JPH1150037A - Liquid jointing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject material that is excellent in heat resistance, processability and adhesion, particularly shows low water absorption and can be suitably used as a mounting material for semiconductor devices by using a specific aromatic polyester imide polymer. SOLUTION: (A) The powder of an aromatic polyester imide polymer that contains recurring units of formula I (R1 and R2 are each a divalent organic group) and has an water absorption of <=1.0% is dissolved in (B) a polar solvent as N-methyl-2-pyrrolidone to obtain the objective material. In the formula I, R1 is methylene, p-phenylene, m-phenylene, a group of formula II (R3 is -O-, -S-, -CO-) and preferably diphenylene. In addition, R2 is preferably p-phenylene, m-phenylene, diphenylene, a group of formula III [R4 is -O-, -S-, -O-CH2 C(CH3 ) CH2 -O], group of formula IV and formula V (R5 is -O-, -S-, -CO-).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid bonding member, and more particularly, to a liquid bonding member which is required to have heat resistance, such as for fixing electronic parts and electronic circuit boards, or for insulation.
In particular, for die bonding of a flexible printed circuit board (hereinafter abbreviated as FPC) or a semiconductor element, or
OC (Lead on Chip), BGA (Ball Grid Array), C
The present invention relates to a liquid bonding member that can be suitably used as a mounting material for a semiconductor device such as a chip size package (SP).

[0002]

2. Description of the Related Art In recent years, electronic devices have become more sophisticated, higher in performance and smaller in size, and accordingly smaller and lighter electronic components have been required. Therefore, a semiconductor element packaging method and a wiring material or a wiring component for mounting the same have been required to have higher density, higher function and higher performance. Especially LOC, CS
Semiconductor packages with structures such as P and BGA, MCM (M
Ultra-high-density packaging materials such as ultra chip modules, printed wiring materials such as multi-layer FPCs, and insulating adhesive materials exhibiting good adhesive properties that can be suitably used for aerospace materials are required.

[0003] As an insulating adhesive material generally used for electronic parts and electronic materials, epoxy resins and acrylic resins are often used because they can be processed at a low temperature (200 ° C) and are easy to handle. When manufacturing a semiconductor device, the adhesive material is used, for example, as a silver paste in which a silver filler is dispersed in an epoxy resin to bond a lead frame and a semiconductor chip.

[0004] However, these joining members are easy to handle at low temperatures, but have a problem in that they have poor heat resistance at high temperatures. In addition, curing requires a long curing time, and a low molecular weight gas is generated during the curing.For example, when used for bonding a lead frame and a semiconductor chip, the generated gas contaminates the chip surface and leads There is also a problem that the adhesion between the frame and the chip is deteriorated and the yield of the product is deteriorated. Therefore, particularly for high-density packaging materials such as when manufacturing semiconductor devices, there has been a strong demand for further high-performance bonding materials.

As a bonding material meeting such demands, polyimide is promising because of its excellent properties such as high heat resistance and mechanical strength, and excellent electrical properties. However, in general, polyimide is almost insoluble and infusible in a ring-closed state, and as an organic insulating material, FPC or TAB is used.
It is used as a base film for FC tapes, but it is difficult to use it for high-density packaging materials.

However, in recent years, despite being polyimide,
Due to the improvement of the characteristics, examples that can be used as a bonding material have been proposed. A silver paste composition has been proposed in which a silver filler is kneaded with a precursor solution of a polyimide resin such as polyamic acid synthesized from pyromellitic anhydride and a normal aromatic diamine. JP-A-60-71662 discloses a conductive silver paste composition in which a silver filler is kneaded in an organic solvent solution of a precursor of a siloxane-modified polyimide resin using siloxane diamine. According to this, the precursor is ring-closed (imidized) by heat curing at the time of die bonding to give a polyimide resin having excellent heat resistance, so that good results are obtained in the high-temperature electrical characteristics of the semiconductor device.

In Japanese Patent Application Laid-Open No. 2-138789, 3,3
3 ^'4,4' - using the adhesive film obtained from benzophenone tetracarboxylic dianhydride and a resin composition obtained by mixing the aromatic polyimide and a maleimide consisting of aromatic diamines, the substrate and the copper foil such as a polyimide film A method for manufacturing an FPC to be bonded has been proposed. Further, Japanese Unexamined Patent Publication No.
JP-A-179224 and JP-A-5-112768 propose various thermoplastic polyimide adhesive materials which can be heated and pressed.

