JP3109707B2 - Heat resistant adhesive and semiconductor package containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a heat-resistant adhesive which is particularly suitable for bonding a semiconductor chip to a lead frame.
The present invention relates to ( an adhesive member using the adhesive ) and a semiconductor package using the same . In particular, the present invention relates to a heat-resistant adhesive which is effective for preventing a package crack at the time of solder reflow after moisture absorption in a semiconductor package, especially a LOC (lead on chip) structure package, ( adhesive member using the adhesive ) And a semiconductor package using the same .

[0002]

2. Description of the Related Art A semiconductor package has a structure as shown in FIGS. 1 to 3, in which a semiconductor chip is connected to a lead frame with an adhesive or eutectic solder, and wire bonding is performed between electrodes of the chip and the lead frame. After being electrically connected by a wire (hereinafter simply referred to as a wire), the whole is molded with a sealing material. Conventionally, a general package has a structure as shown in FIG. 3, in which a chip is mounted on a tab (die pad) of a lead frame, and a connection between the lead frame and the chip is made by an Au-Si eutectic method. , Solder or epoxy-based thermosetting adhesives (die pound materials) are used.

In recent years, as the degree of integration has increased and the size of chips has increased, the proportion of semiconductor chips in packages has increased. Therefore, since the chip cannot be accommodated in the structure of the type shown in FIG. 3, a package having a tabless structure of the type shown in FIGS. 1 and 2 has been disclosed (US Pat. No. 5,140,404). JP-A-61-2
No. 18139, JP-A-61-241959,
U.S. Pat. No. 4,862,245, JP-A-1-7
6732, JP-A-2-36542, JP-A-4-318962).

A package structure of the type shown in FIGS. 1 and 2 has a LOC (lead on chip) and a COL (chip on chip), respectively.
ead), a thermosetting adhesive or a heat-resistant hot-melt adhesive is used to connect the lead frame to the semiconductor chip. In any of the structures shown in FIGS. 1 to 3, the thickness of the encapsulant has been reduced as the package has become smaller and thinner and the proportion of the chip in the package has increased. When the agent or the sealing material absorbs moisture, moisture absorbed by heat at the time of solder connection (solder reflow) evaporates and expands, and as a result, a phenomenon that cracks occur in the package has frequently occurred.

In order to prevent this phenomenon, studies have been made on both sides of the sealing material and the adhesive, and the sealing material is reduced in moisture absorption and improved in mechanical strength (JP-A-5-67703). Is being considered. On the other hand, with respect to the adhesive, water vapor at the time of reflow is released by reducing moisture absorption and separating the adhesive member into a plurality of small pieces to prevent cracks (Japanese Patent Laid-Open No. 3-109975). No solution has been studied from the viewpoint of the physical properties of the adhesive for the package having the LOC structure.

Further, from the viewpoint of lowering the bonding temperature, a solvent is intentionally left to soften the resin (Japanese Unexamined Patent Publication No. 3-64).
No. 386), the flowability is improved by leaving a solvent or the like, and the leak current between the inner leads is reduced by making the adhesion sufficient (Japanese Patent Application Laid-Open No. 2-36542). The adhesive for bonding the semiconductor chip as described above has not yet sufficiently prevented the occurrence of cracks in the semiconductor chip package.

[0007]

SUMMARY OF THE INVENTION The present invention has a high heat resistance, a high adhesive strength, a low water absorption and a high temperature of 260 ° C.
It is an object of the present invention to provide a heat-resistant adhesive exhibiting high package crack resistance even when soldering , and a semiconductor package using the same .

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies on the relationship between package cracks and the physical properties of the adhesive during solder reflow after moisture absorption of a LOC package or the like. Rather, it has been found that the softness of the adhesive at high temperatures, or conversely, the stiffness, is a major factor in package cracking and can be improved by using an adhesive having a certain stiffness ( or difficulty flowing ). Thus, the present invention has been completed.

Conventionally, as to the hardness of the adhesive, as described above, a solvent is intentionally left from the viewpoint of lowering the bonding temperature to soften the resin (JP-A-3-64386) and leave the solvent. To improve liquidity,
The leak current between the inner leads is reduced by making the bonding sufficient (Japanese Patent Laid-Open No. 2-36542). However, as in the present invention, the rigidity ( or difficulty of flowing ) of the adhesive is reduced. It is a major factor of package cracking rather than water absorption or Tg, and it is completely expected that the use of an adhesive having a specific hardness ( or difficulty in flowing ) is effective for improving package cracking resistance. Did not.

That is, the present invention provides: (A) a heat-resistant adhesive: a semiconductor chip is bonded to a lead frame with an adhesive member, and at least the semiconductor chip and the bonding portion between the semiconductor chip and the lead frame are sealed with a sealing material. A heat-resistant adhesive mainly composed of a heat-resistant thermoplastic resin used for an adhesive member for manufacturing a semiconductor package, and having a size of 19 × 50 m
m, 25μm thick adhesive film at 350 ° C, 3MP
a When pressed under the condition of 1 minute, the length of the protruding adhesive is measured at the center in the long side direction. The protruding length is 2 mm or less, the water absorption rate is 3% by weight or less, and the glass transition temperature is 200 ° C. or more. An adhesive is provided. In addition, the semiconductor chip is bonded to the lead frame with an adhesive member, and at least the semiconductor chip and the adhesive portion between the semiconductor chip and the lead frame are sealed with a sealing material to be used as an adhesive member for manufacturing a semiconductor package. A heat-resistant adhesive mainly composed of a thermoplastic resin, wherein (a) the semiconductor package has a LOC (lead-on-chip) structure, and (b) 19 × 50 mm and a thickness of 25 μm.
m adhesive film at 350 ° C, 3MPa, 1 minute
When pressed with, the length of the protruding adhesive is
Provided is a heat-resistant adhesive having a protruding length of 2 mm or less measured at the center , a water absorption of 3% by weight or less, and a glass transition temperature of 200 ° C. or more. It is also characterized in that the adhesive member is a composite adhesive sheet in which the heat-resistant adhesive coating film is provided on both sides of a heat-resistant film. Another characteristic is that the heat-resistant adhesive coating films provided on both sides of the heat-resistant film are made of different heat-resistant adhesives. Also,
It is also characterized in that the adhesive member is a heat-resistant adhesive alone. Another feature is that the heat resistant adhesive is a polyimide adhesive. Also,

[0011]  Polyimide adhesiveIs diamine (A) and acid
(1) the diamine (A) is an alkylenediamine,
Nilendiamine, metatoluylenediamine; 4,4'-diaminodiphenyl ether (DDE),
4,4'-diaminodiphenylmethane, 4,4'-dia
Minodiphenyl sulfone; 3,3'-diaminodiphenyl sulfone, 3,3'-di
Aminobenzophenone; 1,3-bis (4-aminokumi
B) benzene, 1,4-bis (4-aminocumyl) ben
Zen, 1,3-bis (3-aminophenoxy) benze
1,4-bis (3-aminophenoxy) benzene,
1,4-bis (4-aminophenoxy) benzene; 2,2-bis [4- (4-aminophenoxy) phenyl
] Propane (BAPP), 2,2-bis [4- (4-
Aminophenoxy) phenyl] hexafluoropropa
Bis [4- (3-aminophenoxy) phenyl] sulfo
(M-APPS), bis [4- (4-aminophenoki)
4,4'-diamino-3,3 ', 5,5'-tetramethyl
Rudiphenylmethane, 4,4'-diamino-3,3 ',
5,5'-tetraethyldiphenylmethane, 4,4'-
Diamino-3,3 ', 5,5'-tetraisopropyldi
Phenylmethane, 4,4'-diamino-3,3'-dim
Chill-5,5'-diethyldiphenylmethane, 4,4 '
-Diamino-3,3'-dimethyl-5,5'-diisoprop
Ropirdiphenylmethane, 4,4'-diamino-3,
3'-diethyl-5,5'-diisopropyldiphenyl
Methane, 4,4'-diamino-3,3'-dimethyldiph
Phenylmethane, 4,4'-diamino-3,3'-diethyl
Rudiphenylmethane, 4,4'-diamino-3,3'-
Diisopropyldiphenylmethane; selected from the group consisting of siloxane diamines of the following general formula (1)
At least one selected, and

