JP2001247780A - Heat resistant resin paste and semiconductor device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat resistant resin paste widely usable for coating material, adhesive, stress relaxing agent and the like in semiconductor device or the like, having an arbitrarily controllable elastic modulus, capable of forming a resin film excellent in heat resistance, having thixotropic nature, and applicable to a coating method of excellent coating efficiency such as screen printing or dispense, and to provide a semiconductor device containing a resin film which has thixotropic nature, obtainable from a heat resistant resin paste applicable to a coating method having excellent coating efficiency such as screen printing or dispense, is widely usable for a coating material, an adhesive, a stress relaxing agent and the like in a semiconductor device or the like, has an arbitrarily controllable elastic modulus, and is excellent in heat resistance. SOLUTION: The heat resistant resin paste contains (I) a heat resistant resin A which dissolves in the solvent (IV) at room temperature and at a temperature of heat drying, (II) a heat resistant resin B which does not dissolve in the solvent (IV) at room temperature and dissolves in the solvent (IV) at a temperature of heat drying, (III) particles or a liquid C exhibiting rubber elasticity, and (IV) a solvent. The semiconductor device has a resin film obtained from the heat resistant resin paste.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can be widely used for coating materials, adhesives, stress relaxation materials and the like of semiconductor devices and the like, and can control elastic modulus arbitrarily and has a small temperature dependence of elastic modulus. The present invention relates to a heat-resistant resin, a heat-resistant resin paste suitable for forming the heat-resistant resin film, and a semiconductor device using the same.

[0002]

2. Description of the Related Art In recent years, electronic components have become smaller and thinner.
For materials applied to these components, how to relieve stress has become an important consideration. For example, a material for directly coating an electronic component is required to have high stress relaxation. In particular, although the size of the entire component has been reduced, the chip mounted thereon has become larger and thinner, and is more susceptible to damage due to stress during or after curing. Against this background, it has become more demanding to reduce the stress of the resin itself. In particular, in the case of products such as IC cards in which multiple bare chips are mounted on the same substrate or in the formation of resin dams for lead frames, slight stress during curing may cause disconnection of wiring, warpage of the substrate, and distortion of the frame. Cause.

[0003] Epoxy resins and the like have conventionally been used in products in which a plurality of bare chips are mounted on the same substrate, such as an IC card, and in the formation of a resin dam for a lead frame. The accompanying stress is large, and in a heat cycle test after curing or a solder reflow test, disconnection of wiring, cracking of a cured product, and the like have become problems. In addition, regarding the distortion when forming the resin dam on the lead frame, there is a problem that molding resin flows out from the portion where the distortion has occurred and molding defects at the time of molding. To solve these problems, Japanese Patent Laid-Open Publication No. 2-311
No. 520 discloses an attempt to impart flexibility and reduce stress by adding a silicone rubber elastic material to an epoxy resin composition. There is a problem that strength is reduced.

[0004] CSP (chip size package)
In order to ensure high package reliability in heat cycle tests, solder reflow tests, etc., stress relaxation layers and adhesive layers made of low-elastic materials that reduce the difference in the coefficient of thermal expansion between the silicon chip and the mounting board Is being used. In the μBGA, which is an example of the CSP, the purpose is to secure the connection reliability between the lead from the “TAB” (tape automated bonding) tape and the electrode on the silicon chip, and to bond the TAB tape to the silicon chip. Low modulus materials are used.

Further, as a technology for integrating a wafer process and a package process, which have been completely separated until now, a wafer level CSP process for forming a package in a wafer state with the same size as a chip size has been proposed. According to the technology, not only the manufacturing cost of the package can be reduced, but also the wiring length can be shortened, so that there is an advantage that signal delay and noise in the package can be reduced, and high-speed operation can be achieved.

In this package, in order to secure high reliability, similarly to a conventional CSP such as μBGA, a stress made of a low elastic material which reduces a difference in thermal expansion coefficient between a silicon chip and a mounting substrate is used. It is necessary to use a relaxation layer or an adhesive layer. In this wafer-level CSP process, a metal layer called a redistribution layer is formed on the stress relaxation layer by a sputtering method or a plating method in order to connect the electrodes of the chip to the external mounting substrate, so that the elasticity is low. Instead, it is required to have resistance to sputtering and plating. However, the low-elasticity material used for the μBGA has low elasticity but low heat resistance, and therefore has low resistance to sputtering and plating, and cannot be directly applied to the wafer level CSP process.

[0007] On the other hand, attempts have been made to reduce the elastic modulus by adding a monomer component having rubber elasticity to an epoxy resin to relieve stress (Japanese Patent Publication No. 61-48).
544) has a problem that the heat resistance of the resin is reduced by combining these components.

In general, a high heat-resistant thermoplastic resin has a high resin elasticity and a high mechanical strength but is brittle. Therefore, when applied to an electronic component as it is, a cured base material is warped or a resin crack is generated in a thermal shock test. There is a high possibility that such troubles will occur. In view of this, Japanese Patent Application Laid-Open (JP-A) No. 1-123824 proposes a method in which a monomer component having rubber elasticity is copolymerized in a resin. However, these methods are not preferable because they reduce the heat resistance of the resin itself.

As a method of forming a heat-resistant resin on a substrate such as a chip, a spin coating method, a screen printing method, a dispensing method, a film laminating method and the like are known. In the spin coating method, there are problems in terms of environment and cost, such as that the application efficiency of the heat-resistant resin solution is usually 10% or less (90% or more is lost without being applied to the substrate). On the other hand, a screen printing method using a metal plate or a mesh plate has an advantage in that a heat-resistant resin can be efficiently applied to only necessary portions in a short time. Also,
The dispensing method has an advantage in that a heat-resistant resin can be efficiently applied to only necessary portions in a non-contact manner.

As a heat-resistant resin paste applicable to a coating mode having excellent coating efficiency such as screen printing and dispensing, a heat-resistant resin which dissolves in a solvent at the time of heating and drying is used in Japanese Patent Application Laid-Open No. 9-142252. A heat-resistant resin paste capable of forming a pattern has been reported. However, since this heat-resistant resin has a large elastic modulus,
There is a problem that as it is, it cannot be used as a stress relaxation material for relaxing the difference in thermal expansion coefficient between the silicon chip and the mounting substrate.

[0011]

The invention according to claim 1 can be widely used for coating materials, adhesives, stress relaxation materials, etc. of semiconductor devices, etc., and can control elastic modulus arbitrarily and improve heat resistance. Excellent resin film can be formed,
An object of the present invention is to provide a heat-resistant resin paste having thixotropy and applicable to a coating mode excellent in coating efficiency such as screen printing and dispensing. The invention described in claim 2 provides a heat-resistant resin paste that provides a resin film having more excellent heat resistance, in addition to the effects of the invention described in claim 1.

According to a third aspect of the present invention, in addition to the effects of the first or second aspect, there is provided a heat-resistant resin paste which is more excellent in solvent stability and solubility of the heat-resistant resin for imparting thixotropy to the solvent. Is what you do. The invention described in claim 4 provides a heat-resistant resin paste which is excellent in the dispersibility of particles exhibiting rubber elasticity and the surface smoothness of a coating film obtained in addition to the effects of the invention described in claim 1, 2 or 3. Is what you do. The invention according to claim 5 has, in addition to the effects of the invention according to claim 1, 2, 3 or 4, more reliable when widely used for coating materials, adhesives, stress relaxation materials, etc. for semiconductor devices and the like. An object is to provide a heat-resistant resin paste that gives a high resin film.

[0013] The invention according to claim 6 is the invention according to claims 1, 2,
Another object of the present invention is to provide a heat-resistant resin paste that provides a resin film having more excellent process compatibility, in addition to the effects of the invention described in 3, 4, or 5. The invention according to claim 7 is based on claim 1,
Another object of the present invention is to provide a heat-resistant resin paste having excellent printability and resolution in addition to the effects of the invention described in 2, 3, 4, 5, or 6. The invention according to claim 8 has a thixotropy property, a coating material for a semiconductor device or the like obtained from a heat-resistant resin paste applicable to a coating mode having excellent coating efficiency such as screen printing or dispensing, an adhesive, a stress relaxation material, and the like. The present invention provides a semiconductor device having a resin film that can be widely used in a semiconductor device, whose elastic modulus can be arbitrarily controlled, and has excellent heat resistance.

[0014]

SUMMARY OF THE INVENTION The present invention relates to (I) a heat-resistant resin A which is soluble in the solvent (IV) at room temperature and a temperature at the time of heating and drying, and a solvent (II) which is soluble in the solvent (IV) at room temperature. The present invention relates to a heat-resistant resin paste containing a heat-resistant resin B which dissolves at a temperature at the time of drying by heating without heating, (III) particles having rubber elasticity or a liquid C, and (IV) a solvent.

The present invention also relates to an aromatic polyimide obtained by reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine, wherein the heat resistant resin A of (I) and the heat resistant resin B of (II) are reacted. The heat-resistant resin paste, wherein the main component of the particles exhibiting rubber elasticity of (III) is silicone rubber, is a base resin. In addition, the present invention relates to the heat-resistant resin B of (II), wherein the heat-resistant resin B is an aromatic tetracarboxylic dianhydride containing 50 mol% or more of 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride. An aromatic polyimide resin obtained by reacting with an aromatic diamine containing at least 50 mol% of 4,4'-diaminodiphenyl ether;
The present invention relates to the heat-resistant resin paste, wherein the main solvent of V) is γ-butyrolactone.

