JPH11209734A - Liquid joint member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid joint member excellent in heat tolerance, processability and adhesion, and having a low water absorption by including a polyimide polymer having a specific repeating unit, glass transition temperature and water absorption. SOLUTION: This liquid joint member includes a polyimide polymer containing a repeating unit of formula I [R1 is a tetravalent organic group; (n) is 1-10], and having <=200 deg.C glass transition temperature and <=1% water absorption. In formula I, R1 is preferably formulas II or III, or the like. The polyimide polymer is, for example, obtained by using (A) a tetracarboxylic dianhydride of formula IV [e.g. 2,2'-bis(4-hydroxyphenyl) propanedibenzoate-3,3',4,4'-tetracarboxylic dianhydride] and (B) a diamine of formula V e.g. 1,2-bis-[2-(4-aminophenoxy)ethoxy]ethane} as a raw material.

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),
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 CSP (ChipSize Package).

[0002]

2. Description of the Related Art In recent years, electronic devices have become more sophisticated and more sophisticated.
With miniaturization progressing, there has been a demand for miniaturization and weight reduction of electronic components used accordingly. For this reason, a semiconductor element packaging method and a wiring material or a wiring component for mounting the same are required to have higher density, higher function and higher performance. In particular, LO
Good adhesion that can be suitably used as a semiconductor package having a structure such as C, CSP, or BGA, a high-density mounting material such as an MCM (Multi Chip Module), a printed wiring material such as a multilayer FPC, and an aerospace material. There is a need for an insulating adhesive material that exhibits properties.

[0003] In general, an insulating adhesive material used for electronic parts and electronic materials can be processed at a low temperature (200 ° C).
Because of easy handling, epoxy resins and acrylic resins are often used.When manufacturing semiconductor devices, these adhesive materials are used, for example, as a silver paste in which a silver filler is dispersed in an epoxy resin. It is also used for bonding a lead frame and a semiconductor chip.

[0004] However, these joining members are easy to handle at low temperatures, but have a problem that they are inferior in 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 products is deteriorated. Therefore, especially for high-density packaging materials such as when manufacturing semiconductor devices, there is a strong demand for further high-performance bonding members.

As a joining member meeting such demands, polyimide having high heat resistance and mechanical strength and excellent electrical properties is promising because of its excellent properties.
However, in general, polyimide is almost insoluble in the closed state,
It is infusible and used as an organic insulating material for FPC and TAB
It is used as a base film for C tape.

In recent years, examples have been proposed in which polyimide is used as a joining member. A silver paste composition has been proposed in which a silver filler is kneaded in a precursor solution of a polyimide resin such as polyamic acid synthesized from pyromellitic anhydride and a normal aromatic diamine, and according to this, die bonding is performed. The precursor is ring-closed (imidized) by heat curing to give a polyimide resin having excellent heat resistance, and therefore, good results are obtained in the high-temperature electrical characteristics of the semiconductor device. For example, JP-A-60-71662 discloses a conductive silver paste composition in which a silver filler is kneaded in an organic solvent solution of a siloxane-modified polyimide resin precursor using siloxane diamine.

In Japanese Patent Application Laid-Open No. 2-138789, 3,3
3 ', 4,4'-benzophenonetetracarboxylic dianhydride and an aromatic polyimide composed of an aromatic diamine using an adhesive film obtained from a resin composition mixed with maleimide, a substrate such as a polyimide film and a copper foil Glue F
A method for manufacturing a PC has been proposed. Further, Japanese Patent Application Laid-Open No.
JP-A-709224 and JP-A-5-112768 propose various kinds of thermoplastic polyimide adhesive materials which can be heated and pressed.

[0008]

However, an epoxy resin mixed with a silver filler or a resin which is ring-closed (imidized) using a polyimide precursor has a relatively high moisture absorption rate, and the semiconductor device is sealed with the epoxy resin. When a thermal history of about 240 ° C. such as solder reflow is applied, moisture absorbed by the adhesive or the like expands, and a package crack occurs.

Although the polyimide-based film-like joining member described above improves the polyimide melt flowability and can be used as an adhesive, it requires a high temperature and a long time for adhesion and has a problem in workability. there were.

[0010] In addition, the film-shaped joining member cannot use the joining equipment and process used in the conventional silver paste, and requires new equipment for punching a film and bonding the film to a lead frame. Since the film is also flowed on a reel-shaped line, when punching into a predetermined size, the punched film has a margin so as not to be broken in the longitudinal direction, and this 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.