[0008]

However, a bonding material in which a silver filler is kneaded with an epoxy resin or a resin obtained by ring-closing (imidizing) a polyimide precursor has a relatively high moisture absorption rate, and the semiconductor device is sealed with the epoxy resin. Stop, and when a heat history of about 240 ° C is applied at the stage of solder reflow, etc.,
There has been a problem that the moisture absorbed by the adhesive or the like expands, causing a package crack.

Furthermore, the above-mentioned polyimide adhesive film can be used as an adhesive by improving the polyimide melt flowability, but it requires a high temperature and a long time for adhesion and has a problem in workability. . In addition, as for the adhesive film, the bonding equipment and process used in the conventional silver paste cannot be used, and new equipment is required for the process of punching the film and bonding it to the lead frame. Also, since the film is run on a reel-shaped line, when the film is punched into a predetermined size, the punched film has a margin so as not to be broken in the longitudinal direction, and this margin is discarded. As described above, there is also a problem that the transition from the silver paste to the film adhesive leads to an increase in the cost of manufacturing the semiconductor device.

Accordingly, the present inventors have solved the above-mentioned problems and have an object to provide a liquid joining member having excellent properties such as excellent heat resistance, workability, and adhesiveness, and particularly exhibiting a low water absorption rate. As a result of intensive studies, the present invention has been achieved.

[0011]

The gist of the liquid joining member according to the present invention for achieving this object is that of the general formula (1).

[0012]

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(Wherein R ₁ and R ₂ each represent a divalent organic group) and an aromatic polyesterimide polymer having a water absorption of 1.0% or less. To include.

In the general formula (1), R ₁ is a methylene group, a p-phenylene group, an m-phenylene group, a diphenylene group, or a compound represented by the general formula (2).

[0015]

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(Wherein, R ₃ represents —O—, —S—,
_{-SO 2 -, - CO -,} - C (CH 3) 2 -, - C (C
F ₃ ) _2- and-(CH ₂ ) _n- . ).

In the general formula (1), R ₂ is p-phenylene group, m-phenylene group, diphenylene group, or
Formula (3) 8

[0018]

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(Wherein, R_FourIs -O-, -S
-, -SO_Two-, -CO-, -C (CH _Three)_Two, -C
(CF_Three)_Two-,-(CH_Two)_n-, -O- (CH_TwoC
H_TwoO)_n-, -O-CH_TwoC (CH_Three)_TwoCH_Two-O-
Is shown. A group represented by the general formula (4)

[0020]

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Or a group represented by the general formula (5):

[0022]

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(Wherein, R_FiveIs -O-, -S
-, -SO_Two-, -CO-, -C (CH _Three)_Two-, -C
(CF_Three)_Two-,-(CH_Two)_nIndicates-. )
Is to be a group.

[0024]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an example of an embodiment of a liquid bonding member according to the present invention, together with a method of manufacturing the same, will be specifically described.

The polyesterimide used in the present invention is produced by imidizing a polycarboxylic acid produced by polymerizing tetracarboxylic dianhydride and diamine as raw materials.

The tetracarboxylic dianhydride, which is a raw material of the polyesterimide used in the present invention, has the general formula (A):

[0027]

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[0028] (wherein, R R ₁ in the general formula (1) ₁
And the same divalent organic group as described above. ) Is a tetracarboxylic dianhydride containing an ester group represented by the following general formula (B): H ₂ N—R ₂ —NH ₂ (B) (where R ₂ is a general formula ( The diamine represented by the same divalent organic group as R ₂ in 1) is used as a raw material.

The tetracarboxylic dianhydride containing an ester group represented by the general formula (A) can be obtained by reacting trimellitic anhydride monochloride with a dihydric phenol at room temperature or lower, or trimellitic anhydride. And a dimethyl ester of a dihydric phenol at a high temperature of 200 to 300 ° C.

[0030] Here, as the dihydric phenol as a raw material, hydroquinone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, resorcinol, 4,4'-biphenol, 2,2 ^'- biphenol, Four,
4'-dihydroxyphenylmethane, 4,4'-dihydroxyphenyl ether, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylketone,
4,4'-dihydroxydiphenyl sulfide, 2,2-
Bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxy-3,5-diphenyl) propane, 2,2-
Bis- (4-hydroxy-3-methylphenyl) propane;

The most typical examples of the tetracarboxylic dianhydride containing an ester group represented by the general formula (A) include:
2,2 - (. Which hereinafter abbreviated as ESDA) ^'bis (4-hydroxyphenyl) propane dibenzoate-3,3', 4,4'-tetracarboxylic dianhydride, 3,3 ', 4,4' -Hydroxydibenzoate tetracarboxylic dianhydride (hereinafter referred to as TMH
Abbreviated as Q. ).