Embedded image (However, both R ¹⁵ and R ¹⁸ are trimethylene groups, R ¹⁶ and R ¹⁷ are both methyl groups, m is 1, about 10 on average, about 20 on average, about 30 on average, about 50 on average, about 50 on average, [II] acid anhydride (B) is trimellitic anhydride, maleic anhydride, nadic anhydride, allylnadic anhydride; 3, 3 ′, 4, 4′-benzophenonetetracarboxylic diacid Anhydride (BTDA); 2,2-bisphthalic acid hexafluoroisopropylidene dianhydride; bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride , Ethylene glycol bistrimellitate dianhydride (EB
TA), decamethylene glycol bistrimellitate dianhydride (DBTA), bisphenol A bistrimellitate dianhydride (BABT); 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bisphenylbistriene It is also characterized in that it is at least one selected from the group consisting of melitate dianhydride.

(B) Semiconductor package:19 × 50mm, 25μm thick adhesive film
When pressed at 350 ° C, 3MPa, 1 minute,
The length of the exposed adhesive was measured at the center in the long side directionFir
Dispensing length 2mm or less, water absorption 3% by weight or less, Glass transition
Temperature over 200 ° CIsHeat resistant thermoplastic resin as main component
DoA semiconductor chip that uses a heat-resistant adhesive for the adhesive member
To the lead frame with adhesive
Body chip, semiconductor chip and lead frame
A semiconductor package sealed with a stopper is provided. Also,
 19 × 50 mm, 25 μm thick adhesive film
When pressed at 50 ° C, 3MPa, 1 minute
The length of the adhesive was measured at the center in the long side directionProtruding
Length 2mm or less, Water absorption 3% by weight or less, Glass transition temperature
Degree 200 ℃ or moreIsHeat-resistant thermoplastic resin as the main component
ToCharacterized in that a heat-resistant adhesive is used for an adhesive member.
Bonding the semiconductor chip to the lead frame with an adhesive
At least the semiconductor chip, the semiconductor chip and the lead
A semiconductor package in which the bonding part of the frame is sealed with a sealing material
Then, the semiconductor package is LOC (lead on
A semiconductor package having a (chip) structure is provided. Ma
(A) −〜 Heat-resistant adhesive according to any of the above
(B)-Description, characterized in that is used for the adhesive member
Semiconductor package is provided. Also, (A) −〜
Use the heat-resistant adhesive described in any of
(B) The semiconductor package according to-,
I will provide a.

Hereinafter, the present invention will be described in detail. The specific heat-resistant adhesive used in the present invention has a water absorption of 3 wt% or less,
19 × 50 mm, 25 μm thick adhesive film
When pressed under the conditions of 0 ° C, 3MPa and 1 minute, it protrudes
A heat-resistant adhesive mainly composed of a heat-resistant thermoplastic resin having a protruding length of 2 mm or less and a glass transition temperature of 200 ° C. or more measured at the central portion in the long side direction of the adhesive is preferable. For that purpose, a polyimide adhesive (and / or a polyamide adhesive ) is preferable. Here, polyimide includes resins having an imide group such as polyamide imide, polyester imide, and polyether imide.

[0014] heat-resistant adhesive of the present invention, the water absorption 3% by weight or less, preferably 2.5 wt% or less, more preferably Ri der 2.0 wt% or less, and to the particular measuring method
That protrudes is 2mm or less in length, preferably 1mm or less,
More preferably, it needs to be 0.5 mm or less. Further, heat-resistant adhesive of the present invention has a glass transition temperature of 200 ° C. or higher in addition to the characteristics, preferably 225 ° C. or higher, more preferably should have a higher 250 ° C.. In the present invention , when the glass transition temperature is lower than 250 ° C. or when the protrusion length is longer than 1 mm, the water absorption is desirably lower than 1.5% by weight. In addition, it is preferable that the protruding length be shorter for a package having a smaller thickness of the sealing material or a larger proportion of the adhesive.

The adhesive of the present invention may be composed of polyimide (and / or polyamide) alone, but preferably contains an amide group from the viewpoint of adhesive strength. Here, the amide group is an amide group remaining after imide ring closure,
It does not include the amide group in the amide acid that is the imide precursor.
The amide group is 10 to 90 of the total amount of the imide group and the amide group.
Mol% is good, preferably 20 to 70 mol%, more preferably 30 to 50 mol%. If it is less than 10%, the adhesive strength is small, and if it is more than 90%, the water absorption becomes large.

The heat-resistant adhesive of the present invention is basically synthesized from a diamine or diisocyanate (A) and an acid anhydride (B) and / or a dicarboxylic acid or an amide-forming derivative thereof (C). The combination of the above-mentioned reaction components, the reaction ratio, the reaction conditions, the molecular weight, the presence or absence of additives and the It can be easily manufactured by variously adjusting the kind, additional resin such as epoxy resin and the like.

Diamine (A) used in the present invention
Examples thereof include alkylenediamines such as hexamethylenediamine, octamethylenediamine and dodecamethylenediamine; arylenediamines such as paraphenylenediamine, metaphenylenediamine and metatoluylenediamine; 4,4′-diaminodiphenyl ether (DDE);
4,4 ′ diaminodiphenylmethane, 4,4 ′ diaminodiphenyl sulfone, 3,3 ′ diaminodiphenyl sulfone, 4,4 ′ diaminobenzophenone, 3,
Diaminodiphenyl derivatives such as 3 'diaminobenzophenone and 4,4'diaminobenzanilide; 1,4-bis (4-aminocumyl) benzene (BA
P), 1,3-bis (4-aminocumyl) benzene,
1,3-bis (3-aminophenoxy) benzene, 1,
4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), 2,2-bis [4- ( 3-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] sulfone (m-APPS), bis [4- (4-aminophenoxy) phenyl] sulfone,
2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, and

Examples include diamines represented by the following general formula (2) and siloxane diamines represented by the following general formula (2).

Embedded image [In the above formula, Y represents an amino group, and R ¹¹ , R ¹² , R ¹³ , R
¹⁴ is each independently hydrogen or an alkyl group or alkoxy group having 1 to 4 carbon atoms, at least two of which are alkyl groups or alkoxy groups,
X is _{-CH 2 -, - C (CH} 3) 2 -, - O -, - SO
₂ -, - it is a group represented by CO- or -NHCO-. ]

Examples of the compound represented by the general formula (2) include 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylmethane, 4,4'-diamino-3,
3 ′, 5,5′-tetraethyldiphenylmethane, 4,
4'-diamino-3,3 ', 5,5'-tetra-n-propyldiphenylmethane, 4,4'-diamino-3,
3 ′, 5,5′-tetraisopropyldiphenylmethane, 4,4′-diamino-3,3 ′, 5,5′-tetrabutyldiphenylmethane, 4,4′-diamino-3,
3′-dimethyl-5,5′-diethyldiphenylmethane, 4,4′-diamino-3,3′-dimethyl-5,
5′-diisopropyldiphenylmethane, 4,4′-diamino-3,3′-diethyl-5,5′-diisopropyldiphenylmethane, 4,4′-diamino-3,5-dimethyl-3 ′, 5′-diethyldiphenylmethane, 4,
4'-diamino-3,5-dimethyl-3 ', 5'-diisopropyldiphenylmethane, 4,4'-diamino-
3,5-diethyl-3 ', 5'-diisopropyldiphenylmethane, 4,4'-diamino-3,5-diethyl-
3 ', 5'-dibutyldiphenylmethane, 4,4'-diamino-3,5-diisopropyl-3', 5'-dibutyldiphenylmethane, 4,4'-diamino-3,3'-
Diisopropyl-5,5'-dibutyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl-5,
5′-dibutyldiphenylmethane, 4,4′-diamino-3,3′-diethyl-5,5′-dibutyldiphenylmethane,

