JPH0873832A - Resin paste and semiconductor device - Google Patents

Abstract

PURPOSE: To obtain a highly reliable resin paste excellent in adhesive force, developing no reflow cracking, useful as a die bonding material, comprising an electrically conductive filler and a polyimide resin containing a specified proportion of a specific recurring unit. CONSTITUTION: This resin paste comprises (A) 100 pts.wt. of a polyimide resin with a total of a recurring unit of formula I ((n) is an integer of 2-20; R is a divalent organic group) or formula II (R' is H or a monovalent organic group) accounting for >=70mol% of the total of the recurring units of the whole polyimide resin and (B) pref. 1-8000 pts.wt. of an electricaly conductive filler and, pref. (C) 0-200 pts.wt. of a thermosetting resin. The semiconductor device is obtained by bonding a semiconductor element to a substrate with this paste to effect sealing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin paste used as a material for bonding an IC or LSI to a lead frame, that is, a die bonding material, and a semiconductor device (semiconductor device) using the same.

[0002]

2. Description of the Related Art Conventionally, as a method of joining a semiconductor element and a lead frame (support member) in a semiconductor device,
(I) a method of using an inorganic material such as a gold-silicon eutectic as an adhesive, (ii) a silver powder or the like dispersed in an organic material such as an epoxy resin or a polyimide resin to form a paste (silver paste), Is known as an adhesive.

The method (i) is relatively costly, requires high heat treatment at about 350 ° C. to 400 ° C., and has a drawback that the adhesive is hard and chips are broken by thermal stress. Therefore, recently, the method using the silver paste described in (ii) above has become the mainstream. In the method using a silver paste, usually, a silver paste is applied to a die pad of a lead frame by using a dispenser or a stamping machine, and then a semiconductor element is die-bonded and heat-cured to be bonded. The heat curing is known as a batch method in which it is processed in an oven and an in-line method in which it is processed on a heated plate.

The outside of the semiconductor element is sealed with a sealing material, soldered to a substrate, and mounted to form a semiconductor device. The most common solder mounting method for high-density and high-efficiency mounting is the surface mounting method, in which the lead frame of a semiconductor device is directly soldered to the board. For this solder mounting, reflow soldering is used to heat the entire board with infrared rays. Is used.

[0005]

When heated by infrared rays or the like, the package of the semiconductor device is heated to a high temperature of 200 ° C. or higher, and moisture contained in the package, particularly in the adhesive layer or the encapsulant is vaporized to die pad. There is a problem in that a crack (reflow crack) is generated in the package by wrapping around between the sealing material and the sealing material. The present invention provides a resin paste that has excellent adhesive strength to various substrate surfaces and that does not cause reflow cracks during reflow soldering, and a highly reliable semiconductor device using the same.

[0006]

The resin paste of the present invention is the resin paste of the following (1) to (4). (1) Formula (I)

[Chemical 3] (However, n shows an integer of 2-20 and R shows a bivalent organic group.) Or Formula (II)

[Chemical 4] (However, n represents an integer of 2 to 20, R represents a divalent organic group, and R ′ represents hydrogen or a monovalent organic group.) A resin paste containing a polyimide-based resin containing 70 mol% or more of the total of repeating units of the resin, and (B) a conductive filler. (2) The resin paste according to (1) above, which contains (C) a thermosetting resin in addition to (A) a polyimide resin and (B) a conductive filler. (3) (A) Polyimide resin; 100 parts by weight,
(B) Conductive filler; 1 to 8000 parts by weight, The resin paste according to (1) above. (4) (A) Polyimide resin; 100 parts by weight,
The resin paste according to (2) above, which comprises (B) a conductive filler; 1 to 8000 parts by weight, and (C) a thermosetting resin; 0 to 200 parts by weight.

Furthermore, the present invention also relates to a semiconductor device in which a semiconductor element and a substrate are bonded with the resin paste according to any one of the above (1) to (4) and sealed.

In the present invention, the polyimide-based resin is a general term for polyimide, polyamic acid, polyamic acid ester, or polyamic acid partially imidized.