When these tetracarboxylic dianhydrides containing ester groups are polymerized with a diamine and imidized, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. Such as polar solvents. Further, there is an advantage that the water absorption of the manufactured polyimide is reduced.

In the liquid joining member of the present invention, the above-mentioned ester acid alone may be used as the acid dianhydride component. In addition, one or more acid dianhydrides may be mixed in such a ratio that the effect of the present invention is not impaired. However, they can be copolymerized. As the acid dianhydride, pyromellitic dianhydride, 1,2,3,
4-benzenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6- Naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetra Carboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4 '-Biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 1,1 , 1,3,3,3-Hexafluoro-2,2-bis (2,3-
Dicarboxyphenyl) propane dianhydride, 1,1,1,3,3,
3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone Dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride Anhydride, bis (3,4-dicarboxyphenyl) tetramethyldisiloxane dianhydride, bis (2,3-
Acid dianhydrides such as dicarboxyphenyl) tetramethyldisiloxane dianhydride, bis (2,3-dicarboxyphenoxy) dimethylsilane dianhydride and bis (3,4-dicarboxyphenoxy) dimethylsilane dianhydride No.

In this case, the mixing ratio is not particularly limited.
The characteristics of the polyimide are adjusted by mixing these acid dianhydrides and copolymerizing them at various mixing ratios. For example, it is possible to increase the mechanical strength by copolymerizing an acid having a rigid structure, or to perform operations such as raising the glass transition temperature, and conversely, by copolymerizing a flexible structure, Is applied to adjust the water absorption, the dielectric constant, and the like, as a whole, to lower the glass transition temperature, and the like.