Further, the present invention relates to the heat-resistant resin paste, wherein the particles having rubber elasticity have an average particle size of 0.1 to 50 μm. Further, in the present invention, the elastic modulus of the resin film obtained from the heat-resistant resin paste can be arbitrarily controlled in the range of 0.2 to 3.0 GPa, and the elastic modulus at 150 ° C. is −65 ° C. The present invention relates to the heat-resistant resin paste having an elastic modulus of 10 to 100%.

Further, the present invention relates to the above-mentioned heat-resistant resin paste wherein the resin film obtained from the heat-resistant resin paste has a glass transition temperature of 180 ° C. or more and a 5% weight loss temperature of 300 ° C. or more. Further, the present invention has a viscosity of 10 to 10.
1,000 Pa · s and a thixotropy coefficient of 1.
The present invention relates to the heat-resistant resin paste of 2 or more. Also,
The present invention relates to a semiconductor device having a resin film obtained from the heat-resistant resin paste.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The heat-resistant resin paste of the present invention comprises:
(I) Heat-resistant resin A that dissolves in solvent (IV) at room temperature and temperature when heated and dried, heat resistance that dissolves at temperature when heated and dried without dissolving at room temperature in solvent (II) and (IV) Resin B,
(III) Particles or liquids C exhibiting rubber elasticity and (IV) a solvent.

In the present invention, as the heat-resistant resin A which dissolves in the solvent (IV) at room temperature and at the time of heating and drying in the present invention, a heat-resistant resin paste film is formed by screen printing or the like, and the film is dried by heating and dried. When forming a pattern, it is preferable to use a resin which forms a uniform phase with the heat-resistant resin B of (II) after drying by heating. That is, it is preferable to use a material that dissolves well in a solvent at the temperature of heating and drying and that is well compatible with the heat-resistant resin B at the temperature of heating and drying.

Specifically, it is preferable to use a heat-resistant resin having, for example, an amide group, an imide group, an ester group or an ether group. More specifically, there are polyimide resin, polyamide imide resin, polyamide resin, polyester resin, polyether resin and the like. As for the polyimide resin and the polyamide-imide resin, a polyamic acid which is a precursor thereof or a partially imidized resin of a polyamic acid may be used.

In consideration of heat resistance, (I) heat-resistant resin A
It is preferable that the 5% thermogravimetric loss temperature is 300 ° C. or higher. If the temperature is less than 300 ° C., the heat treatment process at a high temperature
For example, outgassing is likely to occur when solder balls are mounted, and it tends to be difficult to obtain reliability of the semiconductor device. Considering the ease of synthesis, heat resistance and storage stability of the paste,
It is more preferable to use a polyimide resin, and among them, an aromatic polyimide resin (for example, a polyamic acid obtained by reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine, a polyimide obtained by imidating the polyamic acid, etc.) is particularly preferable. preferable.

As the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, 3,3 ', 4,
4'-biphenyltetracarboxylic dianhydride, 2,
2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride Anhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride,
1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl)
Sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-
Tetracarboxylic dianhydride, 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride, 2,3,2',
3'-benzophenonetetracarboxylic dianhydride, 2,
3,3 ', 4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1, 2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4
5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,
4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3 4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylbis (trimellitic acid monoester acid anhydride), 2,2- Bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,
2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 4, 4-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride,
1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 1,3
-Bis (2-hydroxyhexafluoroisopropyl)
Benzene bis (trimellitic anhydride), 1,2- (ethylene) bis (trimellitate dianhydride), 1,3-
(Trimethylene) bis (trimellitate dianhydride),
1,4- (tetramethylene) bis (trimellitate dianhydride), 1,5- (pentamethylene) bis (trimellitate dianhydride), 1,6- (hexamethylene) bis (trimellitate dianhydride), 7- (heptamethylene)
Bis (trimellitate dianhydride), 1,8- (octamethylene) bis (trimellitate dianhydride), 1,9-
(Nonamethylene) bis (trimellitate dianhydride),
1,10- (decamethylene) bis (trimellitate dianhydride), 1,12- (dodecamethylene) bis (trimellitate dianhydride), 1,16- (hexadecamethylene)
There are bis (trimellitate dianhydride) and 1,18- (octadecamethylene) bis (trimellitate dianhydride), and these may be used alone or in combination of two or more.

The above-mentioned aromatic tetracarboxylic dianhydride may be replaced with a tetracarboxylic dianhydride other than the aromatic tetracarboxylic dianhydride in an amount of 50 mol% of the aromatic tetracarboxylic dianhydride. It can be used within a range not exceeding. As such a tetracarboxylic dianhydride, for example, ethylene tetracarboxylic dianhydride, 1,
2,3,4-butanetetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride,
Decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,
6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,2
3,4-tetracarboxylic dianhydride, pyrrolidine-2,
3,4,5-tetracarboxylic dianhydride, 1,2,3
4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride) sulfone, bicyclo- (2,2,2)
-Oct (7) -ene-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Anhydride, tetrahydrofuran-2,3,4
5-tetracarboxylic dianhydride and the like.

The acid anhydride (I) used in the heat-resistant resin A in the present invention is selected from the viewpoint that a resin film can be obtained at a low drying temperature without impairing the heat resistance.
1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 1,3
-Bis (2-hydroxyhexafluoroisopropyl)
Benzene bis (trimellitic anhydride), 1,2- (ethylene) bis (trimellitate dianhydride), 1,3-
(Trimethylene) bis (trimellitate dianhydride),
1,4- (tetramethylene) bis (trimellitate dianhydride), 1,5- (pentamethylene) bis (trimellitate dianhydride), 1,6- (hexamethylene) bis (trimellitate dianhydride), 7- (heptamethylene)
Bis (trimellitate dianhydride), 1,8- (octamethylene) bis (trimellitate dianhydride), 1,9-
(Nonamethylene) bis (trimellitate dianhydride),
1,10- (decamethylene) bis (trimellitate dianhydride), 1,12- (dodecamethylene) bis (trimellitate dianhydride), 1,16- (hexadecamethylene)
It is preferable to use trimellitate such as bis (trimellitate dianhydride) and 1,18- (octadecamethylene) bis (trimellitate dianhydride).

Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and 3,4 '
-Diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-
Diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,
3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-
Diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2- (3,4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane,
3-bis (3-aminophenoxy) benzene, 1,4-
Bis (4-aminophenoxy) benzene, 3,3'-
[1,4-phenylenebis (1-methylethylidene)]
Bisaniline, 3,4 '-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4'-
[1,4-phenylenebis (1-methylethylidene)]
Bisaniline, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4 −
(3-Aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] Sulfone, 1,2-diamino-4-carboxybenzene, 1,3-diamino-5-carboxybenzene,
1,3-diamino-4-carboxybenzene, 1,4-
Diamino-6-carboxybenzene, 1,5-diamino-6-carboxybenzene, 1,3-diamino-4,6
-Dicarboxybenzene, 1,2-diamino-3,5-
Dicarboxybenzene, 4- (3,5-diaminophenoxy) benzoic acid, 3- (3,5-diaminophenoxy)
Benzoic acid, 2- (3,5-diaminophenoxy) benzoic acid, 3,3′-dicarboxy-4,4′-diaminobiphenyl, 3,3′-diamino-4,4′-dicarboxybiphenyl, 2, 2-bis (4-carboxy-3-aminophenyl) propane, 2,2-bis (4-carboxy-3-aminophenyl) hexafluoropropane, bis (4-carboxy-3-aminophenyl) ketone, bis (4 -Carboxy-3-aminophenyl) sulfide;
Bis (4-carboxy-3-aminophenyl) ether, bis (4-carboxy-3-aminophenyl) sulfone, bis (4-carboxy-3-aminophenyl) methane, 4-[(2,4-diamino-5) -Pyrimidinyl)
Methyl] benzoic acid, p- (3,6-diamino-s-triazin-2-yl) benzoic acid, bis (4-carboxy-
3-aminophenyl) difluoromethane, 2,2-bis (4-amino-3-carboxyphenyl) propane,
2,2-bis (4-amino-3-carboxyphenyl)
Hexafluoropropane, bis (4-amino-3-carboxyphenyl) ketone, bis (4-amino-3-carboxyphenyl) sulfide, bis (4-amino-3-
Carboxyphenyl) ether, bis (4-amino-3)
-Carboxyphenyl) sulfone, bis (4-amino-
3-carboxyphenyl) methane, bis (4-amino-
3-carboxyphenyl) difluoromethane, 1,2-
Diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 1,3-diamino-4-hydroxybenzene, 1,4-diamino-6-hydroxybenzene, 1,5-diamino-6-hydroxybenzene 1,3-diamino-4,6-dihydroxybenzene, 1,2-diamino-3,5-dihydroxybenzene, 4- (3,5-diaminophenoxy) phenol,
3- (3,5-diaminophenoxy) phenol, 2-
(3,5-diaminophenoxy) phenol, 3,3 ′
-Dihydroxy-4,4'-diaminobiphenyl, 3,
3'-diamino-4,4'-dihydroxybiphenyl,
2,2-bis (4-hydroxy-3-aminophenyl)
Propane, 2,2-bis (4-hydroxy-3-aminophenyl) hexafluoropropane, bis (4-hydroxy-3-aminophenyl) ketone, bis (4-hydroxy-3-aminophenyl) sulfide, bis (4 -Hydroxy-3-aminophenyl) ether, bis (4-
Hydroxy-3-aminophenyl) sulfone, bis (4
-Hydroxy-3-aminophenyl) methane, 4-
[(2,4-diamino-5-pyrimidinyl) methyl] phenol, p- (3,6-diamino-s-triazine-
2-yl) phenol, bis (4-hydroxy-3-aminophenyl) difluoromethane, 2,2-bis (4-
Amino-3-hydroxyphenyl) propane, 2,2-
Bis (4-amino-3-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) ketone, bis (4-amino-3-hydroxyphenyl) sulfide, bis (4-amino-3-hydroxy) Phenyl) ether, bis (4-amino-3-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) difluoromethane,

Embedded image And two or more of these may be used in combination.

