressed between the adhesive and the substrate or the like even if the heating time in the process other than sealing is prolonged is presumed as follows. That is, curing of the adhesive is suppressed at the time of heating in the process before sealing, and a state of high followability to the adhesive surface of a substrate or the like is maintained. As a result, curing of the adhesive is completed at sealing. In the stage, it is presumed that the void between the adhesive and the substrate has disappeared as in the case where the heating time in the process other than sealing is short. The curing of the adhesive is suppressed during heating in steps other than sealing because the epoxy resin and the phenolic resin both have a biphenylene group which may have a substituent, and the molecules of these resins are compared It is speculated that this is because the reaction is rigid and it is difficult for the curing reaction to proceed.

  Hereinafter, in the present specification, the “epoxy resin having a biphenylene group which may have a substituent” is referred to as “epoxy resin (b1)” and has “a biphenylene group which may have a substituent”. The phenol resin may be referred to as "phenol resin (b2)". Moreover, the epoxy-type thermosetting resin which consists of these epoxy resin (b1) and a phenol resin (b2) may be called "epoxy-type thermosetting resin (b)."

  The adhesive has heat curing property, and further preferably has pressure sensitive adhesive property. The adhesive having both pressure-sensitive adhesiveness and heat-curing property can be attached by lightly pressing on various adherends in an uncured state. Further, the adhesive may be applied to various adherends by heating and softening. The adhesive finally becomes a cured product having high impact resistance after heat curing, and the cured product is excellent in shear strength and can retain sufficient adhesive properties even under severe high temperature and high humidity conditions.

<Adhesive composition>
The said adhesive can be manufactured using the adhesive composition containing the component for comprising adhesives, such as said epoxy-type thermosetting resin (b). The ratio of the contents of non-volatile components in the adhesive composition is the same in the adhesive. Each component will be described below.

[Epoxy-based thermosetting resin (b)]
The epoxy-based thermosetting resin (b) comprises the epoxy resin (b1) and the phenol resin (b2).
The epoxy-based thermosetting resin (b) may be used alone or in combination of two or more.

(Epoxy resin (b1))
The epoxy resin (b1) is a biphenyl type epoxy resin having a biphenylene group which may have a substituent. Here, "biphenylene group" means a divalent group obtained by removing two hydrogen atoms from biphenyl (diphenyl, C ₆ H ₅ -C ₆ H ₅ ), and may also be referred to as a diphenylene group. usually it made been removed is one by one hydrogen atom from a single benzene ring skeleton - is a _{(-C 6 H 4 -C 6 H} 4).
The position of the free valence of the biphenylene group which the epoxy resin (b1) has is not particularly limited, but is preferably 4,4′-biphenylene group.

  In the present specification, "a biphenylene group having a substituent" means a biphenylene group in which 1 to 8 hydrogen atoms are substituted by a group (substituent) other than a hydrogen atom, and the number of substituents is 1 to 6 The number of substituents is not particularly limited as long as it is eight, and when the number of substituents is two or more, these two or more substituents may all be identical or all may be different. Only part may be identical. Also, the bonding position of the substituent is not particularly limited.

  The epoxy resin (b1) has a biphenylene group and a group having an epoxy group (hereinafter sometimes abbreviated as “epoxy group-containing group”) in the main chain as an essential constituent unit, and Any epoxy group-containing group may or may not be included in the side chain.

  The structural unit having an epoxy group in the epoxy resin (b1) preferably has a structure in which a hydrogen atom of a hydroxyl group, preferably a phenolic hydroxyl group is substituted by an epoxy group with or without a linking group. As said coupling group, bivalent groups, such as an alkylene group, can be illustrated. For example, a structural unit having a structure in which a hydrogen atom of a hydroxyl group is substituted with an epoxy group via a methylene group, in other words, a structure in which a hydrogen atom of a hydroxyl group is directly substituted with a glycidyl group without a linking group is It can be obtained by a method comprising the step of reacting epichlorohydrin (2-chloromethyl oxirane) with the hydroxyl group.

The weight average molecular weight of the epoxy resin (b1) is preferably 300 to 100,000, and more preferably 300 to 20,000.
In addition, in this specification, a weight average molecular weight is a polystyrene conversion value measured by the gel permeation chromatography (GPC) method unless there is particular notice.

  It is preferable that an epoxy equivalent is 180-350 g / eq, and, as for an epoxy resin (b1), it is more preferable that it is 230-320 g / eq.

  The softening point of the epoxy resin (b1) is preferably 50 to 100 ° C., and more preferably 60 to 85 ° C.

As a preferable epoxy resin (b1), those represented by the following general formula (I) can be exemplified. This epoxy resin (b1) has a biphenyl skeleton (biphenylene group which may have a substituent) and a benzene ring skeleton (a glycidyloxy group as a substituent, and may be a phenylene which may have other substituents) And the group) has a structure in which a methylene group is bonded as a repeating unit. Here, “a phenylene group having a substituent” means a phenylene group (—C ₆ H ₄ —) in which one or more hydrogen atoms are substituted with a group (substituent) other than a hydrogen atom.

（式中、Ｘ^１１、Ｘ^１２、Ｘ^１３、Ｘ^１４、Ｘ^１５、Ｘ^１６及びＸ^１７は、それぞれ独立に水素原子以外の基であり；ｍ１１は０以上の整数であり；ｎ１１、ｎ１２、ｎ１３、ｎ１５、ｎ１６及びｎ１７は、それぞれ独立に０〜４の整数であり、ｎ１４は０〜３の整数であり、ｍ１１個のｎ１２の値は互いに同一でも異なっていてもよく、ｍ１１個のｎ１３の値は互いに同一でも異なっていてもよく、ｍ１１個のｎ１４の値は互いに同一でも異なっていてもよく；ｎ１１が２以上である場合、複数個のＸ^１１は互いに同一でも異なっていてもよく、ｍ１１が２以上であるか又はｎ１２が２以上である場合、複数個のＸ^１２は互いに同一でも異なっていてもよく、ｍ１１が２以上であるか又はｎ１３が２以上である場合、複数個のＸ^１３は互いに同一でも異なっていてもよく、ｍ１１が２以上であるか又はｎ１４が２以上である場合、複数個のＸ^１４は互いに同一でも異なっていてもよく、ｎ１５が２以上である場合、複数個のＸ^１５は互いに同一でも異なっていてもよく、ｎ１６が２以上である場合、複数個のＸ^１６は互いに同一でも異なっていてもよく、ｎ１７が２以上である場合、複数個のＸ^１７は互いに同一でも異なっていてもよく；ｎ１１が２以上である場合、複数個のＸ^１１は互いに結合して環を形成していてもよく、ｎ１２が２以上である場合、複数個のＸ^１２は互いに結合して環を形成していてもよく、ｎ１３が２以上である場合、複数個のＸ^１３は互いに結合して環を形成していてもよく、ｎ１４が２以上である場合、複数個のＸ^１４は互いに結合して環を形成していてもよく、ｎ１５が２以上である場合、複数個のＸ^１５は互いに結合して環を形成していてもよく、ｎ１６が２以上である場合、複数個のＸ^１６は互いに結合して環を形成していてもよく、ｎ１７が２以上である場合、複数個のＸ^１７は互いに結合して環を形成していてもよい。）