Further, a diamine represented by the general formula (B)
Is P-phenylenediamine, m-phenylenediamine
1,4-diaminodiphenyl, 4,4^'-Diaminodiffe
Nyl ether, 3,3^'-Diaminodiphenyl ether,
4,4^'-Diaminobenzophenone, 4,4^'-Diaminodi
Phenylpropane, 4,4 ^'-Diaminodiphenylsulf
, 3,4^'-Diaminodiphenyl sulfide, 3,3^'
-Diaminodiphenyl sulfide, 4,4^'-Diaminodi
Phenyl sulfone, 3,4^'-Diaminodiphenylsulfo
3,3^'-Diaminodiphenyl sulfone, 4,4^'-The
Aminodiphenylamine, 4,4^'-Diaminodiphenyl
-N-methylamine, 4,4^'-Diaminodiphenyl-N-
Phenylamine, 4,4^'-Diaminodiphenylmethane, 1,
2-bis (2- (4-aminophenoxy) ethoxy) ethane,
1,2-bis (2- (3-aminophenoxy) ethoxy) eta
2,2-bis ((4-aminophenoxy) methyl) propa
2,2-bis ((3-aminophenoxy) methyl) propa
1,3-bis (3-aminophenoxy) benzene, 1,3
-Bis (4-aminophenoxy) benzene, 1,4-bis
(4-aminophenoxy) benzene, 1,1-bis (4- (4-a
Minophenoxy) phenyl) methane, 1,1-bis (3-meth
Tyl-4- (4-aminophenoxy) phenyl) methane, 1,1
-Bis (3-ethyl-4- (4-aminophenoxy) phenyl)
Methane, 1,1-bis (3-propyl-4- (4-aminophenoxy)
C) phenyl) methane, 1,1-bis (3-isopropyl-4)
-(4-aminophenoxy) phenyl) methane, 1,1-bis
(3-butyl-4- (4-aminophenoxy) phenyl) meta
1,1-bis (3-sec-butyl-4- (4-aminophenoxy)
C) phenyl) methane, 1,1-bis (3-methoxy-4- (4-
Aminophenoxy) phenyl) methane, 1,1-bis (3-
Ethoxy-4- (4-aminophenoxy) phenyl) methane,
1,1-bis (3,5-dimethyl-4- (4-aminophenoxy) phenyl
Enyl) methane, 1,1-bis (3,5-dimethoxy-4- (4-a
Minophenoxy) phenyl) methane, 1,1-bis-4- (4-
Aminophenoxy) phenyl) ethane, 1,1-bis (3-
Methyl-4- (4-aminophenoxy) phenyl) ethane, 1,
1-bis (3-ethyl-4- (4-aminophenoxy) phenyi
Ethane), 1,1-bis (3-propyl-4- (4-aminophen
Nonoxy) phenyl) ethane, 1,1-bis (3-isopropyl
4- (4-aminophenoxy) phenyl) ethane, 1,1-
Bis (3-butyl-4- (4-aminophenoxy) phenyl) d
Tan, 1,1-bis (3-sec-butyl-4- (4-aminophenoxy)
C) phenyl) ethane, 1,1-bis (3-methoxy-4- (4-
Aminophenoxy) phenyl) ethane, 1,1-bis (3-
Ethoxy-4- (4-aminophenoxy) phenyl) ethane,
1,1-bis (3,5-dimethyl-4- (4-aminophenoxy) phenyl
Enyl) ethane, 1,1-bis (3,5-dimethoxy-4- (4-a
Minophenoxy) phenyl) ethane, 2,2-bis (4- (4-
Aminophenoxy) phenyl) propane, 2,2-bis (3-
Methyl-4- (4-aminophenoxy) phenyl) propane,
2,2-bis (3-ethyl-4- (4-aminophenoxy) phenyl
Le) propane, 2,2-bis (3-propyl-4- (4-aminophen)
Nonoxy) phenyl) propane, 2,2-bis (3-isopropyl
4- (4-aminophenoxy) phenyl) propane, 2,2-
Bis (3-butyl-4- (4-aminophenoxy) phenyl) p
Lopan, 2,2-bis (3-sec-butyl-4- (4-aminophenoxy)
C) phenyl) propane, 2,2-bis (3-methoxy-4- (4-
Aminophenoxy) phenyl) propane, 2,2-bis (3-
Ethoxy-4- (4-aminophenoxy) phenyl) propa
2,2-bis (3,5-dimethyl-4- (4-aminophenoxy)
Phenyl) propane, 2,2-bis (3,5-dimethoxy-4- (4-
Aminophenoxy) phenyl) propane, 1,1-bis (4-
(4-aminophenoxy) phenyl) propane, 1,1-bis
(3-methyl-4- (4-aminophenoxy) phenyl) propa
1,1-bis (3-ethyl-4- (4-aminophenoxy) phene
Nyl) propane, 1,1-bis (3-propyl-4- (4-aminophenyl)
Enoxy) phenyl) propane, 1,1-bis (3-isopro
Pill-4- (4-aminophenoxy) phenyl) propane, 1,
1-bis (3-butyl-4- (4-aminophenoxy) phenyl)
Propane, 1,1-bis (3-sec-butyl-4- (4-aminopheno
Xy) phenyl) propane, 1,1-bis (3-methoxy-4-
(4-aminophenoxy) phenyl) propane, 1,1-bis