In the production of the polyimide resin, as the diamine compound, besides the aromatic diamine, for example,
1,2-diaminoethane, 1,3-diaminopropane,
1,4-diaminobutane, 1,5-diaminopentane,
1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,3-bis (3-amino Propyl) tetramethyldisiloxane, aliphatic diamines such as 1,3-bis (3-aminopropyl) tetramethylpolysiloxane,
A diamine compound other than an aromatic diamine such as diaminosiloxane can be used, but from the viewpoint of heat resistance, it is preferably used at 50% by weight or less based on the total amount of the diamine compound.

In the production of the polyimide resin used in the present invention, it is preferable that the aromatic tetracarboxylic dianhydride and the diamine compound are reacted in substantially equimolar from the viewpoint of film properties. In order to facilitate the control of the end point of the reaction and to obtain a polyimide resin having a desired molecular weight, the compounding molar ratio of any of the acid component and the amine component is slightly excessive (1.01 to 1.01).
(Approximately 1.10). Alternatively, as a terminal blocking agent for the acid component and the amine component, for example, maleic anhydride, phthalic anhydride, dicarboxylic anhydrides such as tetrahydrophthalic anhydride, tricarboxylic monoanhydrides such as trimellitic anhydride, aniline, benzylamine and the like The monoamine is preferably used in an amount of 0.01 to 0.10 mol per 1 mol of either the acid component or the amine component.

The molecular weight of the polyimide resin used in the present invention is 5,000 to 80,000 in number average molecular weight.
It is preferred that If it is less than 5,000, the mechanical properties tend to decrease, and if it exceeds 80,000, the solution viscosity during the synthesis tends to be too high and the workability tends to decrease. The number average molecular weight is a polystyrene-equivalent value determined by gel permeation chromatography using polystyrene having a known molecular weight as a calibration curve. For example, it can be measured under the following conditions. The following examples were measured under the following conditions. Apparatus: Hitachi 655A type Column: Gelpak GL-S300 manufactured by Hitachi Chemical Co., Ltd.
MDT-S (300 mm × 8 mmφ) 2 eluents: tetrahydrofuran / dimethylformamide =
1/1 (volume), H ₃ PO ₄ (0.06 mol / l) / Li
Br · H ₂ O (0.03 mol / l) Flow rate: 1 ml / min Detector: UV (270 nm)

The reaction between the aromatic tetracarboxylic dianhydride and the diamine compound is performed in an organic solvent. Examples of the organic solvent include N-methylpyrrolidone, dimethylacetamide, dimethylformamide, 1,3-dimethyl-3,
Nitrogen-containing compounds such as 4,5,6-tetrahydro-2 (1H) -pyrimidinone, 1,3-dimethyl-2-imidazolidinone, sulfur compounds such as sulfolane and dimethylsulfoxide, γ-butyrolactone, γ-valerolactone; γ
Lactones such as caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, ε-caprolactone, dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl (or diethyl, dipropyl,
Ethers such as dibutyl) ether, triethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether and tetraethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone; Alcohols such as butanol, octyl alcohol, ethylene glycol, glycerin, diethylene glycol monomethyl (or monoethyl) ether, triethylene glycol monomethyl (or monoethyl) ether, tetraethylene glycol monomethyl (or monoethyl) ether, and phenols such as phenol, cresol, and xylenol , Ethyl acetate, butyl acetate, ethyl cellosolve acetate,
Esters such as butyl cellosolve acetate, hydrocarbons such as toluene, xylene, diethylbenzene and cyclohexane, trichloroethane, tetrachloroethane,
Halogenated hydrocarbons such as monochlorobenzene are used. These are used alone or in combination. Lactones, ethers, and ketones are preferably used in consideration of solubility, low hygroscopicity, low-temperature curability, environmental safety, and the like.

The reaction is usually carried out at a temperature of 80 ° C. or lower, preferably 0 to 60 ° C. The reaction solution gradually thickens as the reaction proceeds. In this case, a polyamic acid which is a precursor of the polyimide resin is generated. The polyimide resin is obtained by dehydrating and ring-closing the above reactant (polyimide precursor). The dehydration ring closure can be performed by a method of heat treatment at 120 ° C. to 250 ° C. (thermal imidization) or a method of using a dehydrating agent (chemical imidization). In the case of a method of performing heat treatment at 120 ° C. to 250 ° C., the heat treatment is preferably performed while removing water generated in the dehydration reaction outside the system. At this time, water may be azeotropically removed using benzene, toluene, xylene, or the like. As a method of performing dehydration ring closure using a dehydrating agent, it is preferable to use a carbodiimide compound such as dicyclohexylcarbodiimide or the like. At this time, if necessary, a dehydration catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine, imidazole and the like may be used. The dehydrating agent or the dehydrating catalyst is used in an amount of 1 to 1 mole per mole of the aromatic tetracarboxylic dianhydride.
It is preferable to use it in the range of 8 mol. In order to reduce the number of manufacturing steps and increase economic efficiency, a method of performing heat treatment at 120 ° C. to 250 ° C. (thermal imidization) is preferable.

The polyamideimide resin or its precursor according to the present invention may be obtained by using trimellitic anhydride or trimellitic anhydride instead of part or all of the aromatic tetracarboxylic dianhydride in the production of the polyimide resin or its precursor. It can be produced by using a trivalent tricarboxylic anhydride such as a trimellitic anhydride derivative such as chloride of melitic anhydride or a derivative thereof. Further, it can be produced by using an aromatic diisocyanate instead of the aromatic diamine. The aromatic diisocyanate that can be used is a compound to be obtained by reacting the aromatic diamine with phosgene or thionyl chloride.

As the polyamideimide resin in the present invention, a polyamideimide resin obtained by reacting an aromatic tetracarboxylic dianhydride with a diamine compound containing isophthalic acid dihydrazide as an essential component is preferably used. As the diamine compound other than the aromatic tetracarboxylic dianhydride and isophthalic dihydrazide, those described above are used. The molar ratio of isophthalic dihydrazide in the diamine compound is preferably 1 to 100 mol%. When the content is less than 1 mol%, the solubility of the resin paste of the present invention in an encapsulant tends to decrease when the resin paste of the present invention is used as an adhesive for a semiconductor device. Is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, since the moisture resistance of the adhesive layer formed from
Is particularly preferred. This polyamide-imide resin is a compounding ratio of an aromatic tetracarboxylic dianhydride and a diamine compound,
The organic solvent used, the synthesis method, and the like can be obtained in the same manner as in the synthesis of the polyimide resin.

The polyamide resin according to the present invention is obtained by reacting an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or phthalic acid, or a derivative thereof such as dichloride or anhydride with an aromatic diamine or aromatic diisocyanate having the above-mentioned composition. Can be manufactured.

The heat-resistant resin B, which does not dissolve in the solvent (II) and (IV) at room temperature but dissolves at the temperature when heated and dried in the present invention, is used for imparting thixotropic properties to the paste. While the heat-resistant resin A of (I) is soluble in a solvent at room temperature, the heat-resistant resin B of (II) is insoluble in the solvent (IV) at room temperature.
Both have the property of dissolving in the respective solvents at the temperature at the time of heating and drying.

From the viewpoint of uniformity and mechanical properties of a film obtained by heating and drying the heat-resistant resin paste of the present invention,
It is preferable that (I) heat-resistant resin A and (II) heat-resistant resin B have compatibility after heat-drying, and in particular, after heat-drying, (I) heat-resistant resin A and (II) heat-resistant resin It is preferable that the conductive resin B forms a uniform phase. This homogeneous phase may contain an organic solvent remaining after drying by heating.

(II) As the heat-resistant resin B, an amide group,
It is preferable to use a heat-resistant resin having an imide group, an ester group or an ether group. As the heat-resistant resin, a polyimide resin or a precursor thereof, a polyamideimide resin or a precursor thereof, or a polyamide resin is preferably used from the viewpoint of heat resistance and mechanical properties. As the polyimide resin or its precursor, or polyamide-imide resin or its precursor, or polyamide resin, selected from the polyimide resin or its precursor, polyamide-imide resin or its precursor, or the polyamide resin exemplified above. Used. In addition, each precursor may be a partially imidized resin of polyamic acid.
That is, (II) the heat-resistant resin B is selected and used in a state of fine particles insoluble in the solvent (IV) of the heat-resistant resin paste of the present invention before heating and drying.