4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diamino-3,
3′-di-n-propyldiphenylmethane, 4,4′-diamino-3,3′-diisopropyldiphenylmethane,
4,4'-diamino-3,3'-dibutyldiphenylmethane, 4,4'-diamino-3,3 ', 5-trimethyldiphenylmethane, 4,4'-diamino-3,3', 5
-Triethyldiphenylmethane, 4,4'-diamino-
3,3 ′, 5-tri-n-propyldiphenylmethane,
4,4'-diamino-3,3 ', 5-triisopropyldiphenylmethane, 4,4'-diamino-3,3', 5
-Tributyldiphenylmethane, 4,4'-diamino-
3-methyl-3'-ethyldiphenylmethane, 4,4 '
-Diamino-3-methyl-3'-isopropyldiphenylmethane, 4,4'-diamino-3-ethyl-3'-isopropyldiphenylmethane, 4,4'-diamino-3
-Ethyl-3'-butyldiphenylmethane, 4,4'-
Diamino-3-isopropyl-3′-butyldiphenylmethane,

4,4'-diamino-2,2'-bis (3,3 ', 5,5'-tetramethyldiphenyl) isopropane, 4,4'-diamino-2,2'-bis (3
3 ′, 5,5′-tetraethyldiphenyl) isopropane, 4,4′-diamino-2,2′-bis (3,3 ′,
5,5'-tetra-n-propyldiphenyl) isopropane, 4,4'-diamino-2,2'-bis (3,3 ',
5,5′-tetraisopropyldiphenyl) isopropane, 4,4′-diamino-2,2′-bis (3,3 ′,
(5,5′-tetrabutyldiphenyl) isopropane,

4,4'-diamino-3,3 ', 5,5'
-Tetramethyldiphenyl ether, 4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylether, 4,4'-diamino-3,3', 5,5'-tetra-n-propyldiphenylether, , 4'-Diamino-3,3 ', 5,5'-tetraisopropyldiphenyl ether, 4,4'-diamino-3,3', 5
5′-tetrabutyl diphenyl ether,

4,4'-diamino-3,3 ', 5,5'
-Tetramethyldiphenylsulfone, 4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylsulfone, 4,4'-diamino-3,3', 5,5'-tetran-propyldiphenylsulfone 4,4′-diamino-3,3 ′, 5,5′-tetraisopropyldiphenylsulfone, 4,4′-diamino-3,3 ′, 5,5 ′
-Tetrabutyldiphenylsulfone,

4,4'-diamino-3,3 ', 5,5'
-Tetramethyldiphenylketone, 4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylketone, 4,4'-diamino-3,3', 5,5'-tetran-propyldiphenylketone , 4,4'-diamino-
3,3 ′, 5,5′-tetraisopropyldiphenylketone, 4,4′-diamino-3,3 ′, 5,5′-tetrabutyldiphenylketone,

4,4'-diamino-3,3 ', 5,5'
-Tetramethylbenzanilide, 4,4'-diamino-
3,3 ′, 5,5′-tetraethylbenzanilide,
4,4'-diamino-3,3 ', 5,5'-tetra-n-
Propylbenzanilide, 4,4'-diamino-3,
3 ′, 5,5′-tetraisopropylbenzanilide,
4,4′-diamino-3,3 ′, 5,5′-tetrabutylbenzanilide and the like.

[0026]

Embedded image [In the above formula, R ¹⁵ and R ¹⁸ are divalent organic groups, R ¹⁶ and R ¹⁷ are monovalent organic groups, and m is an integer of 1 to 100. ]

In the general formula (1), R ¹⁵ and R ¹⁸ each independently include a trimethylene group, a tetramethylene group, a phenylene group, a toluylene group and the like, and R ¹⁶ and R ¹⁸ each independently represent a methyl group. , An ethyl group, a phenyl group and the like, and a plurality of R ¹⁶ and a plurality of R ¹⁷ may be the same or different. Preferably, in the siloxane diamine of the general formula (1), when R ¹⁵ and R ¹⁸ are both a trimethylene group and both R ¹⁶ and R ¹⁷ are a methyl group, m is 1 and an average of 10 Before and after, about 20 on average, about 30 on average,
Those with an average of around 50 and those with an average of around 100 were LP-7100, X-22-161AS, X-22-161A, X-22-161B, X-22-161C and X-22-161E, respectively. Shin-Etsu Chemical Co., Ltd.
(Trade name).

The diisocyanate (A) ′ used in the present invention includes the diamines exemplified above:
Examples in which an amino group is replaced with an isocyanate group can be given.

The acid anhydride (B) used in the present invention includes trimellitic anhydride, pyromellitic dianhydride,
3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2-hexafluoroisopropylidene dibisphthalate Anhydride, bis (3, 4
-Dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride,
4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride,

2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, ethylene glycol bistrimellitate dianhydride (EBTA),
Decamethylene glycol bistrimellitate dianhydride (DBTA), bisphenol A bistrimellitate dianhydride (BABT),

2,2-bis [4- (3,4-dicarboxyphenylbenzoyloxy) phenyl] hexafluoropropane dianhydride, 4,4 '-[1,4-phenylenebis (1-methylethylidene)] Bisphenylbistrimellitate dianhydride; maleic anhydride, methylmaleic anhydride, nadic acid, allylnadic anhydride, methylnadic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and the like.

In the present invention, the dicarboxylic acid or its amide-forming derivative (C) which may be used if necessary includes terephthalic acid, isophthalic acid, biphenylcarboxylic acid, phthalic acid, naphthalenedicarboxylic acid, diphenylether dicarboxylic acid and the like. Examples of the amide-forming derivatives of these dicarboxylic acids include dichlorides and dialkyl esters of these dicarboxylic acids.
Further, a part of the diamine (A) and the dicarboxylic acid (C) may be replaced with an aminocarboxylic acid such as aminobenzoic acid.

Preferably, the heat-resistant adhesive of the present invention comprises: (A) alkylene diamine, metaphenylenediamine, metatoluylenediamine, 4,4'-diaminodiphenyl ether (DDE), 4,4'-diaminodiphenylmethane as diamine 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,
3'-diaminobenzophenone, 1,3-bis (4-aminocumyl) benzene, 1,4-bis (4-aminocumyl) benzene, 1,3-bis (3-aminophenoxy)
Benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP),

Bis [4- (3-aminophenoxy) phenyl] sulfone (m-APPS), bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl Hexafluoropropane, 4,4'-diamino-3,3 ', 5
5′-tetramethyldiphenylmethane, 4,4′-diamino-3,3 ′, 5,5′-tetraethyldiphenylmethane, 4,4′-diamino-3,3 ′, 5,5′-tetraisopropyldiphenylmethane, 4, 4'-diamino-3,3'-dimethyl-5,5'-diethyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl-
5,5'-diisopropyldiphenylmethane, 4,4 '
-Diamino-3,3'-diethyl-5,5'-diisopropyldiphenylmethane, 4,4'-diamino-3,
3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, 4,4′-diamino-3,3′-diisopropyldiphenylmethane,
Further, in the siloxane diamine of the general formula (1), L
P-7100, X-22-161AS, X-22-16
A commercial product with a trade name of 1A can be preferably used.

Preferably, the (B) acid anhydride is
Trimellitic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 2,2-
Hexafluoroisopropylidene dianhydride bisphthalate, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 4,4′-bis (3,4 -Dicarboxyphenoxy) diphenylsulfone dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl]
Propane dianhydride, ethylene glycol bistrimellitate dianhydride (EBTA), decamethylene glycol bistrimellitate dianhydride (DBTA), bisphenol A bistrimellitate dianhydride (BABT), 4,
4 '-[1,4-phenylenebis (1-methylethylidene)] bisphenylbistrimellitate dianhydride; maleic anhydride, nadic anhydride, and allylnadic anhydride can be preferably used.

In the present invention, these diamines (A),
The resin produced by appropriately combining the acid anhydride (B) and / or the dicarboxylic acid (C) has a Tg of preferably 200
The monomer may be appropriately selected so as to be at least 250C, more preferably at least 250C.

[0037] To the heat-resistant adhesive with specific properties of the present invention, in the case of mixing the polyimide and polyamide, Tg of the adhesive after mixing may if more than 200 ° C.. As the heat-resistant adhesive of the present invention, the above polyimide
Without limitation to (and / or polyamide ) , polymaleimide and polyallylnadiimide can be used as well. Polyimides are obtained by thermal or chemical ring closure of polyamic acids. The polyimide varnish used in the present invention may not necessarily be 100% imidized, but is preferably completely imidized.

The heat-resistant adhesive of the present invention may be made of polyimide or polyamide alone, or a mixture of polyimide and polyamide, or may be used by adding an epoxy resin, a curing agent, a curing accelerator and the like. In this case, by appropriately mixing an additive resin such as an epoxy resin and the following additives such as a coupling agent, the T
g is water absorption A at 200 ° C. or less, What can be adjusted so that the length protruding in the scope of the present invention.

The epoxy resin which may be mixed with the specific polyimide-based heat-resistant adhesive of the present invention is not particularly limited as long as it has two or more epoxy groups per molecule on average. Diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, phenol novolak type epoxy resin, polyglycidyl ester of polyhydric alcohol, polyglycidyl ester of polybasic acid, alicyclic epoxy resin, hydantoin type epoxy resin, etc. Can be.

Further, a filler such as ceramic powder, glass powder, silver powder, copper powder and the like, and a coupling agent may be added to the heat-resistant adhesive of the present invention. Further, the heat-resistant adhesive of the present invention may be used by impregnating a base sheet such as a glass cloth, an aramid cloth, and a carbon fiber cloth.

Examples of the coupling agent include vinyl silanes such as vinyl triethoxy silane, vinyl trimethoxy silane, and γ-methacryloxy propyl trimethoxy silane; γ-glycidoxy propyl trimethoxy silane;
-Glycidoxypropylmethyldiethoxysilane, β-
Epoxy silanes such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane; aminosilanes such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; Mercaptosilanes such as mercaptopropyltrimethoxysilane; coupling agents such as titanates, aluminum chelates, and zircoaluminates are used, but silane coupling agents are preferable, and epoxysilane coupling agents are particularly preferable.

The heat-resistant adhesive used in the adhesive member of the present invention may be used alone, or may be applied or impregnated on a base film or sheet. When the heat-resistant adhesive is used alone, the heat-resistant adhesive may be directly applied to an adherend such as a semiconductor chip or a lead frame, or may be applied in advance in a sheet form to the adherend, and then thermocompression-bonded. Is also good.

When the heat-resistant adhesive of the present invention is applied on a base film (or sheet) to be used as a composite adhesive sheet, the composite adhesive sheet has a water absorption coefficient on both sides of the heat-resistant film, preferably the surface-treated heat-resistant film. 3% by weight or less, 19 × 50 mm, 25 μm thick adhesive film
When pressed at 350 ° C, 3MPa, 1 minute,
The length of the protruding adhesive was measured at the center in the long side direction. The protruding length was 2 mm or less , and the glass transition temperature was 200 ° C. or more.
It is obtained by applying a heat-resistant adhesive containing a heat-resistant thermoplastic resin as a main component or a varnish thereof and then heating. The heat resistant adhesive applied to both sides may be the same or different.

The heat-resistant film used as the base film in the present invention includes films of polyimide, polyamide, engineering plastics such as polysulfone, polyphenylene sulfide, polyether ether ketone, and polyarylate. The heat-resistant film has a glass transition temperature (Tg) higher than that of the heat-resistant adhesive of the present invention.
Those having a temperature of 0 ° C. or higher, more preferably 250 ° C. or higher, are used. A heat-resistant film having a water absorption of 3% by weight or less, preferably 2% by weight or less is used. Therefore, as the heat resistant film used in the present invention, a polyimide film is preferable in terms of Tg, water absorption, and coefficient of thermal expansion. Tg of 250 ° C. or more, water absorption of 2% by weight or less, thermal expansion coefficient of 3
A film having physical properties of × 10 ⁻⁵ / ° C. or less is particularly preferred.

The heat-resistant film is desirably subjected to a surface treatment in order to increase the adhesive strength with the adhesive. As a method of surface treatment, any treatment such as alkali treatment, chemical treatment such as silane coupling treatment, physical treatment such as sand blast, plasma treatment, corona treatment, etc. can be used.
The most suitable treatment may be used according to the type of the adhesive.
When applying the heat-resistant adhesive of the present invention, a chemical treatment or a plasma treatment is particularly suitable as a surface treatment to be performed on the heat-resistant film. The method for applying the heat-resistant adhesive (varnish) to the heat-resistant film is not particularly limited. The coating may be performed by any method such as a doctor blade, a knife coater, and a die coater. Further, the film may be applied through a film in the varnish, but it is not preferable because the thickness is difficult to control.

When the film coated with the heat-resistant adhesive of the present invention is subjected to a heat treatment for removing a solvent or imidizing, the heat treatment temperature differs depending on whether it is a polyamide acid varnish or a polyimide varnish. In the case of polyamic acid varnish,
Although a temperature of Tg or more is required for imidization,
In the case of a polyimide varnish, any temperature may be used as long as the solvent can be removed. In order to improve the adhesive strength between the adhesive and the heat-resistant film, it is preferable to perform a heat treatment at a temperature of 250 ° C. or more.

An adhesive member using the heat-resistant adhesive of the present invention is particularly effective for bonding a lead frame to a semiconductor chip. When the adhesive member of the present invention is used for connection between a semiconductor chip and a lead frame, there is no particular limitation on the method, and connection may be made by a method most suitable for each package. For example, (i) the heat-resistant adhesive double-sided coated composite sheet of the present invention is first thermocompression-bonded to a lead frame, and then the semiconductor chip is thermocompression-bonded to the opposite heat-resistant adhesive face of the present invention. (ii) The single-sided heat-resistant adhesive sheet of the present invention is thermocompression-bonded to a lead frame, and then the same or another adhesive paste selected from the adhesive of the present invention is applied to the other side, and the semiconductor chip is crimped. When the heat-resistant adhesive is applied to both sides of the heat-resistant film, the adhesives corresponding to the semiconductor chip and the lead frame may be different from each other so as to be better fitted to each other, and specifically, constitute the heat-resistant adhesive. It is preferred that the types and ratios of the components of the thermoplastic resin, the reaction conditions for production, and the like, and the shape (for example, paste, film, etc.) of the heat-resistant adhesive be varied. (iii) The heat-resistant adhesive single film of the present invention is sandwiched between a semiconductor chip and a lead frame and thermocompression-bonded. (Iv) Various methods such as applying the heat-resistant adhesive of the present invention to a semiconductor chip or a lead frame, and thermocompression bonding with the lead frame or the semiconductor chip can be used. A specific method of bonding a semiconductor chip to a lead frame using an adhesive member using the heat-resistant adhesive of the present invention will be described with reference to FIGS.