(3-ethoxy-4- (4-aminophenoxy) phenyl) pro
Bread, 1,1-bis (3,5-dimethyl-4- (4-aminophenoxy)
C) phenyl) propane, 1,1-bis (3,5-dimethoxy-4)
-(4-aminophenoxy) phenyl) propane, 1,1,1,3,
3,3-hexafluoro-2,2-bis (4- (4-aminophenoki
C) phenyl) propane, 1,1,1,3,3,3-hexafluoro
-2,2-bis (3-methyl-4- (4-aminophenoxy) phenyi
Le) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis
(3-ethyl-4- (4-aminophenoxy) phenyl) propa
1,1,1,3,3,3-hexafluoro-2,2-bis (3-propane
4- (4-aminophenoxy) phenyl) propane, 1,1,
1,3,3,3-hexafluoro-2,2-bis (3-isopropyl-4
-(4-aminophenoxy) phenyl) propane, 1,1,1,3,
3,3-hexafluoro-2,2-bis (3-butyl-4- (4-amino
Phenoxy) phenyl) propane, 1,1,1,3,3,3-hexa
Fluoro-2,2-bis (3-sec-butyl-4- (4-aminopheno
Xy) phenyl) propane, 1,1,1,3,3,3-hexafluoro
B-2,2-Bis (3-methoxy-4- (4-aminophenoxy) phenyl
Enyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-
Bis (3-ethoxy-4- (4-aminophenoxy) phenyl)
Propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,
5-dimethyl-4- (4-aminophenoxy) phenyl) propa
1,1,1,3,3,3-hexafluoro-2,2-bis (3,5-dimension
Toxic-4- (4-aminophenoxy) phenyl) propane,
2,2-bis (4- (4-aminophenoxy) phenyl) buta
2,2-bis (3-methyl-4- (4-aminophenoxy) phene
Nyl) butane, 2,2-bis (3-ethyl-4- (4-aminopheno)
Xy) phenyl) butane, 2,2-bis (3-propyl-4- (4-
Aminophenoxy) phenyl) butane, 2,2-bis (3-a
Sopropyl-4- (4-aminophenoxy) phenyl) buta
2,2-bis (3-butyl-4- (4-aminophenoxy) phene
Nyl) butane, 2,2-bis (3-sec-butyl-4- (4-aminophenyl)
Enoxy) phenyl) butane, 2,2-bis (3-methoxy-4
-(4-aminophenoxy) phenyl) butane, 2,2-bis
(3-ethoxy-4- (4-aminophenoxy) phenyl) buta
2,2-bis (3,5-dimethyl-4- (4-aminophenoxy)
Phenyl) butane, 2,2-bis (3,5-dimethoxy-4- (4-a
Minophenoxy) phenyl) butane, 3,3-bis (4- (4-
Aminophenoxy) phenyl) pentane, 3,3-bis (3-
Methyl-4- (4-aminophenoxy) phenyl) pentane,
3,3-bis (3-ethyl-4- (4-aminophenoxy) phenyl
Le) pentane, 3,3-bis (3-propyl-4- (4-aminophen)
Nonoxy) phenyl) pentane, 3,3-bis (3-isopropylene)
4- (4-aminophenoxy) phenyl) pentane, 3,3-
Bis (3-butyl-4- (4-aminophenoxy) phenyl) pe
3,3-bis (3-sec-butyl-4- (4-aminophenoxy)
C) phenyl) pentane, 3,3-bis (3-methoxy-4- (4-
Aminophenoxy) phenyl) pentane, 3,3-bis (3-
Ethoxy-4- (4-aminophenoxy) phenyl) penta
, 3,3-bis (3,5-dimethyl-4- (4-aminophenoxy)
Phenyl) pentane, 3,3-bis (3,5-dimethoxy-4- (4-
Aminophenoxy) phenyl) pentane, 3,5-bis (4-
(4-aminophenoxy) phenyl) pentane, 3,5-bis
(3-methyl-4- (4-aminophenoxy) phenyl) penta
3,5-bis (3-ethyl-4- (4-aminophenoxy) phene
Nyl) pentane, 3,5-bis (3-propyl-4- (4-aminophenyl)
Enoxy) phenyl) pentane, 3,5-bis (3-isopro
Pill-4- (4-aminophenoxy) phenyl) pentane, 3,
5-bis (3-butyl-4- (4-aminophenoxy) phenyl)
Pentane, 3,5-bis (3-sec-butyl-4- (4-aminopheno
Xy) phenyl) pentane, 3,5-bis (3-methoxy-4-
(4-aminophenoxy) phenyl) pentane, 3,5-bis
(3-ethoxy-4- (4-aminophenoxy) phenyl) pen
Tan, 3,5-bis (3,5-dimethyl-4- (4-aminophenoxy)
C) phenyl) pentane, 3,5-bis (3,5-dimethoxy-4)
-(4-aminophenoxy) phenyl) pentane, bis (4-
(4-aminophenoxy) phenyl) sulfone, bis (4-
(3-aminophenoxy) phenyl) sulfone, bis (4-
(4-aminophenoxy) phenyl) ether, bis (3-
(4-aminophenoxy) phenyl) ether, bis (3-
(3-aminophenoxy) phenyl) ether
You.