The polyimide resin whose repeating unit is represented by the formula (I) or the formula (II) has the formula (III)

[Chemical 5] (However, n represents an integer of 2 to 20.) In addition to the method of condensing the tetracarboxylic acid dianhydride represented by the formula (2) and the diamine, a method of condensing the corresponding tetracarboxylic acid and the diamine, A method of subjecting a tetracarboxylic acid dihalide and a diamine to a condensation reaction, a method of subjecting a tetracarboxylic acid diester compound and a diamine to a condensation reaction,
A method of subjecting a tetracarboxylic acid diester dihalide and a diamine to a condensation reaction, a method of reacting a tetracarboxylic acid dianhydride with a diisocyanate, a method of reacting a tetracarboxylic acid dianhydride with trimethylsilyldiamine, and the like. Can be manufactured.

When the tetracarboxylic dianhydride of the formula (III) is produced by a condensation reaction with a diamine, the tetracarboxylic dianhydride, when n is 2 to 5,
1,2- (Ethylene) bis (trimellitate dianhydride), 1,3- (trimethylene) bis (trimellitate dianhydride), 1,4- (tetramethylene) bis (trimellitate dianhydride), 1,5- (Pentamethylene) bis (trimellitate dianhydride), when n is 6 to 20,
1,6- (Hexamethylene) bis (trimellitate dianhydride), 1,7- (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),
There are 1,16- (hexadecamethylene) bis trimellitate dianhydride, 1,18- (octadecamethylene) bis (trimellitate dianhydride), and the like, and two or more of these may be used in combination.

Examples of diamines are 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane and 1,7-diaminoheptane. , 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,1
Aliphatic diamines such as 2-diaminododecane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane,
4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4 ′ -Diaminodiphenyl sulfone,
4,4'-diaminodiphenyl sulfone, 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, 1,
3-bis (3-aminophenoxy) benzene, 1,4-
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
-Phenylene bis (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,
There are aromatic diamines such as bis (4- (4-aminophenoxy) phenyl) sulfone.

This condensation reaction is usually carried out by mixing equimolar amounts of tetracarboxylic dianhydride and diamine in an organic solvent at 80 ° C. or lower. As the organic solvent, dimethylacetamide, dimethylformamide, N-methyl-2-
Pyrrolidone, dimethyl sulfoxide, hexamethylphosphorylamide, cyclohexanone, m-cresol, o
-Chlorophenol and the like.

As the reaction progresses, the viscosity of the reaction solution gradually increases, and polyamic acid, which is a precursor of polyimide, is produced.

When the above polyamic acid is dehydrated and ring-closed, a polyimide is obtained. The dehydration ring closure can be performed by a method of heat treatment at 120 ° C to 250 ° C or a chemical method. In the case of the method of heat treatment at 120 ° C. to 250 ° C., it is usually carried out while removing water generated by the dehydration reaction to the outside of the system.

When dehydration and ring closure are carried out by a chemical method, acid anhydrides such as acetic anhydride, propionic anhydride and benzoic anhydride, carbodiimide compounds such as dicyclohexylcarbodiimide and the like can be used as ring-closing agents. If necessary, a ring-closing catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine, imidazole may be used.

The repeating unit represented by the formula (I) or the formula (II) is contained in an amount of 70 mol% or more based on the repeating units of all polyimide resins. If it is less than 70 mol%, the adhesive strength to various substrate surfaces is lowered, and reflow cracks are likely to occur during reflow soldering.

The tetracarboxylic acid dianhydride of formula (III) or a tetracarboxylic acid (ester) component corresponding thereto is allowed to coexist within a range of less than 30 mol% based on the total of repeating units of all polyimide resins. Examples of acid components that can be used include other tetracarboxylic acids, and examples of acid dianhydrides include pyromellitic dianhydride, 3,3 ′,
4,4′-diphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride,
Bis (3,4-dicarboxyphenyl) ether dianhydride, 3,4,3 ', 4'-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 3 , 4,3 ', 4'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, etc. May be. These are made to coexist as necessary in order to adjust various die bonding characteristics such as wettability and adhesiveness.

In order to improve the adhesive strength of the resin paste,
A silane coupling agent, a titanium coupling agent, a nonionic surfactant, a fluorochemical surfactant, a silicone additive, etc. may be appropriately added to the polyimide resin.

The conductive filler (B) used in the present invention is
Conductive metal powder such as silver powder, gold powder, copper powder, or 2
Used as a mixture of two or more species. It is also possible to mix and use an inorganic insulator such as silica, alumina, titania, glass or iron oxide. The amount of the conductive filler is 1 to 8000 parts by weight, preferably 50 to 4000 parts by weight, based on 100 parts by weight of the polyimide resin. If it is less than 1 part by weight or more than 8000 parts by weight, the adhesiveness is lowered.