Specific examples of such (II) heat-resistant resin B (including a combination with a solvent) are specifically exemplified as (II) heat-resistant resin B in JP-A-11-246777. And the same resins as those listed in Table 1,
3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride / 4,4'-diaminodiphenyl ether (1
/ 1; molar ratio) of polyamic acid (solvent is γ-butyrolactone), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride / 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride Polyamide acid (solvent is γ-butyrolactone) of anhydride / 4,4′-diaminodiphenyl ether (0.5 / 0.5 / 1; molar ratio) and the like. These are examples showing embodiments of the present invention, and the present invention is not particularly limited thereto.

Considering (IV) the stability of the solvent, (IV) the solubility of (II) the heat-resistant resin B in the solvent, and the productivity,
(II) The heat-resistant resin B comprises an aromatic tetracarboxylic dianhydride containing at least 50 mol% of 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether. An aromatic polyimide resin obtained by reacting with an aromatic diamine containing 50 mol% or more, and a combination in which the solvent (IV) is γ-butyrolactone is preferable. The heating and drying temperature of the heat-resistant resin paste of the above combination is usually 50 to 350 ° C., and within this range, it is preferable to gradually increase the temperature from a low temperature to a high temperature.

Further, (II) a heat-resistant resin B and (I) a heat-resistant resin A having compatibility with each other are preferably used. Specifically, preferably, the difference in solubility parameter between (II) heat-resistant resin B and (I) heat-resistant resin A is 2.0
The following combination is more preferably 1.5 or less. Here, the solubility parameter is Polym.Eng.
14, a value [unit: (MJ / m ³ ) ^1/2 ] calculated according to the Fedors method described on pages 147 to 154 of Sci., Vol.

The particles or liquid having rubber elasticity (III) in the present invention are not particularly limited as particles or liquid having rubber elasticity. Examples include body particles or liquids. Among them, particles having a rubber elasticity containing a silicone rubber as a main component are preferable. It is preferable that these rubber elastic bodies have an average particle diameter of 0.1 to 50 μm and are finely divided into spherical or amorphous particles. The average particle size can be measured by an electron microscope method, a particle analyzer method, or the like. If the average particle size is less than 0.1 μm, aggregation between the particles occurs, sufficient dispersion cannot be performed, and the temporal stability of the paste tends to decrease. A good coating cannot be obtained.

The surface of the particles having rubber elasticity used in the present invention is preferably a rubber elastic body itself, a resin coating, or chemically modified with a functional group such as an epoxy group. In place of the epoxy group of the above functional group, those chemically modified with a functional group such as an amino group, an acryl group or a phenyl group can also be used. By adding these rubber elastic particles to the heat-resistant resin,
The elastic modulus can be controlled without impairing the heat resistance and adhesion of the resin. Particles having rubber elasticity are available from Toray Dow Corning Silicone Co., Ltd. under the trade names such as Trefil E-601 and Trefil E-600, and from Shin-Etsu Chemical Co., Ltd., silicone rubber powder KMP59.
4. Silicone composite powder KMP6 such as KMP598
00, KMP605 and the like.

In the present invention, (I) a heat-resistant resin A which dissolves in a solvent at room temperature and at the time of heating and drying, (II)
The elastic modulus of the resin film obtained by combining heat-resistant resin B, (III) particles exhibiting rubber elasticity, or liquid material C, which does not dissolve in the solvent at room temperature but dissolves in the solvent at the temperature when heated and dried, is 0. The elastic modulus at 150 ° C. can be arbitrarily controlled within the range of 2 to 3.0 GPa, and the elastic modulus at 150 ° C. can be 10 to 100% of the elastic modulus at −65 ° C. Further, the resin film obtained from the heat-resistant resin paste of the present invention has a glass transition temperature of
% Weight loss temperature is 300 ° C. or more,
It has excellent resistance to processes such as sputtering, plating resist formation, electroplating or electroless plating, resist peeling, thin film metal etching, solvent treatment, and solder ball mounting used in manufacturing semiconductor devices.

As the solvent (IV) used in the present invention, for example, the solvents described in "Solvent Handbook" (Kodansha, published in 1976), pp. 143 to 852 can be used.
For example, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, 1,3-dimethyl-3,
Nitrogen-containing compounds such as 4,5,6-tetrahydro-2 (1H) -pyrimidinone, 1,3-dimethyl-2-imidazolidinone, sulfur compounds such as sulfolane and dimethylsulfoxide, γ-butyrolactone, γ-valerolactone; γ
Lactones such as caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, ε-caprolactone, dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl (or diethyl, dipropyl,
Ethers such as dibutyl) ether, triethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether and tetraethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether; carbonates such as ethylene carbonate and propylene carbonate; methyl ethyl ketone; methyl isobutyl Ketone,
Ketones such as cyclohexanone and acetophenone, butanol, octyl alcohol, alcohols such as ethylene glycol, glycerin, diethylene glycol monomethyl (or monoethyl) ether, triethylene glycol monomethyl (or monoethyl) ether, and tetraethylene glycol monomethyl (or monoethyl) ether; Phenols such as phenol, cresol and xylenol; esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate and butyl cellosolve acetate; hydrocarbons such as toluene, xylene, diethylbenzene and cyclohexane; halogens such as trichloroethane, tetrachloroethane and monochlorobenzene Hydrocarbons and the like are used. These are used alone or in combination.

(IV) The boiling point of the solvent is preferably 100 ° C. or higher, particularly preferably 150 to 300 ° C., in consideration of the pot life of the paste during screen printing. The solvent (IV) is a non-nitrogen-containing solvent such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-
Heptalactone, α-acetyl-γ-butyrolactone,
lactones such as ε-caprolactone, dioxane, 1,
Ethers such as 2-dimethoxyethane, diethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, triethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, tetraethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, ethylene It is preferable to use carbonates such as carbonate and propylene carbonate, and ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone.

The heat-resistant resin paste of the present invention is, for example,
(I) heat-resistant resin A, (II) heat-resistant resin B and (I)
By mixing the solvent of V) and cooling the solution obtained by heating and dissolving the same, the fine particles of the heat-resistant resin B of (II) are precipitated in the solution of the heat-resistant resin A of (I) and the solvent of (IV). Can be produced by dispersing. The heating melting temperature is
(I) heat-resistant resin A, (II) heat-resistant resin B and (I)
There is no particular limitation as long as the mixture of the solvent (V) becomes a substantially uniform transparent solution.
It is preferably performed at 50 ° C. The time required for dissolution is appropriate, but is preferably 0.1 to 5 hours, and more preferably 1 to 5 hours.

Next, the condition of cooling the solution after heating and dissolving is as follows: the heat-resistant resin B of (II) is formed into fine particles in a mixed solution of the heat-resistant resin A of (I) and the solvent of (IV) to precipitate and disperse. Although there is no particular limitation as long as it is a condition, it is usually preferable to carry out the reaction at a temperature of −20 ° C. to 100 ° C., which is lower than the temperature at which the material is heated and dissolved, and leave it for 1 hour to 60 days under stirring or standing. As cooling conditions for forming fine particles in a short time, 0
It is more preferable to carry out the reaction at a constant temperature of from 0 to 80 ° C for from 5 to 80 hours. -20 from the melting temperature
The speed of cooling to from 100 ° C. to 100 ° C. may be arbitrary, but rapid cooling tends to cause aggregation of precipitated fine particles.
It is preferable to cool at a rate of 0.1 to 10 ° C./min under stirring. The production atmosphere is preferably performed under an inert atmosphere such as a dried nitrogen gas.

The heat-resistant resin paste of the present invention is prepared by dissolving, for example, a raw material constituting the heat-resistant resin B of (II) in a solution of the heat-resistant resin A of (I) and the solvent of (IV). The reaction is then carried out in a solution of the heat-resistant resin A of (I) and the solvent of (IV) at a temperature at which the heat-resistant resin B of (II) does not precipitate,
By synthesizing the heat-resistant resin B of (II) and then cooling, fine particles of the heat-resistant resin B of (II) are precipitated and dispersed in a solution of the solvent of heat-resistant resin A of (I) and the solvent of (IV). It can also be manufactured by doing. As the raw material constituting the heat-resistant resin B of (II), those described above are used.

In the heat-resistant resin paste of the present invention, for example, the raw materials constituting the heat-resistant resin A of (I) were charged and dissolved in a solution of the heat-resistant resin B of (II) and the solvent of (IV). Thereafter, a reaction is carried out in a solution of the heat-resistant resin B of (II) and the solvent of (IV) at a temperature at which fine particles of the heat-resistant resin B of (II) do not precipitate, thereby synthesizing (I) the heat-resistant resin A, and then cooling. By doing so, it can also be produced by precipitating and dispersing fine particles of the heat-resistant resin B of (II) in a solution of the heat-resistant resin A of (I) and the solvent of (IV). As the raw material constituting the heat-resistant resin A of (I), those described above are used.