In the present invention, an aliphatic or alicyclic diamine may be used as long as the effects of the present invention are not significantly reduced. Such diamines include piperazine, hexamethylenediamine, heptamethylenediamine, tetramethylenediamine, p-xylylenediamine,
Examples include m-xylylenediamine and 3-methylheptamethylenediamine. These diamines can be used alone or may be copolymerized.

The mixing ratio with these aliphatic diamines is not particularly limited. Since aliphatics are more flexible than aromatic groups containing a benzene ring, they can be applied by mixing and copolymerizing them when it is desired to lower the elasticity of the resin itself.

The polymerization method for obtaining the aromatic polyesterimide polymer used in the present invention from the above-mentioned tetracarboxylic dianhydride and diamine includes the following general formula (C) in a polar solution.

[0039]

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(Wherein, R ₁ and R ₂ are the same as those in the general formula (1)), synthesized, isolated, imidized, and imidized. ) Or a one-step synthesis method in which an aromatic polyesterimide polymer represented by the general formula (1) is obtained by completing the process up to imidization in a polar solvent to obtain an aromatic polyesterimide polymer represented by the general formula (1). is there.

First, the one-step synthesis method will be described. The diamine is used in an amount of 0.8 to 1.2 equivalents, preferably 0.95 to 1 equivalent, relative to 1 equivalent of the acid dianhydride represented by the general formula (A).
1.05 equivalents, N, N-dimethylformamide, N, N-
After reaction in a polar solvent such as dimethylacetamide or N-methyl-2-pyrrolidone at 0 to 100 ° C. for several tens of minutes to several hours, imidization is performed. For imidation, (1) 50-20
A method in which the reaction is carried out by heating at 0 ° C. for several tens minutes to several hours to carry out imidation, and (2) acetic anhydride 2 at 50 to 180 ° C.
There is a method of chemically promoting imidation by adding up to 5 equivalents and 1 to 2 equivalents of pyridine.

Next, the two-stage synthesis method will be described. The diamine is used in an amount of 0.8 to 1.2 equivalents, preferably 0.95 to 1.1 equivalent, relative to 1 equivalent of the acid dianhydride represented by the general formula (A).
By using 05 equivalents, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone in a polar solvent such as 0 to 100 ℃, preferably by reacting in the range of 0 to 60 ℃, The polyamic acid derivative represented by the general formula (C) is produced, and the aromatic polyesterimide polymer represented by the general formula (C) used in the present invention is produced by a conventionally used dehydration cyclization method. Can be manufactured.

Here, the dehydration cyclization method includes (1) a method in which a polymer is isolated and then cyclized by heating at 150 to 350 ° C., and (2) a solution state at 80 to 400 ° C., preferably 100 ° C. There is a method of cyclizing by heating at ~ 250 ° C. In the case of this method, it is preferable to use a solvent azeotropic with water, such as benzene, toluene and xylene, in combination with the polar solvent.

There is also a method of (3) cyclization in a solution state with a chemical dehydrating agent such as an acid anhydride such as acetic acid, propionic acid, butyric acid and benzoic acid. In this case, it is preferable to use pyridine, quinoline, picoline and the like in combination as a substance that promotes the cyclization reaction.

With respect to the mixing ratio of the acid dianhydride and the diamine, in order to obtain a polyesterimide polymer having a high molecular weight, the acid dianhydride is added to the diamine within the above range, that is, 1 equivalent of the acid dianhydride is added to the diamine. 0.8 to 1.2 equivalents,
Preferably, it is added in an amount of 0.95 to 1.05 equivalents, and if it is out of this range, only low molecular weight compounds tend to be obtained.

The molecular weight of the thus obtained aromatic polyesterimide polymer is not particularly limited, but the average molecular weight is 10,000 or more and 50 or more.
50,000 or less, particularly preferably 50,000 or less.
It is preferably from 0 to 200,000. Molecular weight is 10.
If it is less than 000, the resin becomes brittle and the film forming ability is poor. Further, if the molecular weight exceeds 500,000, soluble
It will be inferior in solvent solubility.

Further, since the glass transition temperature is 300 ° C. or less, the workability is excellent. Furthermore, it has been confirmed that it has an excellent water absorption, and exhibits a low water absorption of 1.0% or less when immersed in pure water at 20 ° C. for 24 hours.

To the reaction solution obtained as described above, a solvent which is compatible with the above-mentioned polar solvent and is a poor solvent for the resin, for example, a lower alcohol, water or the like is poured in a large excess to obtain a precipitate. The mixture is filtered, dried and pulverized to obtain an aromatic polyesterimide polymer powder.

Further, the obtained aromatic polyesterimide polymer powder is dissolved in a polar solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like. Such a liquid joining member is obtained. The compounding ratio can take various values depending on the characteristics of the resin, and for example, can be used in a 10% by weight NMP solution.

When the joining member needs to have thermal conductivity, Ag, Au, Al, 0 to 80% by weight with respect to the resin.
Ni, C, SiC, SiO ₂ , MgO, BN ₃ , Al ₃
A thermally conductive filler such as O ₃ , BaSO ₄ , or ZrO can be mixed. If the amount of the filler exceeds 80% by weight, the adhesiveness is reduced.

When the joining member requires conductivity, 50 to 80% by weight of Ag, Au, A
Metal fillers such as l, Ni, and C can be used. When the amount of the filler is less than 50% by weight, the effect of imparting conductivity is small, and when the amount exceeds 80% by weight, the adhesiveness is reduced.

The liquid bonding member according to the present invention obtained as described above has excellent heat resistance and adhesiveness, exhibits a low moisture absorption rate, and does not cause a package crack due to its structure. Further, since only a necessary amount can be used in the conventional equipment and process, the cost can be reduced as compared with the film-shaped joining member.