[Object of the Invention] Accordingly, the present inventors have solved the above problems and provided a liquid joining member having excellent properties such as excellent heat resistance, workability, and adhesiveness, and particularly exhibiting a low water absorption. As a result of intensive studies for the purpose of doing so, the present invention has been achieved.

[0012]

The liquid joining member of the present invention has the following general formula (1):

Embedded image (Wherein, R ¹ is a tetravalent organic group, n is an integer of 1 to 10), and has a glass transition temperature of 200 ° C. or less and a water absorption of 1% or less. It is a liquid joining member containing a polyimide polymer.

In the above general formula (1), R ¹ is the following general formula (2)

Embedded image (Wherein, X represents a divalent organic group), and is preferably at least one selected from groups represented by the following formula:

[0014]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method for manufacturing a liquid bonding member according to the present invention will be specifically described.

The polyesterimide used in the present invention is produced, for example, as follows.

The following general formula (A)

Embedded image (Wherein, R ¹ represents the same tetravalent organic group as R ¹ in the general formula (1)) and the tetracarboxylic dianhydride represented by the following general formula (B)

Embedded image (Wherein, n represents an integer of 1 to 10) can be obtained as a raw material.

The most typical example of the compound represented by the general formula (A) is pyromellitic dianhydride (hereinafter referred to as PM).
DA), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (hereinafter abbreviated as BTDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter abbreviated) BPDA), 3,3 ', 4,4'-oxydiphthalic dianhydride (hereinafter, referred to as BPDA)
ODPA), 2,2′-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter abbreviated as ESDA), 3,3 ′, 4,4′-ethylene glycol dibenzoate tetracarboxylic dianhydride (hereinafter abbreviated as EGDA), 3,3 ′, 4,4′-hydroquinone dibenzoate tetracarboxylic dianhydride (hereinafter, referred to as EGDA)
TMHQ). These are one or two
A mixture of more than one species can be used.

As the diamine represented by the general formula (B), n is at least one selected from 1 to 10 or 2
More than one species can be used as a mixture, and other diamines can be used as a mixture to the extent that the effects of the present invention are not impaired.