The mixing ratio of the heat-resistant resin A of the present invention (A), the heat-resistant resin B of (II), the particles or liquids having rubber elasticity of (III) and the solvent of (IV) is as follows: Heat-resistant resin A
10 parts by weight of heat-resistant resin B of (II)
To 300 parts by weight, 10 to 700 parts by weight of the particles or liquid having rubber elasticity (III), and 100 to 100 parts by weight of the solvent (IV).
It is preferably 3,000 parts by weight, 20 to 200 parts by weight of the heat resistant resin B of (II), 20 to 400 parts by weight of particles or liquid having rubber elasticity of (III), and 20 to 400 parts by weight of the solvent of (IV). Is more preferably 150 to 2,000 parts by weight, and the heat-resistant resin B of (II) is 20 to 200 parts by weight, (II)
It is particularly preferred that the particles or liquids exhibiting rubber elasticity of I) be 20 to 200 parts by weight, and the solvent of (IV) be 200 to 1,000 parts by weight.

When the amount of the heat-resistant resin B of (II) is less than 10 parts by weight, the thixotropy at the time of forming a pattern by screen printing or dispensing is insufficient, and the resolution tends to be impaired. If it exceeds 300 parts by weight,
Since the fluidity of the paste is impaired, printability and dispensability tend to decrease. When the amount of the particles or the liquid material exhibiting the rubber elasticity of (III) is less than 5 parts by weight, the elastic modulus of the heat-resistant resin film increases, and the stress relaxation ability tends to be impaired. On the other hand, when the amount of the rubbery particles or liquids of (III) exceeds 700 parts by weight, the mechanical strength of the coating film tends to decrease and the function as the coating film tends to decrease. (I
When the amount of the solvent (V) is less than 100 parts by weight, the fluidity of the paste is impaired, so that printability and dispensing property tend to be reduced. On the other hand, if the amount exceeds 3,000 parts by weight, the viscosity of the paste becomes low, so that it is difficult to form a thick film, and the resolution tends to be impaired.

The elastic modulus of the resin film obtained from the heat-resistant resin paste can be arbitrarily controlled within the range of 0.2 to 3.0 GPa, and the elastic modulus at 150 ° C. is 10% of the elastic modulus at −65 ° C. A heat-resistant resin paste having a size of １００100% is preferred. If it exceeds 3.0 GPa, stress relaxation becomes insufficient, cracks and the like tend to occur in the connection part such as solder, and the reliability tends to be impaired.
The wiring layer tends to be disconnected due to the distortion. If the elastic modulus at 150 ° C. is less than 10% of the elastic modulus at −65 ° C., in a thermal shock cycle test, distortion is likely to occur in a solder ball connection portion or the like, and reliability tends to decrease.

The resin film obtained from the heat-resistant resin paste is preferably a heat-resistant resin paste having a glass transition temperature of 180 ° C. or higher and a 5% weight loss temperature of 300 ° C. or higher. When the glass transition temperature is lower than 180 ° C. or 5
When the% weight loss temperature is lower than 300 ° C., the resin tends to be decomposed in a sputtering step or the like.

It is preferable that the heat-resistant resin paste of the present invention has a thixotropy coefficient of 1.2 or more in order to provide good screen printability. If the thixotropy coefficient is less than 1.2, it tends to be difficult to obtain sufficient printability and resolution. The thixotropic coefficient is 2.
0 to 10.0 is more preferable. If it exceeds 10.0, the formed pattern tends to be blurred. Further, the viscosity is preferably from 10 Pa · s to 1,000 Pa · s. 1
If it is less than 0 Pa · s, it is difficult to obtain a sufficient film thickness and resolution,
If it exceeds 1,000 Pa · s, the workability during pattern formation tends to decrease. 50 Pa · s to 700 Pa · s is more preferable, and 100 Pa · s to 600 Pa · s is particularly preferable. here,
The thixotropy coefficient is measured using an E-type viscometer (manufactured by Tokimec Co., Ltd.
EHD-U type), sample amount 0.4 g, measurement temperature 25
The ratio between the apparent viscosities η1 and η10, measured at ° C., of the rotational speeds of 1 min ⁻¹ and 10 min ⁻¹ , is expressed as η1 / η10. The viscosity is represented by an apparent viscosity η 0.5 of a rotation speed of 0.5 min ⁻¹ . The viscosity can be controlled by, for example, the solid content concentration of the resin paste and the amount of (II) the heat-resistant resin B. The larger these are, the higher the viscosity is.

The heat-resistant resin paste of the present invention may optionally contain (II) a solution of the heat-resistant resin A (I) and the solvent (IV) in a solvent.
After forming a paste in which fine particles of heat-resistant resin B are dispersed,
A crosslinking agent having a functional group capable of chemically bonding to a hydroxyl group or a carboxyl group can be added in an amount of 1 to 30 parts by weight based on 100 parts by weight of the total amount of the heat-resistant resin paste. As a crosslinking agent having a functional group capable of chemically bonding to a hydroxyl group or a carboxyl group, a compound having two or more functional groups in a compound molecule, at least one of which has a hydroxyl group in the molecular main chain. Alternatively, it is preferable to use a resin that reacts with a heat-resistant resin having a carboxyl group and reacts with the heat-resistant resin having a hydroxyl group or a carboxyl group in the molecular main chain or reacts with each other. As long as it has such two or more functional groups,
There are no particular restrictions on the molecular structure, molecular weight, etc.

Examples of such a functional group reactive with a hydroxyl group include an epoxy group, an isocyanate group and a methylol group. Examples of the functional group reactive with a carboxyl group include an epoxy group, an amino group, a vinyl group, and an oxazoline group. Examples of the group that reacts with the functional groups include a methoxysilane group and an ethoxysilane group. Coupling agents that can give a loose bridge structure to the cured product of the heat-resistant resin paste and are excellent in storage stability of the heat-resistant resin paste are preferably used as the crosslinking agent. As a coupling agent,
For example, a silane coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent and the like can be mentioned. A silane coupling agent is more preferably used.

As the silane coupling agent, for example, γ
-(2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyl Trimethoxysilane,
Vinyltriacetoxysilane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, γ-methacryloxypropyl Methylenedimethoxysilane and the like can be mentioned.

It is preferable to use a silane coupling agent having an epoxy group and a methoxysilane group in the molecule for a heat-resistant resin having a hydroxyl group in the molecular main chain.
More preferably, glycidoxypropyltrimethoxysilane is used. Since the heat-cured resin paste obtained from such a combination has a loosely bridged structure of the heat-cured product, when used in a resin-encapsulated semiconductor device, it is dissolved in the encapsulant constituent resin at the molding temperature of the encapsulant. Excellent solder reflow resistance. Furthermore, it has high adhesiveness (particularly thermocompression bonding) to a semiconductor chip or a lead frame.

The heat-resistant resin paste obtained according to the present invention may optionally contain a defoaming agent, a pigment, a dye, an inorganic filler, a plasticizer, an antioxidant and the like.

The method for obtaining a resin film pattern using the heat-resistant resin paste of the present invention is not particularly limited. Printing method and lithographic printing method are exemplified.

A semiconductor device using a resin film obtained from the heat-resistant resin paste of the present invention is obtained by applying or attaching the heat-resistant resin paste of the present invention to a substrate or a lead frame, and then bonding the chip. For example, the heat-resistant resin paste of the present invention can be applied to the surface of a semiconductor component and dried to form a protective film, thereby producing the semiconductor component. After applying or attaching this heat-resistant resin paste to the chip surface, it may be adhered to a substrate or a lead frame. The coating and drying can be performed by a known method. The glass transition temperature of the formed resin film is 180 ° C. or more, and the 5% weight loss temperature is 30.
0 ° C. or higher, and has sufficient heat resistance. Further, since the elastic modulus of the resin film can be arbitrarily controlled in the range of 0.2 to 3.0 GPa, it can be applied to any semiconductor device.

In a semiconductor device using a resin film obtained from the heat-resistant resin paste of the present invention, a plurality of resin layers are applied by applying the heat-resistant resin paste of the present invention to a semiconductor substrate on which wiring is formed. Drying, forming a rewiring electrically connected to the electrode on the semiconductor substrate on the resin layer, forming a protective layer on the rewiring, forming external electrode terminals on the protective layer It can be manufactured by performing steps. The semiconductor substrate is not particularly limited, and examples thereof include a silicon wafer. The method of applying the resin layer is not particularly limited, but screen printing or dispensing is preferred. The resin layer can be dried by a known method. The formed resin layer has a glass transition temperature of 180 ° C. or higher and a 5% weight loss temperature of 300 ° C. or higher, and has sufficient heat resistance. Also,
It also has spatter resistance, plating resistance, acid resistance, alkali resistance and the like required in the process of forming the rewiring. Since the elastic modulus of the resin layer can be arbitrarily controlled within the range of 0.2 to 3.0 GPa, it can be applied to any semiconductor device. Thereby, the amount of warpage of the silicon wafer can also be reduced. The yield of semiconductor devices manufactured by this method can be expected to be improved, and productivity can be improved.

[0062]

The present invention will be described below with reference to examples, but the present invention is not limited by these examples.

Synthesis Example 1 (Heat-Resistant Resin A-1) 4,3 ', 4'-benzophenonetetracarboxylic dianhydride (hereinafter abbreviated as BTDA) 9
6.7 g (0.3 mol), 36.0 g of 4,4'-diaminodiphenyl ether (hereinafter, abbreviated as DDE) (0.1 mol
8 mol), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter abbreviated as BAPP) 4
3.1 g (0.105 mol), 3.73 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane
(0.015 mol) and γ-butyrolactone 381.5
g. After the reaction was allowed to proceed at 60 to 65 ° C. for 2 hours under stirring, the reaction was stopped by cooling when the number average molecular weight reached about 50,000 (in terms of polystyrene). The obtained solution was diluted with γ-butyrolactone to give a resin concentration of 30.
By weight, a polyimide precursor (heat-resistant resin A-1) solution was obtained.

Synthesis Example 2 (Heat-Resistant Resin B-1) While passing nitrogen gas through a 1,000 ml four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and cooling tube with oil / water separator, BTDA 109 was used. 6.6 g (0.4 mol), DDE 76.1 g (0.38 mol), 1,3-
4.97 g (0.02 mol) of bis (3-aminopropyl) tetramethyldisiloxane and γ-butyrolactone 4
05.2 g was charged. After the reaction was allowed to proceed at 60 to 65 ° C. for 2 hours under stirring, the reaction was stopped by cooling when the number average molecular weight reached 35,000 (in terms of polystyrene).
The obtained solution is diluted with γ-butyrolactone to prepare a polyimide precursor having a resin concentration of 30% by weight (heat-resistant resin B-1).
A solution was obtained.

Preparation Example 1 (Heat-resistant resin base paste: heat-resistant resin A-1 / heat-resistant resin B-1) 1,000 ml four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and cooling tube 150 g of the heat-resistant resin B-1 polyimide precursor (resin concentration: 30% by weight) immediately after synthesis and the heat-resistant resin A while passing nitrogen gas through
-1 polyimide precursor solution (resin concentration 30% by weight) 3
50 g was added and mixed, and stirring was continued at 60 to 65 ° C. for 1 hour to obtain a uniform transparent solution. When stirring was further continued at 60 to 65 ° C. for 24 hours, heat-resistant resin B-1 polyimide precursor fine particles were precipitated and dispersed in the solution. This was diluted with γ-butyrolactone to obtain a polyimide heat-resistant resin paste (1) having a viscosity of 480 Pa · s and a thixotropy coefficient (hereinafter referred to as TI value) of 3.0. The heat-resistant resin B-1 polyimide precursor fine particles in the polyimide-based heat-resistant resin paste (1) are insoluble in γ-butyrolactone at room temperature,
It was soluble at 0 ° C.

The above polyimide heat-resistant resin paste (1)
On a glass plate (about 2 mm thick) with a thickness of 5 after heating and drying.
A bar coater was applied so as to have a thickness of 0 μm, and at 80 ° C. for 5 minutes, at 100 ° C. for 10 minutes, at 150 ° C. for 10 minutes, and 200 ° C.
A heat treatment was performed at 15 ° C. for 15 minutes and further at 300 ° C. for 60 minutes to obtain a glass plate with the polyimide resin composition (1). The cured film is substantially uniform and transparent, and the heat-resistant resin B-1 in the polyimide-based heat-resistant resin paste dissolves in the γ-butyrolactone in the heating process, and the heat-resistant resin A
By dehydration and ring closure with the -1 polyimide precursor, they were compatible in the state of a polyimide resin.

Synthesis Example 3 (Heat-Resistant Resin A-2) While passing nitrogen gas through a 1,000 ml four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and cooling tube with oil / water separator, BTDA 77 was used. 0.3 g (0.24 mol), 31.4 g (0.06 mol) of 1,10- (decamethylene) bis (trimellitate dianhydride), DDE 3
6.0 g (0.18 mol), BAPP 43.1 g
(0.105 mol), 3.73 g (0.015 g) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane
Mol) and 381.5 g of γ-butyrolactone. After the reaction was allowed to proceed at 60 to 65 ° C. for 2 hours under stirring, the reaction was stopped by cooling when the number average molecular weight reached about 60,000 (in terms of polystyrene). The resulting solution is converted to γ
-Diluted with butyrolactone to obtain a polyimide precursor (heat-resistant resin A-2) solution having a resin concentration of 30% by weight.

Preparation Example 2 (Heat-resistant resin base paste: heat-resistant resin A-2 / heat-resistant resin B-1) 1,000 ml four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and cooling tube 100 g of the above heat-resistant resin B-1 polyimide precursor (resin concentration: 30% by weight) and the heat-resistant resin A immediately after synthesis while passing nitrogen gas through
-2 polyimide precursor solution (resin concentration 30% by weight) 4
After adding and mixing 00 g, stirring was continued at 60 to 65 ° C. for 1 hour to obtain a uniform transparent solution. When stirring was further continued at 60 to 65 ° C. for 34 hours, heat-resistant resin B polyimide precursor fine particles were precipitated and dispersed in the solution. This was diluted with γ-butyrolactone to obtain a polyimide heat-resistant resin paste (2) having a viscosity of 450 Pa · s and a thixotropic coefficient (hereinafter referred to as a TI value) of 5.5. The heat-resistant resin B-1 polyimide precursor fine particles in the polyimide-based heat-resistant resin paste (2) are insoluble in γ-butyrolactone at room temperature, and
Then it was soluble.

The above-mentioned polyimide heat-resistant resin paste (2)
Is dried on a glass plate (about 2 mm thick) with a thickness of 50
Apply a bar coater so that the thickness becomes μm, and at 80 ° C for 5 minutes,
Heat treatment was performed at 100 ° C. for 10 minutes, at 150 ° C. for 10 minutes, at 200 ° C. for 15 minutes, and further at 250 ° C. for 60 minutes to obtain a glass plate with the polyimide resin composition (2). The cured film is substantially uniform and transparent, and the heat-resistant resin B-1 in the polyimide-based heat-resistant resin paste dissolves in the γ-butyrolactone in the heating process, and further heat-resistant resin A-2.
It was compatible with the polyimide resin by dehydration and ring closure with the polyimide precursor.

Synthesis Example 4 (Heat-Resistant Resin A-3) While passing nitrogen gas through a 1,000 ml four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and cooling tube with oil / water separator, BTDA 32 was used. 0.2 g (0.1 mol),
52.2 g (0.1 mol) of 1,10- (decamethylene) bis (trimellitate dianhydride), 36.0 g of DDE
(0.18 mol), 43.1 g of BAPP (0.105
Mol), 3.73 g (0.015 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane and γ
381.5 g of butyrolactone were charged. 6 with stirring
After the reaction was allowed to proceed at 0 to 65 ° C. for 2 hours, the reaction was stopped by cooling when the number average molecular weight reached about 45,000 (in terms of polystyrene). The obtained solution was diluted with γ-butyrolactone to obtain a polyimide precursor (heat-resistant resin A-3) solution having a resin concentration of 30% by weight.

Preparation Example 3 (Heat-resistant resin base paste: heat-resistant resin A-3 / heat-resistant resin B-1) 1,000 ml four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and cooling tube 250 g of the heat-resistant resin B-1 polyimide precursor immediately after synthesis (resin concentration: 30% by weight) and the heat-resistant resin A while passing nitrogen gas through
-3 polyimide precursor solution (resin concentration 30% by weight) 2
50 g was added and mixed, and stirring was continued at 60 to 65 ° C. for 1 hour to obtain a uniform transparent solution. When stirring was further continued at 60 to 65 ° C. for 14 hours, heat-resistant resin B polyimide precursor fine particles were precipitated and dispersed in the solution. This was diluted with γ-butyrolactone to obtain a polyimide heat-resistant resin paste (3) having a viscosity of 400 Pa · s and a thixotropy coefficient (hereinafter referred to as a TI value) of 4.5. The heat-resistant resin B-1 polyimide precursor fine particles in the polyimide-based heat-resistant resin paste (3) are insoluble in γ-butyrolactone at room temperature, and
Then it was soluble.

The above-mentioned polyimide heat resistant resin paste (3)
On a glass plate (about 2 mm thick) with a thickness of 5 after heating and drying.
A bar coater was applied so as to have a thickness of 0 μm, and at 80 ° C. for 5 minutes, at 100 ° C. for 10 minutes, at 150 ° C. for 10 minutes, and 200 ° C.
A heat treatment was performed at 15 ° C. for 15 minutes and further at 250 ° C. for 60 minutes to obtain a glass plate with the polyimide resin composition (3). The cured film is substantially uniform and transparent, and the heat-resistant resin B-1 in the polyimide-based heat-resistant resin paste dissolves in the γ-butyrolactone in the heating process, and the heat-resistant resin A
By dehydration and ring closure with the -3 polyimide precursor, they were compatible with each other in the state of a polyimide resin.

Synthesis Example 5 (Heat-Resistant Resin A-4) BAPP 65 was passed while passing nitrogen gas through a 1,000 ml four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and cooling tube with oil / water separator. 0.69 g (0.16 mol), 143.22 g of bis (3,4-dicarboxyphenyl) sulfone dianhydride (hereinafter abbreviated as DSDA)
(0.40 mol), isophthalic dihydrazide 38.8
4 g (0.20 mol), 9.93 g (0.04 g) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane
Mol) and 478 g of γ-butyrolactone. After agitation at 50-60 ° C for 1 hour under stirring, 195 ° C
The reaction proceeds at the same temperature and the number average molecular weight is 27,
When the reaction reached 000 (polystyrene equivalent), the reaction was stopped by cooling. On the way, distilled water was immediately removed from the reaction system. The obtained solution was diluted with γ-butyrolactone to obtain a polyamideimide resin (heat-resistant resin A-4) solution having a resin content of 30% by weight.