Next, there are the following methods for joining a semiconductor element to a supporting member in a semiconductor device using the liquid joining member of the present invention.

(1) The above-mentioned liquid bonding member is dispensed on a supporting member, and a semiconductor element is mounted thereon to perform a heat treatment. (2) The bonding surface of the supporting member is attached to the bath of the liquid bonding member, and the semiconductor element is mounted thereon and subjected to heat treatment. (3) The liquid bonding member is dispensed on the bonding surface of the semiconductor element, and a supporting member is placed thereon to perform a heat treatment. (4) The bonding surface of the semiconductor element is attached to the bath of the liquid bonding member, and the supporting member is placed thereon to perform heat treatment. The heating conditions may be ordinary heating conditions, for example, pressing is performed at 300 ° C. and a pressure of 2 MPa for 2 seconds.

After such bonding, wire bonding is performed for the purpose of electrical connection between the support member and the semiconductor element, and resin sealing with epoxy resin or the like, glass sealing, or the like.
Sealed by ceramic sealing or the like.

The semiconductor device 1 obtained as described above
As an example, FIGS. 1 to 3 show sectional views of a resin-sealed semiconductor device. FIG. 1 shows a supporting member (lead frame) 14.
The semiconductor element 10 is joined via a joining member 12, and the semiconductor element 10 and the external lead wires 20 are wire-bonded by bonding wires 16.
The entire semiconductor device is sealed with an epoxy resin 18.
FIG. 2 shows that a supporting member 14 also serving as an external lead wire is bonded on a semiconductor element 10 via a bonding member 12, and the semiconductor element 10 and the supporting member 14 are bonded to a bonding wire 16.
Wire bonding. The entire semiconductor element is sealed with an epoxy resin 18. FIG. 3 shows that a semiconductor element 10 is bonded via a bonding member 12 on a support member 14 made of ceramic, plastic, metal, or the like on which a circuit pattern is applied, and a bonding wire 16 is connected to a circuit pattern electrode of the support member 14. Semiconductor element 1
0 is joined. The support member 14 is electrically conductive in the thickness direction by a substrate laminating technique or the like, and the electrodes of the semiconductor element 10 are electrically connected to the external solder balls 22 through the bonding wires 16. The entire semiconductor device is sealed with an epoxy resin 18.

The embodiments of the liquid joining member according to the present invention have been described above together with the manufacturing method thereof. However, the present invention is not limited to only these embodiments.
Various improvements, changes, and modifications can be made based on the knowledge of those skilled in the art without departing from the spirit of the invention.

[0058]

Next, examples of the present invention will be described more specifically, but the present invention is not limited only to these examples.

(Example 1) In an ice bath, 2,2-bis ((4-aminophenoxy) phenyl) propane (hereinafter, referred to as a 3-necked separable flask equipped with a stirrer)
Abbreviated as BAPP. ) 18.7 g (45.6 mmol)
N, N-dimethylformamide (hereinafter abbreviated as DMF) 2
39.6 g was added, and the mixture was stirred under a nitrogen atmosphere and sufficiently dissolved. Next, 25.7 g (44.6 m) of 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride (hereinafter abbreviated as ESDA)
mol), and the wall of the separable flask was washed with 10 g of DMF. After standing for about 1 hour with stirring, 0.6 g of ESDA was previously added to 5.4 g of DMF.
Was gradually poured into the flask while paying attention to the varnish viscosity in the flask. After the viscosity reached 2000 poise, the charging of the ESDA solution was terminated to obtain a polyamic acid solution.

Here, a film was prepared in order to measure the glass transition temperature and the water absorption in the imidized state of the obtained polyamic acid solution. Film formation is performed as follows. Acetic anhydride 1 in 100 g of polyamic acid varnish
After adding 0 g, 10 g of isoquinoline and 10 g of DMF and sufficiently stirring, the mixture was coated on a PET film with a coater at 0.3 mm intervals, and heated in an oven at 80 ° C. for 10 minutes.
After peeling off from the ET film, fix the end,
From 250 ° C., and then heated for 5 minutes to imidize to obtain a 30 μm thick polyimide film. The glass transition temperature was measured by TMA,
Regarding the water absorption, a change in weight after immersion in pure water at 20 ° C. was measured according to ASTM-570.

In order to carry out imidation in the polyamic acid solution state, acetic anhydride is added to the polyamic acid solution at room temperature.
g, 10 g of pyridine and 100 g of DMF were added, and the mixture was stirred for several tens minutes to several hours to perform imidization.