Other diamines include p-phenylenediamine, m-phenylenediamine, 1,4-diaminodiphenyl, 4,4'-diaminodiphenyl ether, 3,3 '
-Diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylpropane, 4,4'-
Diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4 , 4'-diaminodiphenylamine, 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) ethane, 2,2-bis ((4-aminophenoxy) methyl) propane, 2,2-bis ((3-aminophenoxy) methyl) Propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,1-bis (4- ( Four-
Aminophenoxy) phenyl) methane, 1,1-bis (3-methyl-4- (4-aminophenoxy) phenyl) methane, 1,
1-bis (3-ethyl-4- (4-aminophenoxy) phenyl) methane, 1,1-bis (3-propyl-4- (4-aminophenoxy) phenyl) methane, 1,1-bis (3- Isopropyl
-4- (4-aminophenoxy) phenyl) methane, 1,1-bis (3-butyl-4- (4-aminophenoxy) phenyl) methane, 1,1-bis (3-sec-butyl-4- ( 4-aminophenoxy) 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) methane, 1,1-bis (3,5-dimethoxy-4- (4-aminophenoxy) phenyl) methane, 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) phenyl) ethane, 1,1-bis (3-propyl-4- (4-aminophenoxy) phenyl) ethane, 1,1-bis (3- Isopropyl
-4- (4-aminophenoxy) phenyl) ethane, 1,1-bis (3-butyl-4- (4-aminophenoxy) phenyl) ethane, 1,1-bis (3-sec-butyl-4- ( 4-aminophenoxy) 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) ethane, 1,1-bis (3,5-dimethoxy-4- (4-aminophenoxy) 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) propane, 2,2-bis (3-propyl-4- (4 -Aminophenoxy) phenyl) propane, 2,2-bis (3-isopropyl-4- (4-aminophenoxy) phenyl) propane, 2,2-bis (3-butyl-4- (4-aminophenoxy) phenyl) Propane, 2,2-bis (3-sec-butyl-4- (4-
Aminophenoxy) phenyl) propane, 2,2-bis (3-
Methoxy-4- (4-aminophenoxy) phenyl) propane, 2,2-bis (3-ethoxy-4- (4-aminophenoxy)
Phenyl) propane, 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-amino Phenoxy) phenyl) propane, 1,1-bis (3-ethyl-4-
(4-aminophenoxy) phenyl) propane, 1,1-bis (3-propyl-4- (4-aminophenoxy) phenyl) propane, 1,1-bis (3-isopropyl-4- (4-aminophenoxy) Phenyl) propane, 1,1-bis (3-butyl-4-
(4-aminophenoxy) phenyl) propane, 1,1-bis (3-sec-butyl-4- (4-aminophenoxy) phenyl) propane, 1,1-bis (3-methoxy-4- (4-amino Phenoxy) phenyl) propane, 1,1-bis (3-ethoxy)
-4- (4-aminophenoxy) phenyl) propane, 1,1-
Bis (3,5-dimethyl-4- (4-aminophenoxy) 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-aminophenoxy) phenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3- Methyl-4- (4-aminophenoxy) phenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-ethyl-4- (4-aminophenoxy) phenyl) propane ,
1,1,1,3,3,3-hexafluoro-2,2-bis (3-propyl-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-aminophenoxy) phenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis ( 3-sec-butyl-4- (4-aminophenoxy) phenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-methoxy-4- (4-aminophenoxy) ) Phenyl) 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) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,5-dimethoxy-4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) butane, 2,2-bis (3-methyl-4- (4-aminophenoxy) phenyl) butane, 2,2-bis (3-ethyl-4-
(4-aminophenoxy) phenyl) butane, 2,2-bis (3-propyl-4- (4-aminophenoxy) phenyl) butane, 2,2-bis (3-isopropyl-4- (4-aminophenoxy) Phenyl) butane, 2,2-bis (3-butyl-4- (4-
Aminophenoxy) phenyl) butane, 2,2-bis (3-se
c-Butyl-4- (4-aminophenoxy) phenyl) butane, 2,2-bis (3-methoxy-4- (4-aminophenoxy)
Phenyl) butane, 2,2-bis (3-ethoxy-4- (4-aminophenoxy) phenyl) butane, 2,2-bis (3,5-dimethyl-4- (4-aminophenoxy) phenyl) butane, 2,
2-bis (3,5-dimethoxy-4- (4-aminophenoxy) 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) pentane,
3-bis (3-propyl-4- (4-aminophenoxy) phenyl) pentane, 3,3-bis (3-isopropyl-4- (4-aminophenoxy) phenyl) pentane, 3,3-bis (3- Butyl-4- (4-aminophenoxy) phenyl) pentane, 3,
3-bis (3-sec-butyl-4- (4-aminophenoxy) phenyl) pentane, 3,3-bis (3-methoxy-4- (4-aminophenoxy) phenyl) pentane, 3,3-bis ( 3-ethoxy-4- (4-aminophenoxy) phenyl) pentane,
3,3-bis (3,5-dimethyl-4- (4-aminophenoxy) phenyl) propane, 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) pentane, 3,5-bis (3-ethyl-4- (4-aminophenoxy)
Phenyl) pentane, 3,5-bis (3-propyl-4- (4-aminophenoxy) phenyl) pentane, 3,5-bis (3-isopropyl-4- (4-aminophenoxy) phenyl) pentane, 5-bis (3-butyl-4- (4-aminophenoxy)
Phenyl) pentane, 3,5-bis (3-sec-butyl-4-
(4-aminophenoxy) phenyl) pentane, 3,5-bis (3-methoxy-4- (4-aminophenoxy) phenyl) pentane, 3,5-bis (3-ethoxy-4- (4-aminophenoxy) Phenyl) pentane, 3,5-bis (3,5-dimethyl-4-
(4-aminophenoxy) phenyl) propane, 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.

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. Examples of such a diamine include piperazine, hexamethylenediamine, heptamethylenediamine, tetramethylenediamine, p-xylylenediamine, m-xylylenediamine, and 3-methylheptamethylenediamine. These diamines can be used alone or may be copolymerized.

As a polymerization method for obtaining the polyesterimide polymer of the present invention, a compound represented by the following general formula (C) is used in a polar solvent.

Embedded image (Where R ¹ is the same as in the general formula (1), and n is 1 to 1)
A polyamic acid derivative represented by the general formula (1) is synthesized, isolated, and then imidized to obtain a polyimide polymer represented by the general formula (1), or imidation in a polar solvent. To obtain a polyimide polymer represented by the general formula (1).

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 1.1 equivalent, relative to 1 equivalent of the acid dianhydride represented by the general formula (A).
05 equivalents, N, N-dimethylformamide, N, N
After reaction in a polar solvent such as N-dimethylacetamide or N-methyl-2-pyrrolidone at 0 to 100 ° C. for several tens of minutes to several hours, imidization is performed. (1) 5
(2) 2 to 5 equivalents of acetic anhydride and 1 to 2 equivalents of pyridine are added at 50 to 180 ° C. and chemically. There is a method of promoting imidization.

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).
05 equivalents, N, N-dimethylformamide, N, N
0-100 ° C., preferably 0-60 ° C. in a polar solvent such as N-dimethylacetamide and N-methyl-2-pyrrolidone.
By reacting in the range of ° C, the above-mentioned general formula (C)
Is produced, and the polyimide polymer of the present invention represented by the general formula (1) can be produced by a conventionally used dehydration cyclization method. As the dehydration cyclization method, (1) after isolating the polymer,
A method of cyclizing by heating at 350 ° C., (2) in a solution state, 80 to 400 ° C., preferably 100 to 250 ° C.
Cyclization by heating at this time, and in this case, it is preferable to use a solvent azeotropic with water, such as benzene, toluene and xylene. (3) acetic acid, propionic acid,
There is a method of cyclizing with a chemical dehydrating agent such as an acid anhydride such as butyric acid and benzoic acid. At this time, it is preferable to use pyridine, quinoline, picoline, and the like in combination as substances that promote the cyclization reaction. Above all, β-picoline promotes imidation more than other amines and has a relatively low boiling point, so that it is a well-balanced amine when producing a polyimide resin, and is particularly preferable.

To obtain a high molecular weight polyimide polymer,
It is preferable to mix the diamine with the acid dianhydride in the above range, and if it is out of this range, only low molecular weight compounds tend to be obtained.

In the method for obtaining the polyesterimide polymer of the present invention, the reaction solution obtained as described above is compatible with the above-mentioned polar solvents such as lower alcohol and water, and is a poor solvent for the resin. The solvent is poured into a large excess to obtain a precipitate, which is filtered, dried and pulverized to obtain a powder.

Further, in order to use this as a liquid joining member, N, N-dimethylformamide, N, N-
The powder may be dissolved in a polar solvent such as dimethylacetamide and N-methyl-2-pyrrolidone.

When the joining member needs to have thermal conductivity, Ag, Au, Al, Cu, 0 to 80% by weight with respect to the resin.
Ni, C, SiC, SiO ₂ , MgO, BN ₃ , Al ₂
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 conductivity is required, 50 to 80% by weight of Ag, Au, Al, Cu, N
Metal fillers such as i 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.

There are the following methods for joining a semiconductor element to a support member in a semiconductor device using the liquid joining member of the present invention. (1) The liquid bonding member is dispensed on a support member, and a semiconductor element is mounted thereon to perform a heat treatment. (2) The bonding surface of the support member is immersed in 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 immersed in the bath of the liquid bonding member, and a supporting member is placed thereon to perform a heat treatment.

After such bonding, wire bonding is performed for the purpose of electrically connecting the support member and the semiconductor element, and resin sealing such as epoxy resin or glass sealing is performed.
Sealed by ceramic sealing or the like.

FIG. 1 shows the semiconductor device thus obtained.
3 to FIG. 1 to 3 are cross-sectional views of a resin-encapsulated semiconductor device. FIG. 1 is a supporting member (lead frame).
The semiconductor element 1 is bonded to the semiconductor element 3 via a bonding member 2, and the semiconductor element 1 and the external lead wires 6 are wire-bonded by bonding wires 4. The entire semiconductor device is sealed with epoxy resin 5. FIG.
A support member 3 also serving as an external lead wire is joined to the semiconductor element 1 via a joining member 2, and the semiconductor element 1 and the support member 3 are wire-bonded by a bonding wire 4. Epoxy resin 5 for the entire semiconductor device
It is sealed with. FIG. 3 shows a support member 3 made of a ceramic, plastic, metal or the like on which a circuit pattern is applied.
The semiconductor element 1 is joined via the joining member 2, and the semiconductor element 1 is joined to the circuit pattern electrode of the support member 3 by the bonding wire 4. This support member 3
Has electrical continuity in the thickness direction by a substrate laminating technique or the like, and the electrodes of the semiconductor element 1 are electrically connected to the external solder balls 7 through the bonding wires 4. The entire semiconductor device is sealed with epoxy resin 5.

[0031]

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, 16.5 g of 1,2-bis (2- (4-aminophenoxy) ethoxy) ethane (hereinafter abbreviated as DA3EG) was placed in a 500 ml three-neck separable flask equipped with a stirrer.
(49.6 mmol) and 239.6 g of N, N-dimethylformamide (hereinafter abbreviated as DMF) were added, and the mixture was stirred under a nitrogen atmosphere and dissolved sufficiently. Next, 2,2'-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-
27.9 g of tetracarboxylic dianhydride (ESDA) (4
8.6 mmol), and the wall of the separable flask was washed with 10 g of DMF. After being left for about 1 hour while stirring, a solution of 0.6 g of ESDA previously dissolved in 5.4 g of DMF was gradually charged into the flask while paying attention to the varnish viscosity in the flask. Viscosity 200
After reaching 0 poise, the introduction of the ESDA solution was terminated to obtain a polyamic acid solution.

In order to carry out imidation in the state of a polyamic acid solution, 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 of minutes to several hours to perform imidization.

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

The obtained polyesterimide polymerized powder 10
g to 90 g of N-methyl-2-pyrrolidone (hereinafter referred to as NM)
P), DMF, and N, N-dimethylacetamide (hereinafter abbreviated as DMAc) at a concentration of 10% by weight.
Further, the water absorption and the glass transition temperature of the obtained soluble polyimide resin were measured. Hereinafter, the measurement method will be described.

When the solid concentration of the soluble polyimide resin is 10
% NMP solution on a glass plate with an applicator.
After applying to a thickness of 3 mm, using a hot air oven, 100
After drying at 150 ° C. for 5 minutes, peel off from the glass substrate, fix both ends of the obtained semi-dry polyimide film, and further dry at 200 ° C. and 250 ° C. for 5 minutes to obtain a 30 μm thick polyimide film. I got The water absorption of the polyimide film thus obtained was determined by ASTM.
It measured according to D-570. The glass transition temperature of the obtained film was measured by DMS (dynamic viscoelasticity meter, manufactured by Seiko Denshi Co., Ltd.).

The evaluation of the adhesiveness of the obtained 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 of the semiconductor device. Table 2 shows the results.

Examples 2 to 11 Using the raw materials shown in Table 1, a liquid bonding member was obtained and evaluated in the same manner as in Example 1. Table 2 shows the results.

Comparative Examples 1 to 5 Using the raw materials shown in Table 1, powders of a polyimide polymer were obtained in the same manner as in Example 1. Table 2 shows the evaluation results.

[0041]

[Table 1] ESDA; 2,2'-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride EGDA; 3,3', 4,4'-ethylene glycol benzoate tetra 3,3 ′, 4,4′-hydroquinone dibenzoate tetracarboxylic dianhydride BPDA; 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride ODPA; 3,3 ′, 4,4′-hydroquinone dibenzoate tetracarboxylic dianhydride ODPA; ', 4,4'-oxydiphthalic dianhydride BTDA; 3,3', 4,4'-benzophenonetetracarboxylic dianhydride DSDA; 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride Oda; oxydianiline BAPP; 2,2-bis (4-aminophenoxy) phenylpropane BAPS; bis (4- (4-aminophenoxy) phenyl)
Sulfone DA2EG; n of 2 in the above [Chemical Formula 6] is DA3EG; n of 3 in the above [Chemical Formula 6] is DA4EG; n in the above [Chemical Formula 6] is 4 DA5EG; And n is 5 in the above formula. DA6EG;

[0042]

[Table 2]

[0043]

As described above, the liquid bonding member according to the present invention has good solubility in polar solvents such as NMP, excellent adhesiveness, and has a glass transition temperature of 200 ° C. or less and a water absorption rate. Has a low value of 1.0% or less.

[Brief description of the drawings]

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

FIG. 2 is a semiconductor device using a liquid bonding member according to another embodiment.

FIG. 3 is a semiconductor device using a liquid bonding member according to yet another embodiment.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1; Semiconductor element 2; Joint member 3; Support member 4; Bonding wire 5; Epoxy sealing resin 6; External lead wire 7;

Claims (2)

[Claims] (1) The following general formula (1): (Wherein, R ¹ is a tetravalent organic group, and n is an integer of 1 to 10), and has a glass transition temperature of 200 ° C. or less and a water absorption of 1% or less. A liquid joining member containing a polyimide polymer. 2. In the general formula (1), R ¹ represents the following general formula (2): The liquid joining member according to claim 1, wherein the liquid joining member is at least one selected from groups represented by the following formula (where X is a divalent organic group).