FIGS. 1 to 3 show a semiconductor chip bonded to a lead frame with an adhesive member using the heat-resistant adhesive of the present invention, and the semiconductor chip and the bonding portion between the semiconductor chip and the lead frame are sealed with a sealing material. FIG. 7 is a schematic diagram showing a bonding state when the shape of the lead frame and the position of the semiconductor chip bonded to the lead frame are different in the manufactured semiconductor package.

FIG. 1 is a schematic diagram showing a semiconductor package having a LOC (lead on chip) structure. That is, in the semiconductor package, the semiconductor chip 2 is located below the lead frame 3 , and as shown in the drawing, the lead on the side opposite to the bonding surface 7 of the semiconductor chip 2 in the area 6 on the projection surface of the semiconductor chip 2. Wire bonding 4 is performed on the frame surface 8. Therefore, the semiconductor package has a tabless structure in which wire bonding for contacting the semiconductor chip and the lead frame is provided on the semiconductor chip. FIG.
It is a schematic diagram which shows the semiconductor package of L (chip on lead) structure. That is, in the semiconductor package, the semiconductor chip 2 is located above the lead frame 3. FIG. 3 is a schematic diagram when the semiconductor chip 2 is located above the lead frame 3. 1 to 3, reference numeral 1 denotes an adhesive member, 2 denotes a semiconductor chip, 3 denotes a lead frame, 4 denotes a wire, 5 denotes a sealing material, 6 denotes an area of a projection surface of the semiconductor chip, 7 denotes an adhesion surface of the semiconductor chip, 8 Is an end surface of the lead frame opposite to the bonding surface.

An adhesive member using the heat-resistant adhesive of the present invention is effective for connecting a semiconductor chip of the type shown in FIG. 1 to a lead frame. The package having the LOC (lead on chip) structure shown in FIG. 1 is different from the package having the COL (chip on lead) structure shown in FIG. 2 and the package shown in FIG. 3 in that the proportion of the semiconductor chip in the entire package is large. I have. (1) For the package of FIG. 3, the package of FIG. 1 has a tabless structure. (2) In the packages of FIGS. 2 and 3, wire bonding is performed beside the semiconductor chip. On the other hand, the package of FIG. 1 is wire-bonded on the semiconductor chip, and the package of FIG. 1 does not require a space for wire-bonding separately from the semiconductor chip. Therefore, in the package of FIG. 1, the proportion of the semiconductor chip in the entire package can be increased, so that the sealing material inevitably becomes thinner in the entire package, and the influence of the adhesive on the occurrence of package cracks increases.

In the package of FIG. 1, the number of occurrences of package cracks increases more rapidly than in the packages of FIGS. 2 and 3, and a countermeasure has been desired. The adhesive of the present invention is shown in FIG.
This is particularly effective in preventing the occurrence of package cracks in the package. Thus, the heat-resistant adhesive of the present invention has a LOC
The structure package, that is, the wire bonding for bringing the semiconductor chip into contact with the lead frame, is particularly suitable for the connection between the semiconductor chip and the lead frame in the sealed semiconductor package having the tabless structure on the semiconductor chip.

Since the adhesive member of the present invention does not use any adhesive other than the heat-resistant adhesive of the present invention, it is effective for preventing package cracks during solder reflow after moisture absorption in a semiconductor package. The heat-resistant adhesive of the present invention is not limited thereto, and may be a ceramic plate, a metal plate, a metal foil, a plastic film, a plastic plate,
It can also be effectively applied to adherends such as laminates. In that case, the adherend is heated or pressed at a temperature equal to or higher than the softening temperature of the adhesive by being applied on the adherend or sandwiched between the adherends in the case of a sheet, so that the adherend is heated by another material. It can be adhered to.

[0053]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these ranges. Example 1 In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a calcium chloride tube, 4,4′-diamino-3,
3.66 g (10 mmol) of 3 ', 5,5'-tetraisopropyldiphenylmethane (IPDDM) and 28.3 g of N, N-dimethylformamide (DMF)
And dissolved. Next, 5.76 g (10 mmol) of bisphenol A bistrimellitate dianhydride (BABT) was added little by little while cooling so as not to exceed 5 ° C., and then 1 hour while cooling so as not to exceed 5 ° C. Then, the mixture was reacted at room temperature for 6 hours to synthesize a polyamic acid. Acetic anhydride 2.5 was added to the resulting varnish of polyamic acid.
5 g and 1.98 g of pyridine were added, and reacted at room temperature for 3 hours to synthesize a polyimide. The resulting polyimide varnish was poured into water, and the resulting precipitate was separated, crushed and dried to obtain a polyimide powder. This polyimide powder is DM
F was dissolved in F at a concentration of 0.1 g / dl, and the reduced viscosity measured at 30 ° C. was 0.71 dl / g.

A solubility test was conducted by adding the polyimide powder to various organic solvents to a concentration of 5% by weight and observing the dissolution state at room temperature. As a result, the polyimide powder contains DMF, N-methylpyrrolidone (NMP), methylene chloride, dioxane, THF,
It was soluble in toluene. Further, this polyimide powder was dissolved in DMF, and the obtained varnish was cast on a glass plate. After drying at 100 ° C. for 10 minutes, the film was peeled off, fixed to an iron frame, and dried at 250 ° C. for 1 hour to obtain a film.

Using the film thus obtained, the glass transition temperature (Tg) of the polyimide was measured at 262 ° C. by a penetration method under the conditions of a load of 25 kg / cm ² and a temperature rising rate of 10 ° C./min. . The thermal decomposition temperature was 405 ° C. Put the film in water at 25 ° C for 24 hours.
The water absorption when immersed for an hour was 0.3% by weight. 1
9 × 50 mm, 25 μm thick adhesive film
Pressing was performed at 3 ° C. for 1 minute at a temperature of 3 ° C., and the length of the protruding adhesive was measured at the center in the long side direction, and the protruding length was 0.8 mm.

When the obtained film was bent at an angle of 180 degrees and subjected to a flexibility test, the film showed good flexibility without cracking. NMP of polyimide
After applying the varnish on the plasma-treated UPILEX S film, the varnish was applied at 100 ° C. for 10 minutes, and further at 300 ° C. for 1 minute.
After drying for 0 minutes, a composite sheet was obtained. This composite sheet is
After pressing on the alloy at 350 ° C. and 3 MPa for 5 seconds, the 90 ° peel strength was measured to be 0.7 k
N / m. Using this composite sheet, a semiconductor chip is packaged as shown in FIG. 1 (thin small-out-line packa).
ge)) to produce a TSOP type package.
At 48% RH for 48 hours.
Although immersed in a 0 ° C. solder bath, no cracks occurred.

Example 2 3.58 g (10 mmol) of bis (3,4-dicarboxyphenyl) sulfone dianhydride (DSDA), IPD
1.83 g (5 mmol) of DM, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAP
P) A polyamic acid varnish was obtained in the same manner as in Example 1 except that 2.05 g (5 mmol) was used. A polyimide powder was obtained from this polyamic acid varnish in the same manner as in Example 1. Its reduced viscosity is 1.21 dl / g and Tg is 268
℃, the thermal decomposition temperature was 410 ℃. The water absorption is 0.1.
At 7% by weight, the protruding length was 0.01 mm. Using the above polyamic acid varnish, 100 ° C. for 10 minutes, 30
A composite sheet was obtained in the same manner as in Example 1 except that the heat treatment was performed at 0 ° C. for 15 minutes. 1.2kN / m adhesion to 42 alloy
In the semiconductor package (TSOP type) obtained in the same manner as in Example 1, no crack was generated by the solder treatment after moisture absorption.

Example 3 Instead of BABT, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) 3.22
g (10 mmol), NMP 20.6 instead of DMF
A polyamic acid varnish was obtained in the same manner as in Example 1 except that g was used. 10 g of xylene was added to this varnish and heated at 180 ° C. for 5 hours to obtain a polyimide varnish. The reduced viscosity was 0.48 dl / g, the Tg was 300 ° C., and the thermal decomposition temperature was 405 ° C. The water absorption is 1.0% by weight
And the protruding length was 0.5 mm. After the alkali treatment, the above-mentioned polyimide varnish is applied to the Kapton film subjected to the silane coupling treatment, and the resultant is applied at 100 ° C. for 10 minutes.
C. for 10 minutes to obtain a composite sheet. The adhesive force with the 42 alloy was 0.92 kN / m, and no crack occurred in the semiconductor package (TSOP type) obtained in the same manner as in Example 1 by the solder treatment after moisture absorption.

Example 4 5.76 g (10 mmol) of BABT, IPDDM
A polyimide powder was obtained in the same manner as in Example 1, except that 2.38 g (6.5 mmol) and 0.43 g (3.5 mmol) of metatoluylenediamine (MTDA) were used. The reduced viscosity was 0.61 dl / g, the Tg was 275 ° C., and the thermal decomposition temperature was 415 ° C. The water absorption is 0.5% by weight
The protrusion length was 1.5 mm. After applying the above-mentioned NMP varnish of the polyimide onto an alkali-treated Iupirex S film, the mixture was further treated at 100 ° C. for 10 minutes and 30 minutes.
After drying at 0 ° C. for 10 minutes, a composite sheet was obtained. The adhesive strength with the alloy No. 42 was 0.85 kN / m, and the semiconductor package [SOJ (Small outline J-
No cracks occurred in the leaded package) type] due to the solder treatment after moisture absorption.

Example 5 3.58 g (10 mmol) of DSDA, IPDDM
0.92 g (2.5 mmol), BAPP 3.08 g
(7.5 mmol) in the same manner as in Example 3 except that polyimide powder was used. Reduced viscosity is 0.62dl / g, T
g was 255 ° C and the thermal decomposition temperature was 440 ° C. The water absorption was 1.2%, and the protruding length was 0.2 mm. The above-mentioned DMAc varnish of polyimide was coated on a plasma-treated Upilex S film, and then dried at 100 ° C. for 10 minutes and further at 250 ° C. for 10 minutes to obtain a composite sheet. The adhesive strength to 42 alloy was 1.40 kN / m, and the semiconductor package (TS
(OP type), no crack was generated by the solder treatment after moisture absorption.

Example 6 4.10 g (10 mmol) of BAPP was added to DMF24.
After dissolving in 5 g and adding 2.02 g (20 mmol) of triethylamine, 2.03 g (10 mmol) of isophthalic chloride was added little by little while cooling to 5 ° C. or lower. After reacting at 5 ° C. or less for 5 hours, a polyamide powder was obtained in the same manner as in Example 1. 0.45 reduced viscosity
dl / g and Tg were 219 ° C and the thermal decomposition temperature was 425 ° C. The water absorption was 2.3% by weight, and the protruding length was 2.4 mm. Upilex S obtained by plasma-treating DMF varnish obtained by mixing 85% by weight of polyimide obtained in the same manner as in Example 1 and 15% by weight of the above polyamide
After coating on film, 10 minutes at 100 ° C,
After drying at 50 ° C. for 10 minutes, a composite sheet was obtained. After superimposing this composite sheet on 42 alloy and pressing it at 350 ° C. and 3 MPa for 5 seconds, the 90 ° peel strength was measured.
It was 1.2 kN / m. In addition, T of the blend film
g was 255 ° C., the water absorption was 0.6% by weight, and the protrusion length was 1.5 mm. After packaging a semiconductor chip (SOJ type) as shown in FIG. 1 using this composite sheet,
After 48 hours of moisture absorption at 85 ° C. and 85% RH,
It was immersed in a solder bath at 260 ° C., but no cracks occurred.

Example 7 4,4′-Diaminodiphenyl sulfone (DDS)
1.74 g (7 mmol), BAPP 1.23 g (3
Was dissolved in 20 g of DMF, 2.02 g (20 mmol) of triethylamine was added, and then 2.03 g of isophthalic chloride was cooled to 5 ° C. or lower.
(10 mmol) was added in small portions. After reacting at 5 ° C. or less for 5 hours, a polyamide powder was obtained in the same manner as in Example 1. The reduced viscosity was 0.88 dl / g, the Tg was 260 ° C, and the thermal decomposition temperature was 435 ° C. The water absorption was 2.5% by weight, and the protruding length was 0.2 mm. A composite sheet was obtained in the same manner as in Example 1 using an NMP varnish in which 60% by weight of the polyimide of Example 1 and 40% by weight of the above polyamide were mixed. The adhesive strength of this composite sheet with 42 alloy was 1.6 kN / m. The blend film had a Tg of 260 ° C., a water absorption of 1.1% by weight, and a protruding length of 0.5 mm. A semiconductor package (TSOP) obtained in the same manner as in Example 1 using this composite sheet
No cracks were generated in the mold (2) even by the solder treatment after moisture absorption.

Example 8 1.83 g (5 mmol) of IPDDM, BAPP
2.05 g (5 mmol), trimellitic anhydride chloride 0.64 g (3 mmol), triethylamine
A polyamic acid varnish was obtained in the same manner as in Example 6, except that 0.30 g (3 mmol) and 30 g of NMP were used.
2.51 g of bis (3,4-dicarboxyphenyl) sulfone dianhydride (DSDA) was added to the varnish at 5 ° C. or lower.
(7 mmol) was added little by little, and the mixture was reacted at 5 ° C. or lower for 5 hours. Thereafter, acetic anhydride and pyridine were added to obtain a polyamideimide powder in the same manner as in Example 1. This polyamideimide has a reduced viscosity of 1.15 dl / g and a Tg of 2
The temperature was 58 ° C and the thermal decomposition temperature was 385 ° C. The water absorption was 1.0% by weight, and the protruding length was 0.02 mm. After the alkali treatment, a varnish obtained by dissolving the above polyamideimide in DMAc was applied to the Kapton film subjected to the silane coupling treatment, and the varnish was applied at 100 ° C. for 10 minutes and at 275 ° C. for 10 minutes.
The composite sheet was obtained by heat treatment. The adhesive force with the 42 alloy was 1.4 kN / m, and no crack occurred in the semiconductor package (TSOP type) obtained in the same manner as in Example 1 due to the solder treatment after moisture absorption.

Example 9 5.76 g (10 mmol) of BABT, IPDDM
2.74 g (7.5 mmol), BAPP 0.41 g
(1.0 mmol), 1.26 g of X-22-161AS
(1.5 mmol), and a polyimide powder was obtained in the same manner as in Example 1. The reduced viscosity is 0.65dl / g,
Tg was 226 ° C. and thermal decomposition temperature was 396 ° C. The water absorption is 0.3% by weight and the protruding length is 1.7m.
m. After applying the above polyamide NMP varnish on the plasma-treated Upilex S film, 10
The composite sheet was dried at 0 ° C. for 10 minutes and further at 300 ° C. for 10 minutes. 0.80 kN / m adhesion to 42 alloy
In the semiconductor package (SOJ type) obtained in the same manner as in Example 1, no crack was generated by the solder treatment after moisture absorption.

Example 10 3.58 g (10 mmol) of DSDA, bis [4- (4-aminophenoxy) phenyl] sulfone 4.3
A polyimide powder was obtained in the same manner as in Example 1 except that 2 g (10 mmol) was used. Reduced viscosity 0.87dl /
g and Tg were 270 ° C and the thermal decomposition temperature was 520 ° C.
The water absorption was 2.3% by weight and the protruding length was 0.0%.
1 mm. After applying the NMP varnish of the above-mentioned polyamide on the plasma-treated Iupirex S film,
The composite sheet was dried at 100 ° C. for 10 minutes and further at 300 ° C. for 10 minutes. 1.0 kN /
m, and no crack occurred in the semiconductor package (TSOP type) obtained in the same manner as in Example 1 due to the solder treatment after moisture absorption.

Example 11 Using the polyimide of Example 2, a film consisting of the adhesive alone was produced in the same manner as in Example 1. A semiconductor package (TSOP) obtained in the same manner as in Example 1 using this film
No cracks were generated in the (mold) by the solder treatment after moisture absorption. Example 12 An adhesive layer was formed on a semiconductor chip using the polyamide imide NMP varnish of Example 8. After packaging (TSOP type) using the chip with the adhesive as shown in FIG. 1 and performing soldering treatment after absorbing moisture in the same manner as in Example 1, no crack was generated.

Comparative Example 1 A composite sheet was obtained in the same manner as in Example 1 except that the polyamide DMF varnish obtained in Example 6 was used. The adhesive strength with 42 alloy was 1.60 kN / m. In the semiconductor package (TSOP type) obtained in the same manner as in Example 1, cracks occurred due to soldering after moisture absorption.

Comparative Example 2 2.11 g (8.5 mmol) of DDS, BAPP
0.62 g (1.5 mmol) was dissolved in 20 g of DMF, 2.02 g (20 mmol) of triethylamine was added, and then 2.03 g (10 mmol) of isophthalic chloride was added little by little while cooling to 5 ° C. or lower. After reacting at 5 ° C. or less for 5 hours, a polyamide powder was obtained in the same manner as in Example 1. The reduced viscosity is 0.45dl / g, T
g was 280 ° C and the thermal decomposition temperature was 430 ° C. Also,
The water absorption was 3.5% by weight, and the protruding length was 1.2 mm. After the alkali treatment, the above polyamide varnish is applied to the silane-coupled Kapton film, and
Heat treatment was performed at 00 ° C. for 10 minutes and at 250 ° C. for 10 minutes to obtain a composite sheet. The adhesive strength with 42 alloy was 1.5 kN / m. Semiconductor package (TS) obtained in the same manner as in Example 1.
(OP type), cracks were generated by soldering after moisture absorption.

Comparative Example 3 A polyimide powder having a reduced viscosity of 0.35 dl / g was obtained in the same manner as in Example 4. Tg is 275 ° C., pyrolysis temperature is 410
° C. The water absorption was 0.6% by weight, and the protruding length was 3.4 mm. The adhesive force of the composite sheet obtained in the same manner as in Example 4 with 42 alloy was 0.9 kN / m. In the semiconductor package obtained in the same manner as in Example 1, cracks were generated by the solder treatment after absorbing moisture (SOJ type).

(Comparative Example 4) Ethylene glycol bis trimellitate dianhydride
A polyimide powder was obtained in the same manner as in Example 1, except that 10 g (10 mmol) and 4.32 g (10 mmol) of bis [4- (3-aminophenoxy) phenyl] sulfone were used. Reduced viscosity is 0.44 dl / g, Tg is 187
° C and thermal decomposition temperature was 465 ° C. The water absorption was 1.1% by weight, and the protruding length was 2.2 mm.
Semiconductor package (TSOP) obtained in the same manner as in Example 1.
(Type) cracked due to the solder treatment after moisture absorption.

Comparative Example 5 2.87 g (7 mmol) of BAPP and LP-7100
After dissolving 0.75 g (3 mmol) in 23.0 g of NMP, 2.13 g (10 mmol) of trimellitic anhydride chloride was added little by little while cooling to 5 ° C. or lower. After adding 2.02 g (20 mmol) of triethylamine and reacting at 5 ° C. or lower for 5 hours, a polyamideimide powder was obtained in the same manner as in Example 1. Reduced viscosity 0.57d
1 / g, Tg was 185 ° C., the thermal decomposition temperature was 420 ° C., the water absorption was 0.13%, and the protrusion length was 0.8 mm.
100 g of the above polyamideimide powder and 3 g of γ-glycidoxypropyltrimethoxysilane were added to DMF 40
A varnish dissolved in 0 g was applied on a polyimide film (Upilex S film), and then dried at 100 ° C. for 10 minutes.
Drying at 10 ° C. for 10 minutes gave a composite sheet. The adhesive strength of this composite sheet with 42 alloy was 1.6 kN / m. The Tg of the adhesive was 185 ° C. and the water absorption was 1.3%.
And the protruding length was 0.2 mm. This composite sheet is first attached to a lead frame at 350 ° C., 6 MPa for 3 seconds, and then a chip is attached to the opposite surface at 375 ° C., 6 MPa,
Pasted in 3 seconds. After wire bonding, molding with a sealing material and semiconductor package as shown in Fig. 1 (TSOP type)
I got The package 85 ° C., after 48 hours moisture absorption treatment under the conditions of 85% RH, but was subjected to solder reflow in an infrared oven at 245 ° C., cracking did not occur, its
At a temperature of 260 ° C. or higher, a crack was generated .

Comparative Example 6 3.69 g (9 mmol) of BAPP and X-22-16
0.88 g (1 mmol) of 1AS was added to 34.7 of NMP.
g, and 4.10 g (10 mmol) of ethylene glycol bistrimate dianhydride was added little by little at 5 ° C or less. After reacting for 2 hours, 15 g of xylene was added, and the mixture was reacted at 180 ° C. for 5 hours in a nitrogen stream while azeotropically removing condensed water with xylene to synthesize a polyimide.
The resulting polyimide varnish was poured into water, and the resulting precipitate was separated, crushed and dried to obtain a polyid powder. The reduced viscosity is 0.65 dl / g, the Tg is 170 ° C., and the thermal decomposition temperature is 39.
At 0 ° C., the water absorption is 1.0%, and the protruding length is 1.8 mm.
Met. 100 g of the above polyimide powder and 5 g of γ-glycidoxypropylmethyldiethoxysilane were added to DM
Using a varnish dissolved in 400 g of F, a composite sheet was obtained in the same manner as in Example 13. The adhesive strength of this composite sheet with 42 alloy was 1.3 kN / m. The Tg of the adhesive part was 172 ° C., the water absorption was 1.0%, and the protruding length was 1.0 mm. The semiconductor package (SOJ type) obtained in the same manner as in Example 13 was 245 ° C. after moisture absorption.
Any crack was not generated by the solder treatment with,
At 260 ° C. above that temperature, cracks occurred .

Comparative Example 7 The procedure of Example 13 was repeated except that 3.28 g (8 mmol) of BAPP, 0.40 g (2 mmol) of dodecamethylenediamine and 2.13 g (10 mmol) of trimellitic anhydride chloride were used. Thus, a polyamideimide powder was obtained. The reduced viscosity was 0.85 dl / g, the Tg was 190 ° C., the thermal decomposition temperature was 395 ° C., the water absorption was 0.1%, and the protrusion length was 0.6 mm. A varnish prepared by dissolving 100 g of the above-mentioned polyamideimide powder and 10 g of γ-glycidoxypropyltrimethoxysilane in 400 g of NMP was applied to both sides of a polyimide (Upilex S film), and dried at 100 ° C. for 10 minutes.
After drying at 5 ° C. for 10 minutes, a composite sheet was obtained. The adhesive strength of this composite sheet with 42 alloy was 1.4 kN / m.
The Tg of the adhesive was 191 ° C. and the water absorption was 1.1.
%, The protruding length was 0.2 mm. Example 13
In the semiconductor package (TSOP type) obtained in the same manner as above, no crack was generated by soldering at 245 ° C. after moisture absorption , but cracking was observed at 260 ° C. or higher.
Arose . The results are shown in Tables 1 and 2 below.