A 200 g portion of the produced polyesterimide polymer solution was separated, dropped into 2 liters of methanol, and filtered to obtain a polyesterimide ester acid polymer. Furthermore, it was vacuum-dried at 100 ° C. in a vacuum oven for one day to obtain a powder.

The obtained polyesterimide polymer powder 1
0 g to 90 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP).
Abbreviated. ) To obtain a liquid joining member.

The evaluation of the adhesiveness of the manufactured liquid joining member is as follows.
On a support member (42 alloy plate) with a size of 10 × 20 mm, apply it to a thickness of 0.3 mm with an applicator, and then
It was baked in an oven at 00, 150, 200 and 250 ° C. for 5 minutes to obtain a 30 μm coating film. On the supporting member with the joining member (42 alloy plate) thus produced, 2
× 2mm semiconductor element is placed, 300 ℃, 2MPa
For 2 seconds. The shear strength of the support member to which the obtained semiconductor element was bonded was measured at a test speed of 5 mm / min using a shear strength measuring device.

Further, a semiconductor element was bonded on a dummy lead frame under the same conditions as described above, and sealed using a biphenyl-based epoxy resin. After leaving the dummy semiconductor device in an environment of 85 ° C./85% for 168 hours,
The temperature was gradually raised from room temperature and passed through an IR reflow furnace so as to be heated at a maximum temperature of 245 ° C. for about 10 seconds. afterwards,
The sample was subjected to a nondestructive inspection using an X-ray transmission apparatus (Ultra-X125) to confirm the presence or absence of a package crack in the semiconductor device. The raw materials used and the measurement results are shown in Tables 1 and 2, respectively.

[0066]

[Table 1]

[0067]

[Table 2]

(Examples 2 to 6) Using the raw materials shown in Table 1,
A liquid joining member was obtained and evaluated in the same manner as in Example 1. Table 2 shows the results.

(Comparative Examples 1-2) Using the raw materials shown in Table 1,
A polyimide polymer powder was obtained in the same manner as in Example 1. The evaluation is shown in Table 2. However, the adhesive strength and the number of cracks could not be measured because the powder did not dissolve in the solvent and could not be measured.

(Comparative Examples 3 and 4) Using the raw materials shown in Table 1,
A polyimide polymer powder was obtained in the same manner as in Example 1. The evaluation is shown in Table 2. The adhesive strength was the same as in the examples, but cracks occurred frequently because of the high water absorption.

[0071]

As described above, the liquid joining member according to the present invention is excellent in heat resistance and adhesiveness, has good solubility in polar solvents such as NMP, and has a water absorption of 1.0% or less. Because of its low value, it has excellent workability and excellent characteristics that do not cause cracks.

[0072]

[Brief description of the drawings]

FIG. 1 is an embodiment of a semiconductor device using a liquid bonding member according to the present invention.

FIG. 2 is another embodiment of a semiconductor device using the liquid bonding member according to the present invention.

FIG. 3 is still another embodiment of a semiconductor device using the liquid bonding member according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10; Semiconductor element 12; Bonding member 14; Support member 16; Bonding wire 18; Epoxy sealing resin 20; External lead wire 22;

Claims (3)

[Claims] 1. A compound of the general formula (1) (Wherein, R ₁ and R _{2 each} represent a divalent organic group)
And containing a repeating unit represented by
% Of an aromatic polyesterimide polymer. 2. In the general formula (1), R ₁ is a methylene group, a p-phenylene group, an m-phenylene group, a diphenylene group, or a compound represented by the general formula (2). (Where R ₃ is —O—, —S—, —SO ₂ —,
_{-CO -, - C (CH 3} ) 2 -, - C (CF 3) 2 -,
− (CH ₂ ) _n − Is shown. The liquid bonding member according to claim 1, wherein the liquid bonding member is a group represented by the following formula: 3. In the general formula (1), R ₂ is a p-phenylene group, an m-phenylene group, a diphenylene group, or a compound represented by the general formula (3). (Wherein, R ₄ represents —O—, —S—, —SO
_{2 -, - CO -, -} (CH 2) n -, - C (C
_{H 3) 2, -C (CF} 3) 2 -, - O- (CH 2 CH 2
_{O) n -, - O-} CH 2 C (CH 3) 2 CH 2 -O- shown. A group represented by the general formula (4): Or a group represented by the general formula (5): (Wherein, R ₅ represents —O—, —S—, —SO
_{2 -, - CO -, -} (CH 2) n -, - C (CF 3) 2
_{-, - C (CH 3)} 2 - shows a. The liquid bonding member according to claim 1, wherein the liquid bonding member is a group represented by: