JP2016113556A - Adhesive for die adhesion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive for die adhesion that makes it possible to produce a semiconductor package with high reliability even if a heating time in a step other than sealing becomes long.SOLUTION: An adhesive for die adhesion comprises epoxy resin and phenolic resin as epoxy thermosetting resin, and the epoxy resin and phenolic resin has an optionally substituted biphenylene group.SELECTED DRAWING: None

Description

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

  At the time of manufacturing a semiconductor package, a semiconductor chip having a film adhesive for die bonding attached to the back surface opposite to the circuit surface is die-bonded to a lead frame or a substrate with this adhesive, and in some cases, this die After further laminating the semiconductor chip on the circuit surface of the bonded semiconductor chip, the electrode part of the semiconductor chip is connected to the conductor on the lead frame or the substrate with a metal wire, and wire bonding is performed to electrically connect them. . Finally, the entire laminate is covered with resin and sealed by pressurization and heating to obtain a semiconductor package. During this sealing, the curing of the film adhesive is completed.

  Among these manufacturing processes, when die bonding is performed, a gap (hereinafter referred to as “void”) is usually generated between the film adhesive and the substrate to be bonded. Due to the management, this void disappears by the above-described pressurization and heating during sealing with resin.

  However, for example, in a process of performing die bonding or wire bonding, if the heating time is long, voids remain without being lost between the film adhesive and the substrate after sealing. This is because, in the above process, the curing of the film adhesive proceeds beyond the allowable range, and the film adhesive is already hard before sealing, and follows the adhesion surface of the substrate or the like. This is presumed to be caused by the low nature. A semiconductor package in which such voids remain has low reliability, such as cracks occurring under wet heat conditions.

  On the other hand, an adhesive sheet used for manufacturing a semiconductor package, in which a pressure-sensitive adhesive layer and an adhesive layer are laminated in this order on a base material, is disclosed which has excellent adhesion reliability between a semiconductor chip and an adhesive layer. (See Patent Document 1). In this adhesive sheet, the adhesive layer 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.

JP 2004-256695 A

  However, the semiconductor package obtained using the adhesive sheet disclosed in Patent Document 1 has high reliability even when the heating time becomes long in the process of performing die bonding or 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 a die bonding adhesive capable of manufacturing a highly reliable semiconductor package even when the heating time in steps other than sealing becomes long. And

In order to solve the above problems, the present invention includes an epoxy resin and a phenol resin as an epoxy thermosetting resin, and the epoxy resin and the phenol resin have a biphenylene group which may have a substituent. A die attach adhesive is provided.
The adhesive for die bonding of the present invention further contains a polymer component not corresponding to the epoxy resin and the phenol resin, and the mass of “content of the polymer component: content of the epoxy thermosetting resin”. A ratio of 65:35 to 99: 1 is preferred.

  ADVANTAGE OF THE INVENTION According to this invention, even if the heating time in processes other than sealing becomes long, the adhesive agent for die bonding which can manufacture a highly reliable semiconductor package is provided.

<< Die bonding adhesive >>
The adhesive for die bonding according to the present invention (hereinafter sometimes abbreviated as “adhesive”) contains an epoxy resin and a phenol resin as an epoxy thermosetting resin, and the epoxy resin and the phenol resin are substituted. It has a biphenylene group which may have a group.
The adhesive is usually provided as 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. When a support sheet provided with a pressure-sensitive adhesive layer is used, a film adhesive is applied on the pressure-sensitive adhesive layer. Provide. The film adhesive is affixed to the back side opposite to the circuit surface of the semiconductor chip, used for die bonding to a lead frame or a substrate, and sealed with a resin after wire bonding to form a semiconductor package. Curing is completed by heating.

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

  Thus, even if the heating time in processes other than sealing becomes long, the reason that peeling is suppressed between an adhesive agent and a board | substrate etc. is estimated as follows. That is, the adhesive is prevented from being cured during heating in the process before sealing, and the state of high followability to the adhesive surface such as the substrate is maintained. As a result, the curing of the adhesive is completed during sealing. In the stage, it is presumed that the void between the adhesive and the substrate or the like has disappeared as in the case where the heating time in the steps other than the sealing is short. When heating in processes other than sealing, the curing of the adhesive is suppressed because the epoxy resin and the phenol resin both have a biphenylene group that may have a substituent, and the molecules of these resins are compared. It is speculated that this is because the curing reaction is difficult to proceed.

  Hereinafter, in this specification, “an epoxy resin having a biphenylene group which may have a substituent” is referred to as “epoxy resin (b1)”, and it has a biphenylene group which may have a substituent. “Phenolic resin” may be referred to as “phenolic resin (b2)”. The epoxy thermosetting resin composed of the epoxy resin (b1) and the phenol resin (b2) may be referred to as “epoxy thermosetting resin (b)”.

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

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

[Epoxy thermosetting resin (b)]
The epoxy thermosetting resin (b) is composed of the epoxy resin (b1) and the phenol resin (b2).
Epoxy thermosetting resin (b) may be used individually by 1 type, and may use 2 or more types together.