Synthesis Example 6 (Heat-Resistant Resin B-2) BAPP102. 64 g (0.25 mol), bis (3,4-dicarboxyphenyl) ether dianhydride (hereinafter abbreviated as ODPA) 77.55 g (0.5 g).
25 mol) and 335 g of γ-butyrolactone. After agitation at 50-60 ° C for 1 hour under stirring,
The temperature was raised to 95 ° C., and the reaction was allowed to proceed at the same temperature. When the number average molecular weight reached 28,000 (polystyrene equivalent), the reaction was stopped by cooling. On the way, distilled water was immediately removed from the reaction system. This was diluted with γ-butyrolactone to obtain a polyimide resin (heat-resistant resin B-2) solution having a resin concentration of 30% by weight.

Preparation Example 4 (Heat-resistant resin base paste: heat-resistant resin A-4 / heat-resistant resin B-2) 1,000 ml four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and cooling tube 200 g of the heat-resistant resin B-2 polyimide resin solution (resin concentration 30% by weight) immediately after the synthesis and 466.67 g of the heat-resistant resin A-4 polyamideimide resin solution (resin concentration 30% by weight) were added and mixed. Then, stirring was continued at 180 ° C. for 1 hour to obtain a uniform transparent solution. What was cooled to 23 ° C. in about 1 hour was allowed to stand at 23 ° C. for 1 month, and polyimide resin fine particles were precipitated and dispersed in the solution. This was diluted with γ-butyrolactone to obtain a polyimide resin paste (4) having a viscosity of 380 Pa · s and a thixotropy coefficient (hereinafter referred to as TI value) of 2.5. The collected polyimide resin fine particles had a maximum particle size of 5 μm or less, were insoluble in γ-butyrolactone at room temperature, and were soluble at 150 ° C.

The above-mentioned polyimide heat-resistant resin paste (4)
Is dried on a glass plate (about 2 mm thick) with a thickness of 50
A bar coater was applied so as to have a thickness of μm, and a heat treatment was performed at 140 ° C. for 15 minutes, at 200 ° C. for 15 minutes, and further at 300 ° C. for 60 minutes to obtain a glass plate with the polyimide resin composition (4). The cured film is substantially uniform and transparent, and the polyimide resin (heat-resistant resin B) in the polyimide-based heat-resistant resin paste (4) is used.
This indicates that the fine particles of -2) were dissolved in γ-butyrolactone during the curing process and were further compatible with the polyamideimide resin (heat-resistant resin A-4).

Synthesis Example 7 (Heat-Resistant Resin A-5) While passing nitrogen gas through a 1,000 ml four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and cooling tube with oil / water separator, BAPP89. 09 g (0.217 mol), 119.59 g (0.334 mol) of DSDA,
2,2-bis (4-hydroxy-3-aminophenyl)
Hexafluoropropane (hereinafter abbreviated as HAB-6F)
42.85 g (0.117 mol) and 377 g of γ-butyrolactone were charged. After agitation at 50 to 60 ° C. for 1 hour under stirring, the temperature was raised to 195 ° C., and the reaction was advanced at the same temperature. When the number average molecular weight reached 26,000 (polystyrene equivalent value), it was cooled. The reaction was stopped. On the way, distilled water was immediately removed from the reaction system. The resulting solution was diluted with γ-butyrolactone to give a resin concentration of 40% by weight.
Was obtained as a polyimide resin (heat-resistant resin A-5) solution.

Preparation Example 5 (Heat-resistant resin base paste: heat-resistant resin A-5 / heat-resistant resin B-2) 1,000 ml four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and cooling tube Heat-resistant resin B-2 polyimide resin containing a solvent (resin concentration 30% by weight)
400 g was crushed and heated to 180 ° C. 1 at the same temperature
After stirring for a time to obtain a uniform solution, the heat-resistant resin A-5 polyimide resin solution (resin concentration 40% by weight) is added thereto.
300 g was added and stirring was further continued at 180 ° C. for 1 hour.
Then, it is cooled to 60 ° C. in about 1 hour,
After stirring for a day, a paste in which polyimide resin fine particles were precipitated and dispersed in the solution was obtained. 48 g of γ-glycidoxypropyltrimethoxysilane was added to this paste, mixed well at room temperature, and diluted with γ-butyrolactone to a resin concentration of 36% by weight. The viscosity of the obtained polyimide-based heat-resistant resin paste (5) was 150 Pa · s, and the TI value was 3.5.

The above polyimide heat resistant resin paste (5)
On a glass plate (about 2 mm thick) with a thickness of 5 after heating and drying.
Apply a bar coater so that the thickness becomes 0 μm, and
Heat treatment at 200 ° C. for 15 minutes and then at 300 ° C. for 60 minutes to obtain a glass plate with the polyimide resin composition (5). The cured film is substantially uniform and transparent, and the fine particles of the polyimide resin (heat-resistant resin B-2) in the polyimide-based heat-resistant resin paste (5) dissolve in γ-butyrolactone during the curing process. -5).

Example 1 A silicone rubber elastic body having an epoxy group introduced on the surface having an average particle diameter of 2 μm in 200 parts by weight of the polyimide heat-resistant resin paste (1) (resin concentration 30% by weight) obtained in Preparation Example 1 Of fine particles ("Trefl E-601" manufactured by Dow Corning Toray Silicone Co., Ltd.) and 70 parts by weight of γ-butyrolactone were added and kneaded with three rolls to prepare a heat-resistant resin paste (6). After defoaming the obtained heat-resistant resin paste (6), a bar coater was applied on a 5-inch silicon wafer so as to have a thickness of 50 μm after heating and drying.
Heat treatment at 150 ° C. for 10 minutes, 200 ° C. for 15 minutes, and 300 ° C. for 60 minutes to obtain a silicon wafer with the polyimide resin composition (6). Using the obtained polyimide resin composition (6), the elastic modulus, the mechanical strength of the film, and the glass transition temperature were measured. Here, the elastic modulus was measured in air using a viscoelastic analyzer RSAII manufactured by Rheometric Scientific F.E.
The measurement was performed at a heating rate of 5 ° C./min and a frequency of 1 Hz. The mechanical strength of the film was measured using a Tensilon universal tester UCT-5T manufactured by Orientec Co., Ltd. The glass transition temperature was measured using a thermomechanical analyzer TMA / SS6100 manufactured by Seiko Instruments Inc.

Further, the obtained heat-resistant resin paste (6)
Screen printing machine (LS-34 with alignment device, manufactured by Neuron Seimitsu Co., Ltd.) so that the thickness after heating and drying on an 8-inch silicon wafer is 50 μm.
GX), a meshless metal plate made of nickel alloy additive plating (manufactured by Mesh Kogyo Co., Ltd., thickness 100 μm, pattern size 8 mm × 8 mm) and a Permalex metal squeegee (imported by Tomoe Kogyo Co., Ltd.) Was prepared and printability was evaluated. After printing, the pattern was observed with an optical microscope for pattern flow and blurring.

A step of applying a plurality of resin layers by screen printing to the semiconductor substrate on which the wirings are formed with the obtained heat-resistant resin paste (6), and drying. A step of forming electrically conductive rewiring, a step of forming a protective layer on the rewiring, a step of forming external electrode terminals on the protective layer, and forming a protective layer except for a portion where a solder ball is mounted A semiconductor device was fabricated by performing a process and a process of mounting a solder ball, and dicing. The semiconductor device is heated at -65 ° C for 15 minutes at 150 ° C.
A / 15 minute temperature cycle test was performed for 1,000 cycles, and a semiconductor device in which no abnormality occurred was evaluated as good. Table 1 shows the evaluation results of the heat-resistant resin paste (6), the resin film obtained therefrom, and the semiconductor device.

Example 2 Silicone rubber elastic material having an epoxy group introduced on the surface having an average particle size of 2 μm in 233 parts by weight of the polyimide heat-resistant resin paste (2) (resin concentration 30% by weight) obtained in Preparation Example 2 30 parts by weight of fine particles ("Trefle E-601" manufactured by Dow Corning Toray Silicone Co., Ltd.) and 50 parts by weight of γ-butyrolactone were added and kneaded with three rolls to prepare a heat-resistant resin paste (7). Evaluation was performed in the same manner as in Example 1 except that the final heating temperature was 250 ° C. Table 1 shows the evaluation results of the heat-resistant resin paste (7), the resin film obtained therefrom, and the semiconductor device.

Example 3 Silicone rubber elastic material having an epoxy group introduced on the surface having an average particle size of 2 μm in 266 parts by weight of the polyimide heat-resistant resin paste (3) (resin concentration 30% by weight) obtained in Preparation Example 3 Except that 20 parts by weight of fine particles ("Toray Fill E-601" manufactured by Dow Corning Toray Silicone Co., Ltd.) and 26 parts by weight of γ-butyrolactone were added and kneaded with three rolls to prepare a heat-resistant resin paste (8). Was evaluated in the same manner as in Example 2. Table 1 shows the evaluation results of the heat-resistant resin paste (8), the resin film obtained therefrom, and the semiconductor device.

Example 4 Silicone rubber elastic material having an epoxy group-introduced surface with an average particle diameter of 2 μm in 200 parts by weight of the polyimide heat-resistant resin paste (4) (resin concentration: 30% by weight) obtained in Preparation Example 4. Except that 40 parts by weight of the fine particles ("Trefle E-601" manufactured by Dow Corning Toray Silicone Co., Ltd.) and 70 parts by weight of γ-butyrolactone were added and kneaded with three rolls to prepare a heat-resistant resin paste (9). Was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results of the heat-resistant resin paste (9), the resin film obtained therefrom, and the semiconductor device.

Example 5 Silicone rubber elastic material having an epoxy group introduced on the surface having an average particle diameter of 2 μm in 176 parts by weight of the polyimide heat-resistant resin paste (5) (resin concentration 36% by weight) obtained in Preparation Example 5 Except that 40 parts by weight of fine particles ("Trefle E-601" manufactured by Dow Corning Toray Silicone Co., Ltd.) and 95 parts by weight of γ-butyrolactone were added and kneaded with three rolls to prepare a heat-resistant resin paste (10). Is
Evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results of the heat-resistant resin paste (10), the resin film obtained therefrom, and the semiconductor device.

Example 6 Silicone rubber elastic material having 316 parts by weight of the polyimide heat-resistant resin paste (2) (resin concentration 30% by weight) obtained in Preparation Example 2 and having an epoxy group introduced on the surface having an average particle diameter of 2 μm. 5 parts by weight of fine particles ("Toray Fill E-601" manufactured by Dow Corning Toray Silicone Co., Ltd.), and kneaded with a three-roll mill, heat-resistant resin paste (11)
Was evaluated in the same manner as in Example 2 except that was prepared. Table 1 shows the evaluation results of the heat-resistant resin paste (11), the resin film obtained therefrom, and the semiconductor device.

Comparative Example 1 Evaluation was made in the same manner as in Example 1 except that the polyimide heat-resistant resin paste (1) obtained in Preparation Example 1 was used instead of the heat-resistant resin paste (6) of Example 1. Was done. As a result, a failure occurred in a temperature cycle test of the semiconductor device. Table 2 shows the evaluation results of the polyimide heat-resistant resin paste (1), the resin film obtained therefrom, and the semiconductor device.

Comparative Example 2 Evaluation was made in the same manner as in Example 2 except that the polyimide heat-resistant resin paste (2) obtained in Preparation Example 2 was used instead of the heat-resistant resin paste (7) of Example 2. Was done. As a result, a failure occurred in a temperature cycle test of the semiconductor device. Table 2 shows the evaluation results of the polyimide heat-resistant resin paste (2), the resin film obtained therefrom, and the semiconductor device.

Comparative Example 3 Evaluation was performed in the same manner as in Example 1 except that the polyimide-based heat-resistant resin paste (5) obtained in Preparation Example 5 was used instead of the heat-resistant resin paste (6) of Example 1. Was done. As a result, a failure occurred in a temperature cycle test of the semiconductor device. Table 2 shows the evaluation results of the polyimide heat-resistant resin paste (5), the resin film obtained therefrom, and the semiconductor device.

Comparative Example 4 Evaluation was performed in the same manner as in Example 2 except that the heat-resistant resin A-2 solution obtained in Synthesis Example 3 was used instead of the heat-resistant resin paste (6) of Example 1. Was. As a result, a pattern flow occurred during screen printing, and a semiconductor device could not be manufactured. Further, the heat-resistant resin A-2 solution,
Table 2 shows the evaluation results of the resin films obtained therefrom.

Comparative Example 5 In place of the heat-resistant resin paste (8) of Example 3, Aerosil was added to the heat-resistant resin A-3 solution obtained in Synthesis Example 3 to give a viscosity of 350 Pa · s and a TI value of 5 The evaluation was performed in the same manner as in Example 3 except that a resin paste having a pH of 0.0 was used. As a result, the elastic modulus at −65 ° C. was 2.8 GPa, 150
It became 0.2 GPa at ° C, and the variation of the elastic modulus became 7%. Furthermore, the glass transition temperature was lowered to 160 ° C., and cracks occurred on the surface of the resin film during the sputtering process when manufacturing a semiconductor device. As a result, a semiconductor device could not be manufactured. Table 2 shows the evaluation results of the resin paste and the resin film obtained therefrom.

[0093]

[Table 1]

[0094]

[Table 2]

[0095]

The heat-resistant resin paste according to claim 1 is
It can be widely used for coating materials for semiconductor devices, adhesives, stress relaxation materials, etc., and the elastic modulus can be arbitrarily controlled,
In addition, it can form a resin film having excellent heat resistance, has thixotropy, and can be applied to a coating mode excellent in coating efficiency such as screen printing and dispensing. The heat-resistant resin paste according to the second aspect provides a resin film having more excellent heat resistance in addition to the effects of the first aspect.

The heat-resistant resin paste according to the third aspect has, in addition to the effects of the first and second aspects, more excellent stability of the solvent and solubility of the heat-resistant resin for imparting thixotropy to the solvent. . The heat-resistant resin paste according to the fourth aspect is, in addition to the effects of the invention according to the first, second or third aspect, further excellent in dispersibility of particles exhibiting rubber elasticity and surface smoothness of a coating film obtained. . The heat-resistant resin paste according to the fifth aspect has the effect of the invention according to the first, second, third or fourth aspect and is more effective when widely used for a coating material for semiconductor devices, an adhesive, a stress relaxation material, and the like. This provides a highly reliable resin film.

The heat-resistant resin paste according to claim 6 has the effects of the invention according to claim 1, 2, 3, 4, or 5,
This provides a resin film having more excellent process compatibility. Claim 7 is a heat-resistant resin paste according to claim 1,
In addition to the effects of the invention described in 2, 3, 4, 5, or 6, the present invention is further excellent in printability and resolution. The semiconductor device according to claim 8, which has a thixotropic property, and is a coating material, an adhesive, and a stress relaxation material for a semiconductor device or the like obtained from a heat-resistant resin paste applicable to a coating mode having excellent coating efficiency such as screen printing or dispensing. It has a resin film that can be widely used for, for example, elastic modulus can be arbitrarily controlled, and has excellent heat resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 23/12 H01L 23/12 L 23/29 23/30 R 23/31 (72) Inventor 廣 hiro Hiroshi ▼ 4-13-1, Higashi-cho, Hitachi City, Ibaraki F-term in Hitachi Chemical Co., Ltd. Research Laboratory 4J002 CM04W CM04X CP033 EA056 EB006 ED006 EE026 EH006 EL016 EL066 EL106 EP006 EU026 EU116 EU136 EV206 EV306 FD206 GH00 GJ01 GQ01 GQ05 4J002 PA01 QB15 QB26 RA35 SA06 SB01 SB02 TA22 TB01 TB02 UA131 UA132 UB121 UB152 ZA12 ZA32 ZB01 ZB02 ZB03 ZB47 4M109 AA01 BA07 CA04 CA10 EA07 EA10 EC04 5F047 BA21

Claims (8)

[Claims] 1. (I) a heat-resistant resin A which is soluble in the solvent (IV) at room temperature and the temperature at the time of heating and drying; A heat-resistant resin paste comprising a heat-resistant resin B soluble in the above, (III) particles exhibiting rubber elasticity or a liquid C, and (IV) a solvent. 2. The heat-resistant resin A of (I) and the heat-resistant resin B of (II) are aromatic polyimide resins obtained by reacting aromatic tetracarboxylic dianhydride with aromatic diamine. 2. The heat-resistant resin paste according to claim 1, wherein the main component of the rubber-elastic particles (III) is silicone rubber. 3. The method according to claim 2, wherein the heat-resistant resin B of (II) is 3, 4,
An aromatic tetracarboxylic dianhydride containing 50 mol% or more of 3 ', 4'-benzophenonetetracarboxylic dianhydride is reacted with an aromatic diamine containing 50 mol% or more of 4,4'-diaminodiphenyl ether. And the main solvent of (IV) is γ
-The heat-resistant resin paste according to claim 1 or 2, which is butyrolactone. 4. An average particle diameter of particles exhibiting rubber elasticity is 0.1.
The heat-resistant resin paste according to claim 1, 2 or 3, which has a thickness of 1 to 50 µm. 5. The elastic modulus of a resin film obtained from a heat-resistant resin paste can be arbitrarily controlled in the range of 0.2 to 3.0 GPa, and the elastic modulus at 150 ° C. is -65 ° C. The heat-resistant resin paste according to claim 1, 2, 3, or 4, which has a size of 10 to 100%. 6. The resin film obtained from the heat-resistant resin paste has a glass transition temperature of 180 ° C. or higher and a 5% weight loss temperature of 300 ° C. or higher.
The heat-resistant resin paste described in the above. 7. The composition according to claim 1, which has a viscosity of 10 to 1,000 Pa · s and a thixotropy coefficient of 1.2 or more.
7. The heat-resistant resin paste according to 2, 3, 4, 5, or 6. 8. A semiconductor device having a resin film obtained from the heat-resistant resin paste according to claim 1, 2, 3, 4, 5, 6, or 7.