[0074]

[Table 1]

[0075]

[Table 2]

(Abbreviations) IP: isophthalic acid (chloride) TA: trimellitic anhydride (chloride) LP-7100: siloxyamine, Shin-Etsu Chemical Co., Ltd.
Trade name IPDDM: 4,4'-diamino-3,3 ', 5,5'
-Tetraisopropyldiphenylmethane DDS: 4,4'-diaminobiphenylsulfone BTDA: 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane DSDA: bis [3,4-dicarboxyphenyl] sulfone dianhydride 16IAS: X-22-16AS siloxyamine, manufactured by Shin-Etsu Chemical Co., Ltd., trade name p-APPS: bis [4- (4-amino Phenoxy) phenyl] sulfone m-APPS: bis [4- (3-aminophenoxy) phenyl] sulfone EBTA: ethylene glycol bistrimellitate dianhydride DDMA: dodecamethylenediamine γ-GPTM: γ-glycidoxypropyltrimethoxysilane γ-GPME: γ-glycidoxypropyl Methyl diethoxy silane

[0077]

According to the present invention, the semiconductor package of the present invention
The heat-resistant adhesive for mounting members has a specified range of
Water content, glass transition temperature, specific hardness (or difficult to flow)
Since with Is), having exhibit both high <br/> resistance package cracking resistance even at high temperature solder of 260 ° C., high heat resistance and adhesion, water absorption and low characteristics. Therefore, the present invention
The heat-resistant adhesive is particularly effective for improving the reliability of the semiconductor package.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a semiconductor package having a LOC (lead on chip) structure.

FIG. 2 is a schematic diagram showing a semiconductor package having a COL (chip on lead) structure.

FIG. 3 is a schematic diagram when the semiconductor chip is located above a lead frame in the semiconductor package of FIG. 1;

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Adhesive member 2 Semiconductor chip 3 Lead frame 4 Wire 5 Sealing material 6 Projection surface area of semiconductor chip 7 Adhesion surface of semiconductor chip 8 Lead frame surface opposite to adhesion surface

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-287356 (JP, A) JP-A-4-366194 (JP, A) JP-A-5-1224 (JP, A) JP-A-5-224 331445 (JP, A) JP-A-6-231614 (JP, A) JP-A-6-172736 (JP, A) JP-A-5-331425 (JP, A) JP-A-5-331424 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09J 9/00 C09J 179/08 C09J 177/00 H01L 21/00-21/52 EPAT (QUESTEL)

Claims (11)

(57) [Claims] A semiconductor chip is bonded to a lead frame with an adhesive member, and at least the semiconductor chip and an adhesive portion between the semiconductor chip and the lead frame are sealed with a sealing material to be used as an adhesive member for manufacturing a semiconductor package. Heat resistance
A heat-resistant adhesives based on thermoplastic resin, 19
× 50 mm, 25 μm thick adhesive film
When pressed under conditions of 3 ° C, 3MPa for 1 minute, it protrudes
The length of the adhesive measured at the center in the long side direction was 2 mm or less in the protruding length, the water absorption was 3% by weight or less , and the glass transition temperature was 2
A heat-resistant adhesive characterized by being at least 00 ° C. 2. A semiconductor chip is bonded to a lead frame with an adhesive member, and at least the semiconductor chip and an adhesive portion between the semiconductor chip and the lead frame are sealed with a sealing material to be used as an adhesive member for manufacturing a semiconductor package. (A) the semiconductor package has a LOC (lead-on-chip) structure, and (b) 19 × 50 mm and a thickness of 25 μm.
m adhesive film at 350 ° C, 3MPa, 1 minute
When pressed with, the length of the protruding adhesive is
A heat-resistant adhesive having a protruding length of 2 mm or less, a water absorption of 3% by weight or less, and a glass transition temperature of 200 ° C. or more , measured at the center . 3. A heat-resistant adhesive according to any one of claims 1-2, characterized in that the adhesive member is a composite adhesive sheet comprising providing a heat resistant adhesive coating on both sides of the heat resistant film Agent. 4. A heat-resistant adhesive coating provided on both sides of the heat-resistant film, characterized in that it consists of different heat resistant adhesives, heat-resistant adhesive of claim 3 wherein. 5., characterized in that the adhesive member is a single heat-resistant adhesive according to claim 1 or 2 heat-resistant adhesive according. 6. A heat-resistant adhesive according to any one of claims 1 to 5, heat-resistant adhesive is characterized in that it is a polyimide adhesive. 7. The polyimide adhesive is synthesized from a diamine (A) and an acid anhydride (B), and [1] the diamine (A) is an alkylenediamine, a metaphenylenediamine, a metatoluylenediamine. 4,4′-diaminodiphenyl ether (DDE);
4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone;3,3'-diaminodiphenylsulfone,3,3'-diaminobenzophenone; 1,3-bis (4-aminocumyl) benzene, 1,4- Bis (4-aminocumyl) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene,
1,2-bis (4-aminophenoxy) benzene; 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoro Propane; bis [4- (3-aminophenoxy) phenyl] sulfone (m-APPS), bis [4- (4-aminophenoxy) phenyl] sulfone; 4,4′-diamino-3,3 ′, 5,5 '-Tetramethyldiphenylmethane, 4,4'-diamino-3,3',
5,5'-tetraethyldiphenylmethane, 4,4'-
Diamino-3,3 ', 5,5'-tetraisopropyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-diethyldiphenylmethane, 4,4'
-Diamino-3,3'-dimethyl-5,5'-diisopropyldiphenylmethane, 4,4'-diamino-3,
3'-diethyl-5,5'-diisopropyldiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diamino- 3,3'-
Diisopropyldiphenylmethane; at least one member selected from the group consisting of siloxanediamines of the following general formula (1), and (However, both R ¹⁵ and R ¹⁸ are trimethylene groups, R ¹⁶ and R ¹⁷ are both methyl groups, m is 1, about 10 on average, about 20 on average, about 30 on average, about 50 on average, about 50 on average, [II] acid anhydride (B) is trimellitic anhydride, maleic anhydride, nadic anhydride, allylnadic anhydride; 3, 3 ', 4, 4'-benzophenonetetracarboxylic acid Anhydride (BTDA); 2,2-bisphthalic acid hexafluoroisopropylidene dianhydride; bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride , Ethylene glycol bistrimellitate dianhydride (EB
TA), decamethylene glycol bistrimellitate dianhydride (DBTA), bisphenol A bistrimellitate dianhydride (BABT); 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bisphenylbistriene The heat-resistant adhesive according to claim 6 , wherein the adhesive is at least one selected from the group consisting of melitate dianhydride. 8. An adhesive having a size of 19 × 50 mm and a thickness of 25 μm.
Press the film at 350 ° C, 3MPa, 1 minute
Measure the length of the protruding adhesive at the center in the long side direction.
The protruding length is 2mm or less, the water absorption is 3% by weight or less ,
Heat-resistant thermoplastic resin a glass transition temperature of 200 ° C. or higher
A semiconductor chip is bonded to a lead frame with an adhesive member, and at least a semiconductor chip and a bonding portion between the semiconductor chip and the lead frame are sealed with a sealing material. A sealed semiconductor package. 9. An adhesive having a size of 19 × 50 mm and a thickness of 25 μm.
Press the film at 350 ° C, 3MPa, 1 minute
Measure the length of the protruding adhesive at the center in the long side direction.
The protruding length is 2mm or less, the water absorption is 3% by weight or less ,
Heat-resistant thermoplastic resin with a glass transition temperature of 200 ° C or higher
A semiconductor chip is bonded to a lead frame with an adhesive member, and at least a semiconductor chip and a bonding portion between the semiconductor chip and the lead frame are sealed with a sealing material. A sealed semiconductor package, wherein the semiconductor package is LOC (lead-on-chip)
A semiconductor package having a structure. 10. The semiconductor package according to claim 8 , wherein the heat-resistant adhesive according to any one of claims 3 to 7 is used for an adhesive member. 11., characterized by using the adhesive member of the heat-resistant adhesive according to any one of claims 3-7, a semiconductor package according to claim 9, wherein.