(Epoxy resin (b1))
The epoxy resin (b1) is a biphenyl type epoxy resin having a biphenylene group which may have a substituent. Here, the “biphenylene group” means a divalent group in which two hydrogen atoms are removed from biphenyl (diphenyl, C ₆ H ₅ -C ₆ H ₅ ), and may be referred to as a diphenylene group. Usually, it is one obtained by removing one hydrogen atom from one benzene ring skeleton (—C ₆ H ₄ —C ₆ H ₄ —).
The position of the free valence of the biphenylene group that the epoxy resin (b1) has is not particularly limited, but is preferably a 4,4′-biphenylene group.

  In this specification, the “biphenylene group having a substituent” means a biphenylene group in which 1 to 8 hydrogen atoms are substituted with a group other than a hydrogen atom (substituent), and the number of substituents is 1 to 1. The number of substituents is not particularly limited as long as it is eight. When the number of substituents is two or more, these two or more substituents may all be the same or different. Only the part may be the same. Further, 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”) as essential constituent units in the main chain, Any epoxy group-containing group may or may not be present 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 with an epoxy group with or without a linking group. Examples of the linking group include a divalent group such as an alkylene group. For example, a structural unit having a structure in which a hydrogen atom of a hydroxyl group is substituted with an epoxy group through 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 through a linking group, It is obtained by a method having a step of reacting epichlorohydrin (2-chloromethyloxirane) with the hydroxyl group.

The epoxy resin (b1) preferably has a weight average molecular weight of 300 to 100,000, and more preferably 300 to 20,000.
In the present specification, the weight average molecular weight is a polystyrene conversion value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

  The epoxy resin (b1) preferably has an epoxy equivalent of 180 to 350 g / eq, and more preferably 230 to 320 g / eq.

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

Preferred examples of the epoxy resin (b1) include those represented by the following general formula (I). This epoxy resin (b1) is composed of a biphenyl skeleton (biphenylene group which may have a substituent) and a benzene ring skeleton (which has a glycidyloxy group as a substituent and may have another substituent). Group) has a structure bonded with a methylene group as a repeating unit. Here, the “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; m11 is an integer of 0 or more; n11, n12, 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 as or different from each other. values may be the same or different from each other, the value of m11 amino n14 may be the same or different from each other; when n11 is 2 or more, a plurality of X ¹¹ may be the same or different from each other , When m11 is 2 or more, or when n12 is 2 or more, a plurality of X ¹² may be the same or different from each other, and when m11 is 2 or more or n13 is 2 or more, a plurality 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, A plurality of X ¹⁵ may be the same as or different from each other. When n16 is 2 or more, a plurality of X ¹⁶ may be the same or different from each other. When n17 is 2 or more, a plurality of X 15 ¹⁷ to each other may be the same or different; when it is n11 is 2 or more, a plurality of X ¹¹ may be bonded to each other to form a ring, when n12 is 2 or more, plural X 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, Multiple X ^14's are connected to each other To may form a ring, when n15 is 2 or more, plural X ¹⁵ may be bonded to each other to form a ring, when n16 is 2 or more, plural X ¹⁶ may be bonded to each other to form a ring, and when n17 is 2 or more, a plurality of X ¹⁷ may be bonded to each other to form a ring.)

In the 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.
If n12 is not 0, X ¹² is attached to one of the phenylene group constituting the biphenylene group (a benzene ring skeleton), the binding position is not particularly limited. If n13 is not 0, X ¹³ is attached to the other phenylene group constituting the biphenylene group (a benzene ring skeleton), the binding position is not particularly limited.
Similarly, when n15 is not 0, X ¹⁵ is bonded to one phenylene group (benzene ring skeleton) constituting the biphenylene group, and the bonding position is not particularly limited. If n16 is not 0, X ¹⁶ is attached to the other phenylene group constituting the biphenylene group (a benzene ring skeleton), the binding position is not particularly limited.

If n11 is not zero, the bonding position of the benzene ring skeleton of X ¹¹ 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, if n17 is not zero, the bonding position of the benzene ring skeleton of X ¹⁷ is not particularly limited.

  The group (substituent) other than the hydrogen atom is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyloxy group, a heterocyclic group, a halogen atom, and a hydroxyl group. 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 includes 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. 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.
As the alkenyl group, one single bond (C—C) between carbon atoms in the alkyl group such as ethenyl group (vinyl group), 2-propenyl group (allyl group), cyclohexenyl group, etc. is doubled. Examples thereof include a group substituted with a bond (C = C). The alkenyl group preferably has 2 to 5 carbon atoms.

  The aryl group may be monocyclic or polycyclic, preferably has 6 to 12 carbon atoms, and includes a phenyl group, 1-naphthyl group, 2-naphthyl group, o-tolyl group, m-tolyl group, A p-tolyl group, a xylyl group (dimethylphenyl group) and the like can be exemplified, but are not limited thereto.

Examples of the alkoxy group include monovalent groups in which the alkyl group is bonded to an oxygen atom, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and a cyclopropoxy group.
Examples of the aryloxy group include monovalent groups formed by bonding the aryl group to an oxygen atom, such as a phenyloxy group (phenoxy group) and a 1-naphthyloxy group.
Examples of the alkenyloxy group include monovalent groups formed by bonding the alkenyl group to an oxygen atom, such as an ethenyloxy group, a 2-propenyloxy group, and a cyclohexenyloxy group.

The heterocyclic group may have one or more heteroatoms as atoms constituting the ring skeleton, and may be either an aromatic cyclic group (heteroaryl group) or an aliphatic cyclic group. Either monocyclic or polycyclic may be used.
Examples of the hetero atom that the heterocyclic group has include an oxygen atom, a sulfur atom, and a nitrogen atom.
When the heterocyclic group has two or more heteroatoms, these heteroatoms may be the same as or different from each other. That is, two or more heteroatoms may all be the same, may all be different, or may be partially the same.
Examples of the heterocyclic group include those in which in the cyclic alkyl group or aryl group, one or more carbon atoms are substituted by a heteroatom alone or together with a hydrogen atom bonded to the carbon atom. It can be illustrated.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

If X ¹² is plural, i.e., when m11 is or n12 is 2 or more is two or more (2, 3 or 4), a plurality of ^{X 12} and these may be the same or different from each other. That is, all X ¹² may be the same, all X ¹² may be different, or only some of the X ¹² may be the same.
^Similarly, when ^{X 13} is a plurality, i.e., when m11 is or n13 is 2 or more is two or more (2, 3 or 4), a plurality of ^{X 13} these be the same or different from each other Also good.
Similarly, when there are a plurality of X ^14s , that is, when m11 is 2 or more or n14 is 2 or more (2 or 3), the plurality of Xs ¹⁴ may be the same as or different from each other. .

When there are a plurality of X ¹¹ , that is, when 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 of the X ¹¹ may be the same.
Similarly, when there are a plurality of X ¹⁵ , that is, when n ¹⁵ is 2 or more (2, 3 or 4), these plurality of X ¹⁵ may be the same or different from each other.
^Similarly, when ^{X 16} is a plurality, i.e., when n16 is 2 or more (2, 3 or 4), a plurality of ^{X 16} and these may be the same or different from each other.
^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 together with the carbon atom to which these X ¹¹ are bonded. The ring in question may be either monocyclic or polycyclic, and may be either an aromatic ring or an aliphatic ring.
When n12 is 2 or more (2, 3 or 4), as in the case of X ¹¹ described above, a plurality of X ¹² are bonded to each other to form a ring together with the carbon atom to which these X ¹² are bonded. You may do it.
When n13 is 2 or more (2, 3 or 4), as in the case of X ¹¹ above, a plurality of X ¹³ are bonded to each other to form a ring together with the carbon atom to which these X ¹³ are bonded. You may do it.
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 these X ¹⁴ are 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 together with the carbon atom to which these X ¹⁵ are bonded. You may do it.
When n16 is 2 or more (2, 3 or 4), as in the case of X ¹¹ described above, a plurality of X ¹⁶ are bonded to each other to form a ring together with the carbon atom to which these X ¹⁶ are bonded. You may do it.
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 together with the carbon atom to which these X ¹⁷ are bonded. You may do it.

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

  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 should just be an integer greater than or equal to 0, and the upper limit is not specifically limited.

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

  The epoxy resin (b1) is obtained by reacting a monomer that derives its structural 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 optionally having 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-derived group”) as essential constituent units in the main chain, and the biphenylene group And the phenol-derived groups may or may not be present in the side chain.
Here, “phenols” means both phenol and phenol in which one or more hydrogen atoms other than hydrogen atoms constituting a hydroxyl group are substituted with groups other than hydrogen atoms (substituents). A concept that includes

  The phenol resin (b2) preferably has a weight average molecular weight of 400 to 1000000, more preferably 400 to 20000.

  The phenol resin (b2) preferably has a hydroxyl group equivalent of 140 to 310 g / eq, more preferably 190 to 280 g / eq.

  The phenol resin (b2) has a softening point of preferably 90 to 140 ° C, and more preferably 110 to 130 ° C.

Preferred examples of the phenol resin (b2) include those represented by the following general formula (II). 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 bonded with a methylene group. It has a structure as a repeating unit. Here, the “phenol diyl group having a substituent” means a phenol diyl group (—C ₆ H ₃ (—OH) — in which one or more hydrogen atoms are substituted with a group other than a hydrogen atom (substituent). ).

（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; m21 is an integer of 0 or more; n21, n22, 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 values may be the same or different from each other, the value of m21 amino n24 may be the same or different from each other; when n21 is 2 or more, a plurality of X ²¹ may be the same or different from each other when m21 is or n22 is 2 or more is 2 or more, a plurality of X ²² may be the same or different, when m21 is or n23 is 2 or more is 2 or more, a plurality 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 as or different from each other. When n26 is 2 or more, the plurality of X ²⁶ may be the same or different from each other. When n27 is 2 or more, the plurality of X ^{25 27} may be the same or different from each other; when n21 is 2 or more, a plurality of X ²¹ may be bonded to each other to form a ring, and when n22 is 2 or more, a plurality of X ²² may also be bonded to each other to form a ring, when n23 is 2 or more, may form a plurality of X ²³ may combine with each other to form a ring, when n24 is 2 or more, Multiple X ²⁴ 's connected to each other And when n25 is 2 or more, a plurality of X ²⁵ may be bonded to each other to form a ring, and when n26 is 2 or more, a plurality of X ²⁶ may be bonded to each other to form a ring, and when n27 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 the same as X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , in the general formula (I). it is similar to the 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 these X ²¹ are bonded, The ring formed in this case may be either monocyclic or polycyclic, and may be either an aromatic ring or an aliphatic ring.
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 together with the carbon atom to which these X ²² are bonded. You may do it.
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 together with the carbon atom to which these X ²³ are bonded. You may do it.
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 together 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 together with the carbon atom to which these X ²⁵ are bonded. You may do it.
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 together with the carbon atom to which these X ²⁶ are bonded. You may do it.
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 together with the carbon atom to which these X ²⁷ are bonded. You may do it.

  In the phenol resin (b2) represented by the general formula (II), a phenol skeleton (having a substituent) of a methylene group bonded to a biphenyl skeleton (an optionally substituted biphenylene group). The bonding position to the phenoldiyl group that may be present is not particularly limited, and may be the same for all phenol skeletons, may be different for all phenol skeletons, or may be the same for 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 should just be an integer greater than or equal to 0, and the upper limit is not specifically limited.

  A phenol resin (b2) may be used individually by 1 type, and may use 2 or more types together.

  A phenol resin (b2) is obtained by making the monomer which induces the structural unit react by a well-known method, and you may use a commercial item as a phenol resin (b2).

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

  When the epoxy resin (b1) has the same structure as 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 in which hydrogen atoms are substituted with epoxy groups is preferably 80% or more, more preferably 90% or more, and 95% or more with respect to 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 thermosetting resin (b) relative to the total solid content of the adhesive composition (the epoxy resin (b1) and The ratio of phenol resin (b2) (total content of epoxy thermosetting resin (b) in the adhesive) is preferably 20% by mass or more, and preferably 25% by mass or more. More preferred.

  Moreover, when the said adhesive composition contains the polymer component (a) mentioned later, content (epoxy resin (b1) and epoxy-type thermosetting resin (b) of adhesive composition (the said adhesive)) 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). It is more preferable, and it is especially preferable that it is 2-70 mass parts. When the content of the epoxy thermosetting resin (b) is within 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 The wire bonding aptitude is improved. In addition, the easy pick-up property of 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 phenol resin (b2) is too small, the adhesiveness may not be obtained due to insufficient curing, and if the content of the phenol resin (b2) is excessive, the moisture absorption rate of the adhesive increases, Reliability may be reduced.

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

(Polymer component (a))
The polymer component (a) is a component that can be regarded as formed by polymerization reaction of a polymerizable compound, and imparts film-forming properties, flexibility, etc. to the adhesive, and adheres to an adhesion target such as a semiconductor chip. It is a polymer compound for improving the property (sticking property).
A polymer component (a) may be used individually by 1 type, and may use 2 or more types together.

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

A publicly known acrylic polymer can be used as the 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 adhesive force between the film-like adhesive and the pressure-sensitive adhesive layer, which will be described later, is increased, which may cause a pickup failure of the semiconductor chip. If 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 a void or the like.

  The glass transition temperature (Tg) of the acrylic resin is preferably −60 to 70 ° C., and more preferably −30 to 50 ° C. If the Tg of the acrylic resin is too low, the peeling force between the film-like adhesive and the pressure-sensitive adhesive layer to be described later increases, which may cause a pickup failure of the semiconductor chip. Further, if the Tg of the acrylic resin is too high, the adhesive force for fixing the semiconductor wafer may be insufficient.

As monomers constituting the 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, dicyclopentenyloxyethyl (meth) acrylate, imide (meth) (Meth) acrylate having a cyclic skeleton such as acrylate;
Hydroxyl group-containing (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate;
Examples include (meth) acrylic acid esters such as glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate.
The acrylic resin may be one obtained by copolymerizing monomers such as acrylic acid, methacrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide.
In this specification, “(meth) acrylate” is a concept including both “acrylate” and “methacrylate”.

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

  The acrylic resin may have a functional group that can be bonded to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxyl group, and an isocyanate group. Bonding with another compound may be performed via a crosslinking agent (f) described later, or the functional group may be directly bonded to another compound without passing through the crosslinking agent (f). . When the acrylic resin is bonded to other compounds by these functional groups, the reliability of the semiconductor package tends to be improved.

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

  In the present invention, the peelability of the pressure-sensitive adhesive layer, which will be described later, is improved to improve the pick-up property, or the film-like adhesive follows the uneven surface of the adherend, so that voids and the like can be obtained. In order to suppress the generation, as the polymer component (a), a thermoplastic resin other than an acrylic resin (hereinafter sometimes simply referred to as “thermoplastic resin”) may be used alone, or an acrylic resin 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, more preferably 3,000 to 80,000.
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-described effects can be obtained. On the other hand, the hardness of the uncured film-like adhesive when it is exposed to a high temperature is reduced, and the film-like adhesion in an uncured or semi-cured state is achieved. There is a concern that the wire bonding suitability of the agent may decrease. Therefore, the content of the acrylic resin in the adhesive composition is preferably set in consideration of such influence.

  As described above, even if the heating time in the steps other than the sealing is increased, the effect of obtaining a highly reliable semiconductor package is further increased. The mass ratio of “content (mass): content (mass) of epoxy thermosetting resin (b)” is preferably 65:35 to 99: 1, and 70:30 to 99: 1. Is more preferable, and 70:30 to 95: 5 is particularly preferable.

In order to improve the various physical properties, the adhesive contains, in addition to the polymer component (a) and the epoxy-based thermosetting resin (b), other components not corresponding to these as necessary. May be.
Preferred other components contained in the adhesive include inorganic filler (c), curing accelerator (d), coupling agent (e), cross-linking agent (f), and other heats that do not fall under the epoxy resin. Examples thereof include a curable resin (g) and a general-purpose additive (h).

(Inorganic filler (c))
When the adhesive further contains an inorganic filler (c), the thermal expansion coefficient thereof can be easily adjusted, and the thermal expansion coefficient of the cured film adhesive with respect to a semiconductor chip, metal, or organic substrate. By optimizing the above, 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).

Preferable inorganic fillers (c) include silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, and the like; beads made by spheroidizing these silicas; single crystal fibers such as these silicas; A 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 using the inorganic filler (c), the ratio of the content of the inorganic filler (c) to the total content of the solid content of the adhesive composition (content of the inorganic filler (c) of the adhesive) is It is preferable that it is 5-80 mass%, and it is more preferable that it is 7-60 mass%. When the content of the inorganic filler (c) is within such a range, it becomes easier to obtain the effect of adjusting the thermal expansion coefficient.

(Curing accelerator (d))
The curing accelerator (d) is used for adjusting the curing rate of the adhesive composition.
Preferred curing accelerators (d) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, 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 (groups in which one or more hydrogen atoms are other than hydrogen atoms) Substituted imidazole); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (phosphine in which one or more hydrogen atoms are substituted with organic groups); tetraphenylphosphonium tetraphenylborate, trif 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 the curing accelerator (d) is used, the ratio of the content of the curing accelerator (d) in the adhesive composition (adhesive) is 100 parts by mass with respect to the content of the epoxy thermosetting resin (b). The content 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. However, the semiconductor package can achieve high reliability. When there is too little content of a hardening accelerator (d), the effect by using a hardening accelerator (d) will not fully be acquired, but when the content of a hardening accelerator (d) is excessive, it will be highly polar. The curing accelerator (d) moves to the adhesion interface side with the adherend in the film adhesive under high temperature and high humidity conditions, and segregates, thereby reducing the reliability of the semiconductor package.

(Coupling agent (e))
Improving the adhesion and adhesion of the film adhesive to the adherend 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. Can do. Further, by using the coupling agent (e), the water resistance of the cured product obtained by curing the film adhesive can be improved without impairing the heat resistance.

The coupling agent (e) is preferably a compound having a functional group that reacts with the functional group of the polymer component (a), the epoxy thermosetting resin (b), etc., and is a silane coupling agent. Is desirable.
Preferred examples of the silane coupling agent include 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 thereof include orchid, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane.
A coupling agent (e) may be used individually by 1 type, and may use 2 or more types together.

  When the coupling agent (e) is used, the ratio of the content of the coupling agent (e) in the adhesive composition (the adhesive) is that of the polymer component (a) and the epoxy 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. . If the content of the coupling agent (e) is too small, the above-mentioned effect due to the use of the coupling agent (e) may not be obtained. If the content of the coupling agent (e) is too large, Outgas may occur.

(Crosslinking agent (f))
When a polymer component (a) having a functional group that can be bonded to another compound such as an isocyanate group is used, a crosslinking agent (f) is used to bond this functional group to the other compound for crosslinking. be able to. By crosslinking using the crosslinking agent (f), the initial adhesive force and cohesive force of the film adhesive can be adjusted.
Examples of the crosslinking agent (f) include organic polyvalent isocyanate compounds and organic polyvalent imine compounds.

  Examples of the organic polyvalent isocyanate compounds include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, trimers of these compounds, isocyanurates, and adducts (ethylene glycol, propylene glycol). A reaction product with a low molecular active hydrogen-containing compound such as neopentyl glycol, trimethylolpropane or castor oil, such as trimethylolpropane adduct xylylene diisocyanate), or an organic polyvalent isocyanate compound and a polyol compound. The terminal isocyanate urethane prepolymer obtained can be exemplified.

  More specifically, as the organic polyvalent isocyanate compound, 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. Examples include compounds in which tolylene diisocyanate or hexamethylene diisocyanate is added to all or some of the hydroxyl groups of polyol, lysine diisocyanate, and the like.

  Examples of the organic polyvalent imine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri Examples include -β-aziridinyl propionate, N, N′-toluene-2,4-bis (1-aziridinecarboxyamide) triethylenemelamine, and the like.

  When using an isocyanate type crosslinking agent as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the polymer component (a). When the cross-linking agent (f) has an isocyanate group and the polymer component (a) has a hydroxyl group, the cross-linking structure can be easily added to the adhesive by the reaction between the cross-linking agent (f) and the polymer component (a). Can be introduced.

  When the crosslinking agent (f) is used, the content ratio of the crosslinking agent (f) in the adhesive composition (adhesive) is 0.01 parts per 100 parts by mass 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))
The other thermosetting resin (g) should just be what does not correspond to an epoxy resin and a phenol resin, and a thermosetting polyimide resin, a polyurethane resin, an unsaturated polyester resin, a silicone resin etc. can be illustrated.

(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)
When the adhesive composition further contains a solvent, the handleability is improved by dilution.
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 Examples include alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
The solvent contained in the adhesive composition may be only one type or two or more types.
The solvent contained in the adhesive composition is preferably methyl ethyl ketone from the viewpoint of uniformly mixing the components used in the adhesive composition.

[Other epoxy thermosetting resins (z)]
The adhesive does not correspond to the other epoxy thermosetting resin (z) that does not correspond to 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 may be abbreviated as “epoxy resins (z1)”) and other thermosetting agents (z2) not applicable to the phenol resin (b2) (hereinafter referred to as “thermosetting agents ( z2) ”may be abbreviated).

(Epoxy resin (z1))
Examples of the epoxy resin (z1) include known ones, specifically, polyfunctional epoxy resins, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Bifunctional or higher functional epoxy compounds such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin (excluding biphenyl type epoxy resin) can be exemplified.

Moreover, as an epoxy resin (z1), you may use the epoxy resin which has an unsaturated hydrocarbon group. Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound obtained by converting a part of an epoxy resin of a polyfunctional epoxy resin into a group containing an unsaturated hydrocarbon group. Such a compound can be produced, for example, by 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. An unsaturated hydrocarbon group is a polymerizable unsaturated group, and specifically includes an ethenyl group (vinyl group), a 2-propenyl group (allyl group), an acryloyl group, a methacryloyl group, an acrylamide group, and a methacrylamide group. Etc., and an acryloyl group is preferable.
An epoxy resin having an unsaturated hydrocarbon group is more compatible with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. For this reason, the reliability of a semiconductor package improves by using the adhesive composition containing the epoxy resin which has an unsaturated hydrocarbon group.

  The epoxy resin (z1) preferably has a high softening point or glass transition temperature from the viewpoint of improving easy pick-up properties.

Although the number average molecular weight of an epoxy resin (z1) is not specifically limited, From the viewpoint of the sclerosis | hardenability of the said adhesive agent, the intensity | strength after hardening, and heat resistance, it is preferable that it is 300-30000, and it is 400-10000. More preferably, it is particularly preferably 500 to 3000.
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 the epoxy resin (z1) is used, the content ratio of the epoxy resin (z1) in the adhesive composition (adhesive) is 5 parts by mass or less with respect to 100 parts by mass of the epoxy resin (b1). Preferably, it is 3 parts by mass or less, more preferably 1 part by mass or less.

(Thermosetting agent (z2))
The thermosetting agent (z2) functions as a curing agent for at least the epoxy resin (z1) and sometimes functions 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, a group in which an acid group is anhydrideized, and the like, and a phenolic hydroxyl group, an amino group, and an acid group are groups in which an anhydride is converted. Are preferred, more preferably a phenolic hydroxyl group or an amino group, and particularly preferably a phenolic hydroxyl group.

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

The thermosetting agent (z2) may have an unsaturated hydrocarbon group.
As the thermosetting agent having an unsaturated hydrocarbon group (z2), a compound obtained by substituting a part of the hydroxyl group of the phenol resin with a group containing an unsaturated hydrocarbon group, an aromatic ring of the phenol resin, Examples thereof include a compound in which a group containing a hydrogen group is directly bonded. 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 thermosetting agent (z2) is preferably one having a high softening point or glass transition temperature from the viewpoint of improving easy pick-up properties.

  The number average molecular weight of the thermosetting agent (z2) is preferably 300 to 30000, more preferably 400 to 10000, and particularly preferably 500 to 3000.

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

  When using a thermosetting agent (z2), the ratio of content of the thermosetting agent (z2) in adhesive composition (the said adhesive agent) is 5 mass with respect to 100 mass parts of content of a phenol resin (b2). Is preferably 3 parts by mass or less, more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less.