(Wherein, X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , X ¹⁶ and X ¹⁷ are each independently a group other than a hydrogen atom; m 11 is an integer of 0 or more; n 11, n 12, n13, n15, n16 and n17 are each independently an integer of 0 to 4, n14 is an integer of 0 to 3, and the values of m11 n12 may be the same or different from each other, and m11 n13 The values of m may be the same or different, and the values of m11 n14 may be the same or different; when n11 is 2 or more, a plurality of X ¹¹ may be the same or different , M11 is 2 or more, or when n12 is 2 or more, plural X ¹² may be the same or different from each other, and when m11 is 2 or more or n13 is 2 or more, plural X of ³ may be the same or different, when m11 is or n14 is 2 or more is 2 or more, may be the same or different from each other a plurality of X ^14, when n15 is 2 or more, The plurality of X ¹⁵ may be the same or different, and when n ¹⁶ is 2 or more, the plurality of X ¹⁶ may be the same or different, and when n 17 is 2 or more, the plurality of X 15 ¹⁷ may be the same as or different from each other; when n11 is 2 or more, a plurality of X ¹¹ may combine with each other to form a ring, and when n12 is 2 or more, a plurality of X 11 ¹² may be bonded to each other to form a ring, and when n13 is 2 or more, a plurality of X ¹³ may be bonded to each other to form a ring, and when n14 is 2 or more, Several X ¹⁴ combine with each other And when n15 is 2 or more, a plurality of X ¹⁵ may combine with each other to form a ring, and when n ¹⁶ is 2 or more, a plurality of X ¹⁵ may form a ring. ¹⁶ may be bonded to each other to form a ring, and when n ¹⁷ is 2 or more, a plurality of X ¹⁷ may be bonded to each other to form a ring)

In general formula (I), X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , X ¹⁶ and X ¹⁷ are each independently a group other than a hydrogen atom.
When n12 is not 0, X ¹² is bonded to one phenylene group (benzene ring skeleton) constituting a biphenylene group, and the bonding position is not particularly limited. When n13 is not 0, X ¹³ is bonded to the other phenylene group (benzene ring skeleton) constituting the biphenylene group, and the bonding position is not particularly limited.
Similarly, if n15 is not 0, X ¹⁵ is attached to one of the phenylene group constituting the biphenylene group (a benzene ring skeleton), the binding position is not particularly limited. When n16 is not 0, X ¹⁶ is bonded to the other phenylene group (benzene ring skeleton) constituting the biphenylene group, and the bonding position is not particularly limited.

When n11 is not 0, the bonding position of X ^{11 to} the benzene ring skeleton is not particularly limited.
Similarly, if n14 is not zero, the bonding position of the benzene ring skeleton of X ¹⁴ is not particularly limited.
Similarly, when n17 is not 0, the bonding position of X ^{17 to} the benzene ring skeleton is not particularly limited.

  The group (substituent) other than the hydrogen atom is not particularly limited, and an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyloxy group, a heterocyclic group, a halogen atom, a hydroxyl group and the like can be exemplified. However, it is not limited to these.

  The alkyl group may be linear, branched or cyclic, and when it is cyclic, it may be monocyclic or polycyclic. The alkyl group preferably has 1 to 5 carbon atoms, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. And n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group and the like.

The alkenyl group may be linear, branched or cyclic, and when it is cyclic, it may be monocyclic or polycyclic.
Examples of the alkenyl group include ethenyl group (vinyl group), 2-propenyl group (allyl group), cyclohexenyl group, etc., and one single bond (C-C) between carbon atoms in the alkyl group is double. A group substituted by a bond (C = C) can be exemplified. And as for the said alkenyl group, it is preferable that carbon number is 2-5.

  The aryl group may be either monocyclic or polycyclic, and preferably has 6 to 12 carbon atoms, and is preferably a phenyl group, 1-naphthyl group, 2-naphthyl group, o-tolyl group, m-tolyl group, Although p-tolyl group, xylyl group (dimethylphenyl group) etc. can be illustrated, it is not limited to these.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group and a cyclopropoxy group, and a monovalent group formed by bonding the alkyl group to an oxygen atom.
Examples of the aryloxy group include a phenyloxy group (phenoxy group), a 1-naphthyloxy group, and a monovalent group formed by bonding the aryl group to an oxygen atom.
As said alkenyloxy group, the monovalent group which the said alkenyl group couple | bonds with an oxygen atom, such as an ethenyl oxy group, 2-propenyl oxy group, cyclohexenyloxy group, etc. can be illustrated.

The heterocyclic group may have at least one hetero atom as an atom constituting a ring skeleton, and may be any of an aromatic cyclic group (heteroaryl group) and an aliphatic cyclic group, It may be either monocyclic or polycyclic.
As a hetero atom which the said heterocyclic group has, an oxygen atom, a sulfur atom, a nitrogen atom etc. can be illustrated.
When the said heterocyclic group has 2 or more hetero atoms, these hetero atoms may mutually be same or different. That is, two or more hetero atoms may be all identical, all different, or only part of them may be identical.
As said heterocyclic group, in said cyclic alkyl group or aryl group, one or more carbon atoms are substituted alone or together with a hydrogen atom to which a carbon atom is bonded, a hetero atom It can be illustrated.

  As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. can be illustrated.

When there are a plurality of X ¹² , that is, m 11 is 2 or more, or n 12 is 2 or more (2, 3 or 4), the plurality of X ¹² may be the same or different from each other. That is, all X ¹² may be identical, all X ¹² may be different, or only a part of X ¹² may be identical.
Similarly, when there are a plurality of X ¹³ , ie, m 11 is 2 or more, or n 13 is 2 or more (2, 3 or 4), the plurality of X ¹³ are identical or different from each other. It is also good.
Similarly, when there are a plurality of X ¹⁴ , ie, m 11 is 2 or more or n ¹⁴ is 2 or more (2 or 3), the plurality of X ¹⁴ may be the same or different from each other .

When there are a plurality of X ¹¹ , that is, n ¹¹ is 2 or more (2, 3 or 4), the plurality of X ¹¹ may be the same as or different from each other. That is, all X ¹¹ may be the same, all X ¹¹ may be different, or only some X ¹¹ may be the same.
Similarly, in the case where there are a plurality of X ¹⁵ , that is, n ¹⁵ is 2 or more (2, 3 or 4), the plurality of X ¹⁵ may be the same as or different from each other.
Similarly, when there are a plurality of X ¹⁶ , that is, n ¹⁶ is 2 or more (2, 3 or 4), the plurality of X ¹⁶ may be the same or different.
^Similarly, when ^{X 17} is a plurality, i.e., when n17 is 2 or more (2, 3 or 4), a plurality of ^{X 17} and these may be the same or different from each other.

When n11 is 2 or more (2, 3 or 4), a plurality of X ¹¹ may be bonded to each other to form a ring with the carbon atom to which X ¹¹ is bonded, in which case The ring may be either monocyclic or polycyclic, and may be either aromatic or aliphatic.
When n12 is 2 or more (2, 3 or 4), as in the case of X ¹¹ above, a plurality of X ¹² are bonded to each other to form a ring with the carbon atom to which these X ¹² are bonded It may be done.
When n13 is 2 or more (2, 3 or 4), as in the case of X ¹¹ described above, a plurality of X ¹³ are bonded to each other to form a ring with the carbon atom to which X ¹³ is bonded It may be done.
When n14 is 2 or more (2 or 3), as in the case of X ¹¹ described above, a plurality of X ¹⁴ are bonded to each other to form a ring together with the carbon atom to which X ¹⁴ is bonded May be
When n15 is 2 or more (2, 3 or 4), as in the case of X ¹¹ above, a plurality of X ¹⁵ are bonded to each other to form a ring with the carbon atom to which X ¹⁵ is bonded It may be done.
When n16 is 2 or more (2, 3 or 4), as in the case of X ¹¹ above, a plurality of X ¹⁶ are bonded to each other to form a ring with the carbon atom to which these X ¹⁶ are bonded It may be done.
When n17 is 2 or more (2, 3 or 4), as in the case of X ¹¹ described above, a plurality of X ¹⁷ are bonded to each other to form a ring with the carbon atom to which X ¹⁷ is bonded It may be done.

  In the epoxy resin (b1) represented by the above general formula (I), a benzene ring skeleton (as a substituent) of a methylene group bonded to a biphenyl skeleton (biphenylene group which may have a substituent) The bonding position to a phenylene group which has a group and may have other substituents is not particularly limited, and may be the same in all benzene ring skeletons, or different in all the benzene ring skeletons Or only part of the benzene ring skeleton may be the same.

  The epoxy resin (b1) represented by the general formula (I) is preferably one in which n11, n12, n13, n14, n15, n16 and n17 are all 0.

  m11 may be an integer of 0 or more, and the upper limit thereof is not particularly limited.

  An epoxy resin (b1) may be used individually by 1 type, and may use 2 or more types together.

  The epoxy resin (b1) may be obtained by reacting a monomer that derives the constituent unit by a known method, and a commercially available product may be used as the epoxy resin (b1).

(Phenolic resin (b2))
The phenol resin (b2) functions as a curing agent for the epoxy resin (b1).
The phenol resin (b2) is a biphenyl type phenol resin having a biphenylene group which may have a substituent. Here, the “biphenylene group which may have a substituent” is the same as in the case of the epoxy resin (b1).

The phenol resin (b2) has a biphenylene group and a group derived from phenols (hereinafter sometimes abbreviated as "phenols derivative group") as an essential constituent unit in the main chain, and a biphenylene group And the above-mentioned phenol derivative group may or may not have in the side chain.
Here, “phenols” refers to both phenol and phenol in which one or more hydrogen atoms other than hydrogen atoms constituting a hydroxyl group are substituted with groups (substituents) other than hydrogen atoms. It is a concept that encompasses

  The weight average molecular weight of the phenol resin (b2) is preferably 400 to 1,000,000, and more preferably 400 to 20,000.

  It is preferable that a hydroxyl equivalent is 140-310 g / eq, and, as for a phenol resin (b2), it is more preferable that it is 190-280 g / eq.

  It is preferable that a softening point is 90-140 degreeC, and, as for a phenol resin (b2), it is more preferable that it is 110-130 degreeC.

As a preferable thing as a phenol resin (b2), what is represented with the following general formula (II) can be illustrated. In this phenol resin (b2), a biphenyl skeleton (biphenylene group which may have a substituent) and a phenol skeleton (phenol diyl group which may have a substituent) are linked by a methylene group It has a structure as a repeating unit. Here, “a phenoldiyl group having a substituent” means a phenoldiyl group (—C ₆ H ₃ (—OH) — in which one or more hydrogen atoms are substituted by a group (substituent) other than a hydrogen atom) Means).

（式中、Ｘ^２１、Ｘ^２２、Ｘ^２３、Ｘ^２４、Ｘ^２５、Ｘ^２６及びＸ^２７は、それぞれ独立に水素原子以外の基であり；ｍ２１は０以上の整数であり；ｎ２１、ｎ２２、ｎ２３、ｎ２５、ｎ２６及びｎ２７は、それぞれ独立に０〜４の整数であり、ｎ２４は０〜３の整数であり、ｍ２１個のｎ２２の値は互いに同一でも異なっていてもよく、ｍ２１個のｎ２３の値は互いに同一でも異なっていてもよく、ｍ２１個のｎ２４の値は互いに同一でも異なっていてもよく；ｎ２１が２以上である場合、複数個のＸ^２１は互いに同一でも異なっていてもよく、ｍ２１が２以上であるか又はｎ２２が２以上である場合、複数個のＸ^２２は互いに同一でも異なっていてもよく、ｍ２１が２以上であるか又はｎ２３が２以上である場合、複数個のＸ^２３は互いに同一でも異なっていてもよく、ｍ２１が２以上であるか又はｎ２４が２以上である場合、複数個のＸ^２４は互いに同一でも異なっていてもよく、ｎ２５が２以上である場合、複数個のＸ^２５は互いに同一でも異なっていてもよく、ｎ２６が２以上である場合、複数個のＸ^２６は互いに同一でも異なっていてもよく、ｎ２７が２以上である場合、複数個のＸ^２７は互いに同一でも異なっていてもよく；ｎ２１が２以上である場合、複数個のＸ^２１は互いに結合して環を形成していてもよく、ｎ２２が２以上である場合、複数個のＸ^２２は互いに結合して環を形成していてもよく、ｎ２３が２以上である場合、複数個のＸ^２３は互いに結合して環を形成していてもよく、ｎ２４が２以上である場合、複数個のＸ^２４は互いに結合して環を形成していてもよく、ｎ２５が２以上である場合、複数個のＸ^２５は互いに結合して環を形成していてもよく、ｎ２６が２以上である場合、複数個のＸ^２６は互いに結合して環を形成していてもよく、ｎ２７が２以上である場合、複数個のＸ^２７は互いに結合して環を形成していてもよい。）

(Wherein, X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ and X ²⁷ are each independently a group other than a hydrogen atom; m ²¹ is an integer of 0 or more; n ²¹ , n ²² , n23, n25, n26 and n27 are each independently an integer of 0 to 4, n24 is an integer of 0 to 3, and the values of m21 n22 may be the same as or different from each other, and m21 n23 The values of n may be the same as or different from each other, and the values of n 24 of m ²¹ may be the same as or different from each other; when n ²¹ is 2 or more, a plurality of X ²¹ may be the same as or different from each other , When m21 is 2 or more or n22 is 2 or more, the plurality of X ²² may be the same or different from each other, and when m21 is 2 or more or n23 is 2 or more, a plurality of X ²² X of ³ may be the same or different, when m21 is or n24 is 2 or more is 2 or more, plural X ²⁴ may be the same or different, when n25 is 2 or more, The plurality of X ²⁵ may be the same or different, and when n ²⁶ is 2 or more, the plurality of X ²⁶ may be the same or different, and when n 27 is 2 or more, the plurality of X 25 ²⁷ may be the same as or different from each other; when n ²¹ is 2 or more, a plurality of X ²¹ may be bonded to each other to form a ring, and when n ²² is 2 or more, a plurality of X ^{21 22} may be bonded to each other to form a ring, and when n23 is 2 or more, a plurality of X ²³ may be bonded to each other to form a ring, and when n24 is 2 or more, Multiple X's ²⁴ combine with each other And when n ²⁵ is 2 or more, a plurality of X ²⁵ may combine with each other to form a ring, and when n 26 is 2 or more, a plurality of X ²⁵ may form a ring. ²⁶ may be bonded to each other to form a ring, and when n ²⁷ is 2 or more, a plurality of X ²⁷ may be bonded to each other to form a ring)

X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ and X ²⁷ in the general formula (II) are X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ and X in the general formula (I) Similar to X ¹⁶ and X ¹⁷ .
M21 in the general formula (II) is the same as m11 in the general formula (I).
N21, n22, n23, n25, n26 and n27 in the general formula (II) are the same as n11, n12, n13, n15, n16 and n17 in the general formula (I), and in the general formula (II) n24 is the same as n14 in the general formula (I).

Thus, for example, when n21 is 2 or more (2, 3 or 4), a plurality of X ²¹ may be bonded to each other to form a ring together with the carbon atom to which X ²¹ is bonded, The ring formed in this case may be either monocyclic or polycyclic, and may be either aromatic or aliphatic.
When n22 is 2 or more (2, 3 or 4), as in the case of X ²¹ described above, a plurality of X ²² are bonded to each other to form a ring with the carbon atom to which these X ²² are bonded It may be done.
When n23 is 2 or more (2, 3 or 4), as in the case of X ²¹ described above, a plurality of X ²³ are bonded to each other to form a ring with the carbon atom to which these X ²³ are bonded It may be done.
When n24 is 2 or more (2 or 3), as in the case of X ²¹ described above, a plurality of X ²⁴ are bonded to each other to form a ring with the carbon atom to which these X ²⁴ are bonded May be
When n25 is 2 or more (2, 3 or 4), as in the case of X ²¹ described above, a plurality of X ²⁵ are bonded to each other to form a ring with the carbon atom to which these X ²⁵ are bonded It may be done.
When n26 is 2 or more (2, 3 or 4), as in the case of X ²¹ described above, a plurality of X ²⁶ are bonded to each other to form a ring with the carbon atom to which these X ²⁶ are bonded It may be done.
When n27 is 2 or more (2, 3 or 4), as in the case of X ²¹ described above, a plurality of X ²⁷ are bonded to each other to form a ring with the carbon atom to which these X ²⁷ are bonded It may be done.

  The phenol resin (b2) represented by the above general formula (II) has a phenol skeleton (substituent group) of a methylene group bonded to a biphenyl skeleton (biphenylene group which may have a substituent group) The bonding position to the (optionally phenoldiyl group) is not particularly limited, and may be the same in all phenol skeletons, or may be different in all phenol skeletons, and may be the same in only some phenol skeletons It may be

  The phenol resin (b2) represented by the general formula (II) is preferably one in which n21, n22, n23, n24, n25, n26 and n27 are all 0.

  m21 may be an integer of 0 or more, and the upper limit thereof is not particularly limited.

  As the phenol resin (b2), one type may be used alone, or two or more types may be used in combination.

  The phenol resin (b2) can be obtained by reacting a monomer that derives the constituent unit by a known method, and a commercially available product may be used as the phenol resin (b2).

  A preferred structure of the epoxy-based thermosetting resin (b) is a structure in which the contained epoxy resin (b1) is bonded to the same one as the phenol resin (b2) used in combination with or without an epoxy group via a linking group Those having the same structure are preferred, and those having the structure in which the hydrogen atom of the phenolic hydroxyl group of the same one as the phenol resin (b2) used in combination is substituted with an epoxy group with or without a linking group is more preferred. It is particularly preferable that the same as the resin (b2) has a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted with a glycidyl group without a linking group. Here, the linking group is the same as described above.

  In the case where the epoxy resin (b1) has the same structure as that of the phenol resin (b2) used in combination as described above, the hydrogen atom of the phenolic hydroxyl group is substituted with an epoxy group with or without a linking group Thus, the ratio of the number of hydroxyl groups substituted with hydrogen atoms by epoxy groups is preferably 80% or more, more preferably 90% or more, and more preferably 95% or more based on the total number of hydroxyl groups. More preferably, it may be 100%.

  When the adhesive composition does not contain the polymer component (a) described later, the content of the epoxy-based thermosetting resin (b) relative to the total content of the solid content of the adhesive composition (epoxy resin (b1) and The proportion of the total content of the phenol resin (b2) (the content of the epoxy-based thermosetting resin (b) of the adhesive) is preferably 20% by mass or more, and 25% by mass or more More preferable.

  When the adhesive composition contains a polymer component (a) described later, the content of the epoxy-based thermosetting resin (b) in the adhesive composition (the adhesive) (epoxy resin (b1) and The ratio of the total content of the phenol resin (b2) is preferably 1 to 100 parts by mass, and 1.5 to 85 parts by mass with respect to 100 parts by mass of the polymer component (a). Is more preferable, and 2 to 70 parts by mass is particularly preferable. When the content of the epoxy-based thermosetting resin (b) is in such a range, the hardness of the adhesive layer before curing tends to be maintained, and the adhesive layer in an uncured or semi-cured state Wire bonding suitability is improved. In addition, the ease of picking up the semiconductor chip is improved.

  The content ratio of the phenol resin (b2) in the adhesive composition (the adhesive) is preferably 0.1 to 500 parts by mass with respect to 100 parts by mass of the epoxy resin (b1). 1 to 200 parts by mass is more preferable. If the content of the phenolic resin (b2) is too small, curing may be insufficient and adhesion may not be obtained, and if the content of the phenolic resin (b2) is excessive, the moisture absorption rate of the adhesive increases and the semiconductor package Reliability may decrease.

  The adhesive preferably further contains a polymer component (a) which does not correspond to the epoxy resin (b1) and the phenol resin (b2). That is, the adhesive composition preferably contains an epoxy-based thermosetting resin (b) and a polymer component (a).

(Polymer component (a))
The polymer component (a) is a component that can be considered to be formed by the polymerization reaction of the polymerizable compound, imparts film forming property and flexibility to the adhesive, and adheres to an adhesion target such as a semiconductor chip. It is a polymer compound for improving the property (stickability).
As the polymer component (a), one type may be used alone, or two or more types may be used in combination.

  As the polymer component (a), acrylic resins, polyester resins, urethane resins, acrylic urethane resins, silicone resins, rubber polymers, phenoxy resins and the like can be used, and acrylic resins are preferable.

A well-known acrylic polymer can be used as said acrylic resin.
The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,500,000. If the weight average molecular weight of the acrylic resin is too small, the adhesion between the film adhesive and the adhesive layer described later may be high, which may cause pickup failure of the semiconductor chip. When the weight average molecular weight of the acrylic resin is too large, the film adhesive may not follow the uneven surface of the adherend, which may cause generation of voids and the like.

  It is preferable that it is -60-70 degreeC, and, as for the glass transition temperature (Tg) of acrylic resin, it is more preferable that it is -30-50 degreeC. If the Tg of the acrylic resin is too low, the peeling force between the film adhesive and the adhesive layer to be described later may be increased to cause pickup failure of the semiconductor chip. In addition, when the Tg of the acrylic resin is too high, the adhesive force for fixing the semiconductor wafer may be insufficient.

As a monomer which comprises acrylic resin, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n- Octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate , Tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl ( Data) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylates such as), alkyl carbon atoms the alkyl group having a chain is 1 to 18 (meth) acrylate;
Cycloalkyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, imide (meth) (Meth) acrylates having a cyclic skeleton such as acrylates;
Hydroxyl-containing (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate;
Examples thereof include (meth) acrylic esters such as glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate.
Further, the acrylic resin may be one obtained by copolymerizing monomers such as acrylic acid, methacrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylol acrylamide and the like.
In the present specification, "(meth) acrylate" is a concept including both "acrylate" and "methacrylate".

  The monomers constituting the acrylic resin may be only one type or two or more types.

  The acrylic resin may have a functional group capable of binding to other compounds such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group and isocyanate group. The bonding to another compound may be performed via a crosslinking agent (f) described later, or the functional group may be directly bonded to another compound without crosslinking agent (f) . There is a tendency for the reliability of the semiconductor package to be improved by the acrylic resin being bonded to other compounds by these functional groups.

  The ratio of the content of the acrylic resin to the total content of the solid content of the adhesive composition (the content of the acrylic resin in the adhesive) is preferably 20 to 85 mass%, and 30 to 80 mass. More preferably, it is%.

  In the present invention, the releasability from the film adhesive of the pressure-sensitive adhesive layer to be described later is improved to improve the easy pick-up property, and the film adhesive adheres to the uneven surface of the adherend and so on. In order to suppress generation, as the polymer component (a), thermoplastic resins other than acrylic resins (hereinafter, may be simply abbreviated as “thermoplastic resins”) may be used alone, or acrylic resins may be used. You may use together with resin.

The thermoplastic resin preferably has a weight average molecular weight of 1,000 to 100,000, and more preferably 3,000 to 100,000.
The glass transition temperature (Tg) of the thermoplastic resin is preferably -30 to 150 ° C, and more preferably -20 to 120 ° C.
Examples of the thermoplastic resin include polyester resin, urethane resin, phenoxy resin, polybutene, polybutadiene and polystyrene.
The said thermoplastic resin may be used individually by 1 type, and may use 2 or more types together.

  By using the thermoplastic resin, the above-mentioned effects can be obtained, while the hardness when the film adhesive before curing is exposed to high temperature is reduced, and the film adhesion in the uncured or semi-cured state There is a concern that the wire bonding suitability of the agent may be reduced. Therefore, the content of the acrylic resin in the adhesive composition is preferably set in consideration of such an influence.

  As described above, the “polymer component (a)” in the adhesive composition has a higher effect of obtaining a highly reliable semiconductor package even when the heating time in steps other than sealing is prolonged. The mass ratio of the content (mass): the content (mass) of the epoxy-based thermosetting resin (b) is preferably 65: 35 to 99: 1, and is 70:30 to 99: 1. Is more preferable, and 70:30 to 95: 5 is particularly preferable.

The adhesive contains, in addition to the polymer component (a) and the epoxy-based thermosetting resin (b), as necessary, other components which do not fall under these, in order to improve various physical properties. May be
Among the other components contained in the adhesive, preferred are inorganic filler (c), curing accelerator (d), coupling agent (e), crosslinking agent (f), and other heats not falling under epoxy resin. A curable resin (g), a general purpose additive (h), etc. can be illustrated.

(Inorganic filler (c))
The adhesive further contains an inorganic filler (c) to facilitate adjustment of the thermal expansion coefficient thereof, and the thermal expansion coefficient of the film adhesive after curing with respect to the semiconductor chip, the metal or the organic substrate. Thus, the reliability of the semiconductor package can be improved.
Moreover, the said adhesive composition can also reduce the moisture absorption rate of the film adhesive after hardening by containing an inorganic filler (c).

Preferred examples of the inorganic filler (c) include powders of silica, alumina, talc, calcium carbonate, titanium white, bengala, silicon carbide, boron nitride and the like; beads obtained by spheroidizing such silica and the like; single crystal fibers such as these silica and the like; Glass fiber etc. can be illustrated.
Among these, the inorganic filler (c) is preferably a silica filler or an alumina filler.
An inorganic filler (c) may be used individually by 1 type, and may use 2 or more types together.

  When the inorganic filler (c) is used, the ratio of the content of the inorganic filler (c) to the total content of the solid content of the adhesive composition (the content of the inorganic filler (c) of the adhesive) is The content is preferably 5 to 80% by mass, and more preferably 7 to 60% by mass. When the content of the inorganic filler (c) is in such a range, it is easier to obtain the above-mentioned effect of adjusting the thermal expansion coefficient.

(Hardening accelerator (d))
The curing accelerator (d) is used to adjust the curing rate of the adhesive composition.
Preferred curing accelerators (d) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2 -Imidazoles such as -phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (one or more hydrogen atoms are groups other than hydrogen atom Imidazoles substituted by: organic phosphines such as tributyl phosphine, diphenyl phosphine, triphenyl phosphine (a phosphine in which one or more hydrogen atoms are substituted with an organic group); tetraphenylphosphonium tetraphenylborate, trifluoro Tetraphenyl boron salts such as sulfonyl phosphine tetraphenyl borate can be mentioned.
A hardening accelerator (d) may be used individually by 1 type, and may use 2 or more types together.

  When using a curing accelerator (d), the ratio of the content of the curing accelerator (d) in the adhesive composition (the adhesive) is 100 parts by mass of the content of the epoxy-based thermosetting resin (b) The amount is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass. When the content of the curing accelerator (d) is in such a range, the adhesive has excellent adhesive properties even under high temperature and high humidity conditions and is exposed to severe reflow conditions. Even semiconductor packages can achieve high reliability. When the content of the curing accelerator (d) is too small, the effect of using the curing accelerator (d) can not be sufficiently obtained, and when the content of the curing accelerator (d) is excessive, high polarity is obtained. The curing accelerator (d) moves to the adhesion interface side with the adherend in the film-like adhesive under high temperature and high humidity conditions and is segregated, thereby reducing the reliability of the semiconductor package.

(Coupling agent (e))
By using a coupling agent (e) having a functional group that reacts with an inorganic compound and a functional group that reacts with an organic functional group, it is possible to improve the adhesion and adhesion of the film adhesive to an adherend Can. Moreover, water resistance can be improved by using a coupling agent (e), without impairing the heat resistance about the hardened | cured material obtained by hardening | curing a film adhesive.

The coupling agent (e) is preferably a compound having a functional group that reacts with the functional group possessed by the polymer component (a), the epoxy-based thermosetting resin (b), etc., and is a silane coupling agent Is desirable.
As the preferable silane coupling agent, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (methacryloxy) Propyl) trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N -Phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltri Methoxysi Examples include orchid, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane.
As the coupling agent (e), one type may be used alone, or two or more types may be used in combination.

  When the coupling agent (e) is used, the ratio of the content of the coupling agent (e) in the adhesive composition (the adhesive) is the ratio of the polymer component (a) and the epoxy-based thermosetting resin (b) It is preferable that it is 0.03-20 mass parts with respect to 100 mass parts of total content, It is more preferable that it is 0.05-10 mass parts, It is especially preferable that it is 0.1-5 mass parts . When the content of the coupling agent (e) is too small, the above-mentioned effects of using the coupling agent (e) may not be obtained, and when the content of the coupling agent (e) is too large, Outgassing may occur.

(Crosslinking agent (f))
When a polymer component (a) having a functional group capable of binding to another compound such as an isocyanate group is used, a crosslinking agent (f) is used to link and crosslink the functional group to another compound. be able to. By crosslinking with the crosslinking agent (f), the initial adhesion and cohesion of the film adhesive can be controlled.
As a crosslinking agent (f), an organic polyhydric isocyanate compound, an organic polyhydric imine compound, etc. can be illustrated.

  As the organic polyvalent isocyanate compound, aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, trimers of these compounds, isocyanurates and adducts (ethylene glycol, propylene glycol By reaction with a low molecular weight active hydrogen-containing compound such as neopentyl glycol, trimethylolpropane or castor oil, for example, trimethylolpropane adduct xylylene diisocyanate), or an organic polyvalent isocyanate compound with a polyol compound. The terminal isocyanate urethane prepolymer etc. which can be obtained can be illustrated.

  More specifically, examples of the organic polyvalent isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4,4. '-Diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, trimethylolpropane etc. Compounds obtained by adding tolylene diisocyanate or hexamethylene diisocyanate to all or part of the hydroxyl groups of the polyol, lysine diisocyanate, etc. can be exemplified

  Examples of the organic polyhydric imine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinyl propionate, and tetramethylolmethane-triol. -Β-aziridinyl propionate, N, N'-toluene-2,4-bis (1-aziridine carboxamide) triethylene melamine and the like can be exemplified.

  When using an isocyanate type crosslinking agent as a crosslinking agent (f), it is preferable to use a hydroxyl-containing polymer as a polymer component (a). When the crosslinker (f) has an isocyanate group and the polymer component (a) has a hydroxyl group, the crosslinker (f) and the polymer component (a) react to simply form a crosslink structure in the adhesive. It can be introduced.

  When the crosslinking agent (f) is used, the content ratio of the crosslinking agent (f) in the adhesive composition (the adhesive) is 0.01 relative to 100 parts by mass of the content of the polymer component (a). It is preferably 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass.

(Other thermosetting resin (g))
Other thermosetting resins (g) may be those which do not correspond to epoxy resins and phenol resins, and examples thereof include thermosetting polyimide resins, polyurethane resins, unsaturated polyester resins, silicone resins and the like.

(General-purpose additive (h))
Examples of the general-purpose additive (h) include known plasticizers, antistatic agents, antioxidants, pigments, dyes, gettering agents and the like.

(solvent)
The adhesive composition further improves the handleability by dilution by further containing a solvent.
The solvent contained in the adhesive composition is not particularly limited, but preferred are hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), 1 Alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
The solvent contained in the adhesive composition may be only one or two or more.
The solvent contained in the adhesive composition is preferably methyl ethyl ketone or the like from the viewpoint of uniformly mixing the components used in the adhesive composition.

[Other epoxy thermosetting resin (z)]
The adhesive does not fall under the other epoxy thermosetting resin (z) which does not fall under the epoxy thermosetting resin (b), that is, the epoxy resin (b1), as long as the effect of the present invention is not impaired. Other epoxy resins (z1) (hereinafter sometimes abbreviated as "epoxy resin (z1)"), and other thermosetting agents (z2) not corresponding to the phenol resin (b2) (hereinafter, "thermosetting agents ( z2) may be included.

(Epoxy resin (z1))
As an epoxy resin (z1), a well-known thing is mentioned, Specifically, polyfunctional epoxy resin, bisphenol A diglycidyl ether and its hydrogenated substance, ortho cresol novolak epoxy resin, dicyclopentadiene type epoxy resin, Examples thereof include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins (except biphenyl type epoxy resins), and epoxy compounds having two or more functional groups.

In addition, an epoxy resin having an unsaturated hydrocarbon group may be used as the epoxy resin (z1). As an epoxy resin which has an unsaturated hydrocarbon group, the compound formed by converting a part of epoxy resin of polyfunctional epoxy resin into the group containing an unsaturated hydrocarbon group can be illustrated. Such compounds can be produced, for example, by the addition reaction of acrylic acid to an epoxy group. Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group containing an unsaturated hydrocarbon group directly couple | bonded with the aromatic ring etc. which comprise an epoxy resin can be illustrated. The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specifically, ethenyl group (vinyl group), 2-propenyl group (allyl group), acryloyl group, methacryloyl group, acrylamide group, methacrylamide group Etc., and an acryloyl group is preferable.
An epoxy resin having an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. For this reason, the reliability of the semiconductor package is improved by using the adhesive composition containing the epoxy resin having an unsaturated hydrocarbon group.

  The epoxy resin (z1) is preferably one having a high softening point or glass transition temperature, from the viewpoint of easy pick up property improvement.

The number average molecular weight of the epoxy resin (z1) is not particularly limited, but is preferably 300 to 30,000, and is 400 to 10,000, from the viewpoint of the curability of the adhesive and the strength and heat resistance after curing. More preferably, it is particularly preferably 500 to 3,000.
The epoxy equivalent of the epoxy resin (z1) is preferably 100 to 1000 g / eq, and more preferably 300 to 800 g / eq.

  An epoxy resin (z1) may be used individually by 1 type, and may use 2 or more types together.

  When using an epoxy resin (z1), the content ratio of the epoxy resin (z1) in the adhesive composition (the adhesive) is 5 parts by mass or less with respect to 100 parts by mass of the epoxy resin (b1) content Is preferably, it is more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less.

(Thermosetting agent (z2))
The heat curing agent (z2) functions at least as a curing agent for the epoxy resin (z1), and may sometimes function as a curing agent for the epoxy resin (b1).
As a thermosetting agent (z2), the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule can be illustrated. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and a group in which an acid group is anhydrated, and the phenolic hydroxyl group, an amino group, and a group in which an acid group is an anhydride. It is preferably a phenolic hydroxyl group or an amino group, and particularly preferably a phenolic hydroxyl group.

Among the thermosetting agents (z2), examples of phenol-based curing agents (curing agents having a phenolic hydroxyl group) include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-based phenol resins, aralkyl phenol resins, etc. it can.
Among the thermosetting agents (z2), examples of amine curing agents (curing agents having an amino group) include DICY (dicyandiamide).

The thermosetting agent (z2) may have an unsaturated hydrocarbon group.
As a thermosetting agent (z2) having an unsaturated hydrocarbon group, a compound obtained by substituting a part of hydroxyl groups of a phenol resin with a group containing an unsaturated hydrocarbon group, unsaturated carbonization to an aromatic ring of a phenol resin The compound etc. which the group containing a hydrogen group directly couple | bonded can be illustrated. The unsaturated hydrocarbon group in the thermosetting agent is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.

  The heat curing agent (z2) is preferably one having a high softening point or glass transition temperature, from the viewpoint of easy pick-up property improvement.

  The number average molecular weight of the thermosetting agent (z2) is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000.

  A thermosetting agent (z2) may be used individually by 1 type, and may use 2 or more types together.

  When a thermosetting agent (z2) is used, the content of the thermosetting agent (z2) in the adhesive composition (the adhesive) is 5 parts by mass with respect to 100 parts by mass of the content of the phenolic resin (b2) The amount is preferably at most parts, more preferably at most 3 parts by mass, and particularly preferably at most 1 part by mass.

An adhesive composition is obtained by mix | blending the above-mentioned each component for comprising the said adhesive, such as epoxy-type thermosetting resin (b).
There is no particular limitation on the order of addition of each component at the time of blending, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting this compounding component in advance, or by previously diluting any compounding component other than the solvent A solvent may be used by mixing with these compounding ingredients without storage.

The method of mixing each component at the time of compounding is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc .; a method of mixing using a mixer; a method of adding ultrasonic waves and mixing, etc. It may be selected as appropriate.
The temperature and time of the addition and mixing of the respective components are not particularly limited as long as the respective blended components do not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

<< Composite sheet for die bonding >>
The adhesive may be provided in a film form on a support sheet to form a film-like adhesive, which can be used as a die bonding composite sheet such as a die bonding sheet or a dicing die bonding sheet.

<Support sheet>
As the support sheet, a substrate or a substrate provided with a pressure-sensitive adhesive layer can be used. When using a support sheet provided with an adhesive layer, a film adhesive is provided on the adhesive layer.

[Base material]
The material of the substrate is preferably various resins, and specifically, polyethylene (low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE etc.)), polypropylene, polybutene , Polybutadiene, polymethylpentene, polyvinyl chloride film, vinyl chloride copolymer, polyethylene terephthalate, polybutylene terephthalate, polyurethane, polyurethane acrylate, polyimide, ethylene vinyl acetate copolymer, ionomer resin, ethylene (meth) acrylic acid copolymer Examples thereof include polymers, ethylene / (meth) acrylic acid ester copolymers, polystyrenes, polycarbonates, fluororesins, and water additives, modified products, cross-linked products, copolymers and the like of any of these resins.

  The base material may consist of one layer (single layer), or may consist of two or more layers, and in the case of two or more layers, the material of each layer may be the same or different. , And only part may be the same.

  Although the thickness of a base material can be suitably selected according to the objective, it is preferable that it is 50-300 micrometers, and it is more preferable that it is 60-100 micrometers.

When the substrate is provided with a pressure-sensitive adhesive layer thereon, in order to improve the adhesion to the pressure-sensitive adhesive layer, the surface is roughened by sand blasting, solvent treatment, etc., corona discharge treatment, electron beam irradiation treatment, plasma treatment The surface may be subjected to oxidation treatment such as ozone / ultraviolet radiation treatment, flame treatment, chromic acid treatment, hot air treatment or the like. In addition, the substrate may be one having a surface subjected to primer treatment.
Among these, from the viewpoint of suppressing the generation of fragments of the substrate due to the friction of the blade at the time of dicing, it is particularly preferable that the substrate is subjected to electron beam irradiation treatment.

[Pressure-sensitive adhesive layer]
A well-known thing can be suitably used for the said adhesive layer.
The pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing various components for constituting the pressure-sensitive adhesive layer. The ratio of the content of non-volatile components in the pressure-sensitive adhesive composition is the same in the pressure-sensitive adhesive layer.
In the case where the pressure-sensitive adhesive layer contains a component that is polymerized by irradiation of energy rays, the adhesion of the energy rays is reduced to enable pickup of the semiconductor chip. Such a pressure-sensitive adhesive layer can be formed, for example, using various pressure-sensitive adhesive compositions containing an energy ray-polymerizable acrylic polymer which is polymerized by irradiation of energy rays.

  Preferred as the pressure-sensitive adhesive composition are those containing the acrylic polymer and an energy ray-polymerizable compound (pressure-sensitive adhesive composition (i)), having a hydroxyl group and having a polymerizable group in a side chain. An example (adhesive composition (ii)) containing an acrylic polymer (for example, one having a hydroxyl group and having a polymerizable group in a side chain via a urethane bond) and an isocyanate-based crosslinking agent And those further containing a solvent are preferred.

  The pressure-sensitive adhesive composition further includes any of various additives such as a photopolymerization initiator, a dye, a pigment, an antidegradant, an antistatic agent, a flame retardant, a silicone compound, and a chain transfer agent, in addition to the components described above. You may contain.

  The thickness of the pressure-sensitive adhesive layer can be appropriately selected according to the purpose, but is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.

  The pressure-sensitive adhesive composition is obtained by blending the components for forming the pressure-sensitive adhesive layer, such as an acrylic polymer, and, for example, the same as the adhesive composition described above except that the blending components are different. It is obtained by the method.

  The pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive composition to the surface of the substrate and drying it. At this time, if necessary, the applied pressure-sensitive adhesive composition may be crosslinked by heating. The heating conditions may be, for example, 100 to 130 ° C. for 1 to 5 minutes, but not limited thereto. In addition, an adhesive composition formed by applying an adhesive composition on the surface of a release layer of a release material and drying it is adhered to the surface of a substrate, and the release agent is also removed to form an adhesive on the substrate. Can form a layer.

  The application of the pressure-sensitive adhesive composition to the surface of the substrate or the release material may be performed by a known method, and an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain The method using various coaters, such as a coater, a die coater, a knife coater, a screen coater, a Mayer bar coater, a kiss coater, can be illustrated.

<Film adhesive>
The thickness of the film-like adhesive can be appropriately selected according to the purpose, but it is preferably 1 to 100 μm, more preferably 5 to 75 μm, and particularly preferably 5 to 50 μm.

The composite sheet for die bonding can be produced by forming a film adhesive on the support sheet.
When a support sheet is the said base material, the film-like adhesive agent forms an adhesive layer on a base material as mentioned above except using the adhesive composition instead of an adhesive composition, and It can be formed on a substrate in a similar manner.
When the support sheet has a pressure-sensitive adhesive layer on a substrate, it is usually difficult to apply the adhesive composition directly on the pressure-sensitive adhesive layer. Therefore, in this case, for example, the adhesive composition is applied to the surface of the release layer of the release material and dried to form a film-like adhesive, and the side of the film-like adhesive on which the release material is not provided. The film adhesive is formed by bonding a film adhesive separately to the surface of the pressure-sensitive adhesive layer, such as removing the release material, and bonding the film-like adhesive to the surface of the pressure-sensitive adhesive layer. It is preferable to form on a material.

Moreover, the composite sheet for die bonding provided with the pressure-sensitive adhesive layer is, for example, using the pressure-sensitive adhesive composition to form a pressure-sensitive adhesive layer and using the adhesive composition to form a film adhesive After the formation, the pressure-sensitive adhesive layer and the film-like adhesive may be laminated to form a laminate, and a substrate may be laminated to the surface of the pressure-sensitive adhesive layer of the laminate.
The conditions for forming the pressure-sensitive adhesive layer and the film-like adhesive in this case are the same as those described above.

  The semiconductor package can be manufactured by using the composite sheet for die bonding in the same manner as the composite sheet for die bonding, such as a conventional die bonding sheet and a dicing die bonding sheet.

  Hereinafter, the present invention will be described in more detail by way of specific examples. However, the present invention is not limited at all to the examples shown below.

<Production of adhesive for die bonding and dicing die bonding sheet>
[Examples 1 to 3, Comparative Examples 1 to 3]
(Production of adhesive composition)
Each component was blended in the amount shown in Table 1 or 2 and further diluted with methyl ethyl ketone to obtain an adhesive composition.
In addition, the symbol of each component in Table 1 and 2 respectively has the following meaning.

・ Polymer component (a)
(A) -1: Acrylic resin ("Teisan resin SG-P3" manufactured by Nagase ChemteX Corporation)
・ Epoxy resin (b1)
(B1) -1: biphenyl type epoxy resin represented by the following general formula (I) -101 (epoxy equivalent 280 to 298 g / eq, softening point 63 to 75 ° C., weight average molecular weight 1.4 × 10 ³ )
・ Epoxy resin (z1)
(Z1) -1: triphenylene type epoxy resin represented by the following general formula (IX) -101 (epoxy equivalent 162 to 172 g / eq, softening point 51 to 57 ° C., weight average molecular weight 0.6 × 10 ³ )
・ Phenolic resin (b2)
(B2) -1: biphenyl type phenol resin represented by the following general formula (II) -101 (hydroxy group equivalent 237 g / eq, softening point 122.4 ° C., weight average molecular weight 7.5 × 10 ³ )
・ Heat curing agent (z2)
(Z2) -1: Zyloc-type phenolic resin represented by the following general formula (X) -101 (hydroxy group equivalent 168 g / eq, softening point 65 ° C., weight average molecular weight 1.4 × 10 ³ )
· Filler (c)
(C) -1: Spherical silica (manufactured by Admatics, "YA050C-MJA")
· Hardening accelerator (d)
(D) -1: Triphenylphosphine (manufactured by Hokuko Chemical Industry Co., Ltd.)
・ Coupling agent (e)
(E) -1: Silane coupling agent ("KBM-402" manufactured by Shin-Etsu Chemical Co., Ltd.)

（式中、ｍ１１及びｍ２１は前記と同じであり；ｑ１１及びｑ２１は、それぞれ独立に０以上の整数である。）

(Wherein, m 11 and m 21 are the same as above; q 11 and q 21 are each independently an integer of 0 or more)

In the formula, m11 is the same as m11 in the general formula (I), and m21 is the same as m21 in the general formula (II).
In the above formulae, q11 and q21 are each independently an integer of 0 or more.

(Production of adhesive for die bonding and dicing die bonding sheet)
The adhesive composition obtained above is applied to the release-treated surface of a release sheet in which one surface of a polyethylene terephthalate film has been release-treated, and dried at 120 ° C. for 3 minutes to form a film having a thickness of 20 μm. An adhesive (die adhesive) was formed. Furthermore, the same release sheet as described above was bonded to a film-like adhesive to produce a noncarrier film.
Next, one of the release sheets of this non-carrier film is peeled off, and the film adhesive is transferred onto the pressure-sensitive adhesive layer of dicing tape ("G-562" manufactured by Lintec Corporation) provided with the pressure-sensitive adhesive layer on the substrate. A dicing die bonding sheet was obtained.

<Evaluation of semiconductor package>
The reliability of the semiconductor package was evaluated by the following method using the dicing die bonding sheet obtained above.

  Using a tape mounter ("Adwill RAD 2500" manufactured by Lintec Corporation), the dicing die bonding sheet of the example and the comparative example is formed on the polished surface of a dry polished silicon wafer (150 mm diameter, 75 μm thickness) using the film adhesive The silicon wafer was fixed to a ring frame for wafer dicing. Then, a silicon wafer was diced (50 mm / sec, 30000 rpm) to a size of 8 mm × 8 mm using a dicing apparatus (“DFD651” manufactured by Disco) to obtain a chip. At the time of this dicing, the base material was cut by 20 μm from the surface.

  The above chip to which the dicing die bonding sheet was attached was picked up from the substrate together with the film adhesive of the dicing die bonding sheet. Then, a circuit pattern is formed on the copper foil (thickness 18 μm) of a copper foil-clad laminate (“CCL-HL 830” manufactured by Mitsubishi Gas Chemical Co., Ltd.), and a solder resist (“PSR-4000” manufactured by Solar Ink Co., Ltd.) is formed on this circuit pattern. AUS 303 ") is laminated on a substrate (" LN 001 E-001 PCB (Au) AUS 303 "manufactured by Chigiken Co., Ltd.), and the chip with the above film adhesive is attached to this substrate through the film adhesive Crimping was performed under the conditions of 120 ° C., 2.45 N (250 gf) for 0.5 seconds. Such a laminate of the substrate and the chip with a film adhesive is as it is, heated at 175 ° C. for 1 hour, heated at 175 ° C. for 2 hours, heated at 175 ° C. for 3 hours, 175 What was heated at 4 ° C for 4 hours and one heated at 175 ° C for 5 hours were prepared for each example and comparative example.

  Then, the unheated laminate and the heated laminate are sealed using a sealing resin ("KE-G1250" manufactured by Kyocera Chemical Co., Ltd.) to a sealing thickness of 400 μm, at 175 ° C. The sealing resin was cured by heating for 5 hours. Then, the sealed laminate is attached to a dicing tape ("Adwill D-510T" manufactured by Lintec Corporation) and diced into a size of 15 mm x 15 mm using a dicing apparatus ("DFD 651" manufactured by Disco Corporation). Semiconductor package for reliability evaluation.

  The obtained semiconductor package was allowed to absorb moisture by standing for 168 hours under the conditions of 85 ° C. and relative humidity 60%, and then IR reflow was performed three times under the conditions of the maximum heating temperature 260 ° C. and the heating time 1 minute. Then, using the scanning ultrasonic flaw detector (“Hye-Focus” manufactured by Hitachi Construction Machinery Finetech Co., Ltd.) for the IR-reflowed semiconductor package, the presence or absence of peeling at the joint between the substrate and the semiconductor chip, And the presence or absence of generation | occurrence | production of the package crack was observed. About the said junction part, it was judged that peeling generate | occur | produced the case where float and peeling of 0.5 mm or more were observed. Such evaluation is performed with six semiconductor packages for each example and comparative example, and the heat history time until the peeling or package crack occurs in any of the six (the above-mentioned substrate Heating time at a temperature of 175 ° C. for a laminate of a chip and a chip with a film adhesive, and the reliability of the semiconductor package against the heat history was examined. The results are shown in Tables 1 and 2. In the table, for example, “0/6” in the column of the evaluation result is evaluated for six semiconductor packages, and the occurrence of peeling or package crack in the joint is observed in 0 out of 6 semiconductor packages. That is, it means that there was no semiconductor package in which the occurrence of peeling or cracking was observed. The evaluation results are separately described in Table 1 as Example 1 and Comparative Examples 1 to 3 and in Table 2 as Example 1 and Examples 1 and 3.

  In Example 1 and Comparative Examples 1 to 3 shown in Table 1, the mass ratio of "content of polymer component (a): content of epoxy-based thermosetting resin (b)" is the same. And as is clear from the results shown in Table 1, in Example 1 in which biphenyl type epoxy resin and phenol resin were used as epoxy resin thermosetting resin (b), epoxy resin and phenol resin were used. The reliability of the semiconductor package was significantly higher than that of Comparative Examples 1 to 3 in which one other than the biphenyl type was used at least on one side.

  Examples 1 to 3 shown in Table 2 use the biphenyl type as both the epoxy resin and the phenol resin. And, as apparent from the results shown in Table 2, the higher the ratio of the content of the polymer component (a) to the content of the epoxy-based thermosetting resin (b), that is, Example 2, Example 1 The reliability of the semiconductor package was high in the order of Example 3.

  The present invention is applicable to the manufacture of semiconductor packages.

Claims (2)

It contains an epoxy resin and a phenol resin as an epoxy-based thermosetting resin, and further contains a polymer component not corresponding to the epoxy resin and the phenol resin,
The epoxy resin and the phenol resin have a biphenylene group which may have a substituent,
The epoxy resin is a polymer compound having a structural unit containing the biphenylene group and a group having an epoxy group in an amount of 2 or more as an essential structural unit in the main chain,
The adhesive agent for die bonding, wherein the polymer component comprises an acrylic resin.   The adhesive agent for die bonding according to claim 1, wherein a mass ratio of "the content of the polymer component: the content of the epoxy-based thermosetting resin" is 65: 35 to 99: 1.