An adhesive composition is obtained by mix | blending each above-mentioned component for comprising the said adhesive agents, such as an epoxy-type thermosetting resin (b).
The order of addition at the time of blending each component is not particularly limited, 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 the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.

The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.

<< Composite sheet for die bonding >>
A film adhesive obtained by providing the adhesive on a support sheet 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 an adhesive layer on the substrate 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 base material is preferably various resins, specifically, polyethylene (low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE, etc.)), polypropylene, polybutene. , Polybutadiene, polymethylpentene, polyvinyl chloride fill, 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 a polymer, an ethylene / (meth) acrylic acid ester copolymer, polystyrene, polycarbonate, a fluororesin, a water additive, a modified product, a crosslinked product, or a copolymer of any of these resins.

  The substrate may be composed of one layer (single layer), may be composed of two or more layers, and when composed of a plurality of layers, the material of each layer may be the same or all may be different. , Some 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 a base material is provided with a pressure-sensitive adhesive layer on it, in order to improve the adhesiveness with the pressure-sensitive adhesive layer, uneven processing such as sandblasting, solvent processing, corona discharge processing, electron beam irradiation processing, plasma processing The surface may be subjected to oxidation treatment such as ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment. Further, the base material may have a surface subjected to primer treatment.
Among these, the substrate preferably has a surface subjected to electron beam irradiation treatment from the viewpoint that generation of fragments of the substrate due to blade friction during dicing is suppressed.

[Adhesive layer]
A well-known thing can be used suitably for the said adhesive layer.
An adhesive layer can be formed using the adhesive composition containing the various components for comprising this. The ratio of the content of non-volatile components in the pressure-sensitive adhesive composition is the same in the pressure-sensitive adhesive layer.
When the pressure-sensitive adhesive layer contains a component that is polymerized by irradiation with energy rays, the semiconductor chip can be picked up by irradiating the energy rays to reduce the adhesiveness. Such a pressure-sensitive adhesive layer can be formed using, for example, various pressure-sensitive adhesive compositions containing an energy ray-polymerizable acrylic polymer that is polymerized by irradiation with energy rays.

  Preferred examples of the pressure-sensitive adhesive composition include the acrylic polymer and an energy ray polymerizable compound (pressure-sensitive adhesive composition (i)), a hydroxyl group, and a polymerizable group in the side chain. Examples include acrylic polymers (for example, those having a hydroxyl group and a polymerizable group in the side chain via a urethane bond) and an isocyanate-based crosslinking agent (adhesive composition (ii)). Further, those containing a solvent are preferable.

  In addition to the above-mentioned components, the pressure-sensitive adhesive composition further includes any one of various additives such as a photopolymerization initiator, a dye, a pigment, a deterioration preventing agent, an antistatic agent, a flame retardant, a silicone compound, and a chain transfer agent. It may be contained.

  Although the thickness of an adhesive layer can be suitably selected according to the objective, it is preferable that it is 1-100 micrometers, it is more preferable that it is 1-60 micrometers, and it is especially preferable that it is 1-30 micrometers.

  The pressure-sensitive adhesive composition is obtained by blending each component for constituting the pressure-sensitive adhesive layer, such as an acrylic polymer. For example, except that the blending components are different, the same as in the case of the above-described adhesive composition 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, you may bridge | crosslink by heating the apply | coated adhesive composition as needed. The heating conditions can be, for example, 100 to 130 ° C. for 1 to 5 minutes, but are not limited thereto. Alternatively, the pressure-sensitive adhesive layer formed by applying and drying the pressure-sensitive adhesive composition on the surface of the release layer of the release material may be bonded to the surface of the base material, and the release material may be removed to remove the pressure-sensitive adhesive on the base material. Layers can be formed.

  Application to the surface of the base material of the adhesive composition or the surface of the release layer of the release material may be carried out by a known method. Air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain Examples of the method include using various coaters such as a coater, a die coater, a knife coater, a screen coater, a Meyer bar coater, and a kiss coater.

<Film adhesive>
Although the thickness of the said film adhesive can be suitably selected according to the objective, it is preferable that it is 1-100 micrometers, it is more preferable that it is 5-75 micrometers, and it is especially preferable that it is 5-50 micrometers.

The composite sheet for die bonding can be manufactured by forming a film adhesive on the support sheet.
When the support sheet is the base material, the film-like adhesive forms a pressure-sensitive adhesive layer on the base material as described above, except that the adhesive composition is used instead of the pressure-sensitive adhesive composition. It can be formed on a substrate in the same manner.
When the support sheet has a pressure-sensitive adhesive layer on a substrate, it is usually difficult to directly apply the adhesive composition onto 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 release side of this film-like adhesive is not provided. A film-like adhesive is separately formed on the surface of the pressure-sensitive adhesive layer, such as by removing the release material, and then bonding this to the surface of the pressure-sensitive adhesive layer. It is preferable to form on a material.

Moreover, the composite sheet | seat for die adhesion | attachment provided with the adhesive layer forms a adhesive layer using an adhesive composition other than the above-mentioned method, for example, and forms a film adhesive using an adhesive composition After the formation, the pressure-sensitive adhesive layer and the film-like adhesive are bonded to form a laminate, and the substrate can be bonded to the surface of the pressure-sensitive adhesive layer of the laminate.
The conditions for forming the pressure-sensitive adhesive layer and the film adhesive in this case are the same as those described above.

  The die bonding composite sheet can be used in the same manner as a die bonding composite sheet such as a conventional die bonding sheet or a dicing die bonding sheet to produce a semiconductor package.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

<Manufacture of die bonding adhesive and dicing die bonding sheet>
[Examples 1-3, Comparative Examples 1-3]
(Manufacture of adhesive composition)
Each component was blended in the amounts 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 has the following meaning, respectively.

-Polymer component (a)
(A) -1: Acrylic resin (“Taisan 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: 280-298 g / eq, softening point: 63-75 ° 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 162-172 g / eq, softening point 51-57 ° 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 (hydroxyl equivalent: 237 g / eq, softening point: 122.4 ° C., weight average molecular weight: 7.5 × 10 ³ )
-Thermosetting agent (z2)
(Z2) -1: a sylock type phenol resin represented by the following general formula (X) -101 (hydroxyl equivalent: 168 g / eq, softening point: 65 ° C., weight average molecular weight: 1.4 × 10 ³ )
・ Filler (c)
(C) -1: Spherical silica (“YA050C-MJA” manufactured by Admatechs)
・ Curing accelerator (d)
(D) -1: Triphenylphosphine (made by Hokuko Chemical 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, m11 and m21 are the same as above; q11 and q21 are each independently an integer of 0 or more.)

In the above 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 formula, q11 and q21 are each independently an integer of 0 or more.

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

<Evaluation of semiconductor packages>
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 RAD2500” manufactured by Lintec Corporation), the dicing die bonding sheets of Examples and Comparative Examples were applied to the polished surface of a dry polished silicon wafer (150 mm diameter, 75 μm thickness) as a film adhesive. The silicon wafer was fixed to a ring frame for wafer dicing. Next, the silicon wafer was diced into a size of 8 mm × 8 mm (50 mm / second, 30000 rpm) using a dicing apparatus (“DFD651” manufactured by Disco Corporation) to obtain a chip. At the time of this dicing, the substrate 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. A circuit pattern is formed on the copper foil (thickness 18 μm) of the copper foil-clad laminate (“CCL-HL830” manufactured by Mitsubishi Gas Chemical Company), and a solder resist (“PSR-4000” manufactured by Taiyo Ink Co., Ltd.) is formed on this circuit pattern. AUS303 ") is used, and the chip with the above film adhesive is placed on the substrate via the film adhesive (" LN001E-001 PCB (Au) AUS303 "manufactured by Chiken Giken). Crimping was performed under the conditions of 120 ° C., 2.45 N (250 gf), and 0.5 seconds. Such a laminate of a substrate and a 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 heated at 4 degreeC for 4 hours, and what heated at 175 degreeC for 5 hours were produced for every Example and the comparative example, respectively.

  Next, the unheated laminate and the heated laminate are sealed using a sealing resin (“KE-G1250” manufactured by Kyocera Chemical Co., Ltd.) so that the sealing thickness is 400 μm, and the temperature is 175 ° C. The sealing resin was cured by heating for 5 hours. Then, the sealed laminate is affixed to a dicing tape (“Adwill D-510T” manufactured by Lintec) and diced to a size of 15 mm × 15 mm using a dicing apparatus (“DFD651” manufactured by Disco). Thus, a semiconductor package for reliability evaluation was obtained.

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

  Example 1 and Comparative Examples 1 to 3 shown in Table 1 have the same mass ratio of “content of polymer component (a): content of epoxy thermosetting resin (b)”. As is apparent from the results shown in Table 1, in Example 1 in which both epoxy resin and phenol resin were biphenyl type as the epoxy thermosetting resin (b), epoxy resin and phenol resin At least on the other hand, the reliability of the semiconductor package was significantly higher than those of Comparative Examples 1 to 3 using a material other than the biphenyl type.

  Examples 1 to 3 shown in Table 2 use biphenyl type epoxy resins and phenol resins. As is 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 thermosetting resin (b), that is, Example 2 and Example 1. In the order of Example 3, the reliability of the semiconductor package was high.

  The present invention can be used for manufacturing a semiconductor package.

Claims (2)

  An adhesive for die bonding, comprising an epoxy resin and a phenol resin as an epoxy thermosetting resin, wherein the epoxy resin and the phenol resin have a biphenylene group which may have a substituent.   Furthermore, the polymer component which does not correspond to the said epoxy resin and a phenol resin is contained, The mass ratio of "content of the said polymer component: content of the said epoxy-type thermosetting resin" is 65: 35-99: 1. The adhesive for die bonding according to claim 1, wherein the adhesive is for die bonding.