The thermosetting resin (C) used in the present invention is a resin containing an epoxy resin, a phenol resin and a curing accelerator, or an imide compound having at least two thermosetting imide groups in one molecule. Is good. Here, the thermosetting resin is a resin that is cured by forming a three-dimensional network structure by heating.

When a resin containing an epoxy resin, a phenol resin and a curing accelerator is used as the thermosetting resin, the epoxy resin contains at least two epoxy groups in the molecule from the viewpoint of curability and cured product characteristics. Resins are preferred. Examples of such epoxy resin include bisphenol A, bisphenol AD, bisphenol S, bisphenol F or a condensate of halogenated bisphenol A and epichlorohydrin, glycidyl ether of phenol novolac resin, glycidyl ether of cresol novolak resin, glycidyl of bisphenol A novolac resin. Examples include ether. The amount of epoxy resin is
It is 0 to 200 parts by weight, preferably 0 to 100 parts by weight, based on 100 parts by weight of the polyimide resin. If it exceeds 200 parts by weight, the adhesiveness will decrease.

The phenol resin used has at least two phenolic hydroxyl groups in the molecule, and examples of such a resin include phenol novolac resin, cresol novolac resin, bisphenol A novolac resin and poly-p-vinyl. Examples thereof include phenol and phenol aralkyl resin. The amount of the phenol resin is 2 to 150 parts by weight, preferably 50 to 120 parts by weight, based on 100 parts by weight of the epoxy resin. If the amount is less than 2 parts by weight or exceeds 150 parts by weight, curability becomes insufficient.

The curing accelerator is not particularly limited as long as it is used to cure the epoxy resin. Examples of such compounds include imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazides, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole-
Tetraphenyl borate, 1,8-diazabicyclo (5,4,0) undecene-7-tetraphenyl borate and the like are used. These may be used in combination of two or more. The amount of the curing accelerator is 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the epoxy resin. If it exceeds the limit, the storage stability will deteriorate.

When an imide compound having at least two thermosetting imide groups in one molecule is used as the thermosetting resin, examples of the compound include para-bis-maleimidobenzene, meta-bis-maleimidobenzene and para-bis-maleimidobenzene. Maleimidobenzene, 1,4-bis (p-maleimidocumyl) benzene, 1,4-bis (m-maleimidocumyl)
In addition to benzene, there are imide compounds represented by the following formulas (IV) to (VI).

[Chemical 6] [In the formula (IV), X is O, CH ₂ , CF ₂ , SO ₂ , S, C
O, C (CH ₃ ) ₂ or C (CF ₃ ) ₂ is shown, and R ₁ , R ₂ ,
R ₃ and R ₄ each independently represent hydrogen, a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine, and D represents a dicarboxylic acid residue having an ethylenically unsaturated double bond. ]

[Chemical 7] [In the formula (V), Y is O, CH ₂ , CF ₂ , SO ₂ , S, C
O, C (CH ₃ ) ₂ or C (CF ₃ ) ₂ is shown, and R ₅ , R ₆ ,
R ₇ and R ₈ each independently represent hydrogen, a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine, and D represents a dicarboxylic acid residue having an ethylenically unsaturated double bond. ]

Embedded image [In formula (VI), n shows the integer of 0-4. ]

The amount of the imide compound used in the present invention is
It is 0 to 200 parts by weight, preferably 0 to 100 parts by weight, based on 100 parts by weight of the polyimide resin. If it exceeds 200 parts by weight, the adhesiveness will decrease.

Examples of the imide compound of the formula (IV) include 4,4-bismaleimide diphenyl ether, 4,
4-bismaleimide diphenylmethane, 4,4-bismaleimide-3,3'-dimethyl-diphenylmethane,
4,4-Bismaleimidodiphenyl sulfone, 4,4-
Bismaleimide diphenyl sulfide, 4,4-bismaleimide diphenyl ketone, 2,2'-bis (4-maleimidophenyl) propane, 4,4-bismaleimide diphenylfluoromethane, 1,1,1,3,3,3- Hexafluoro-2,2-bis (4-maleimidophenyl) propane, and the like.

Examples of the imide compound of the formula (V) include bis [4- (4-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] methane, bis [4- (4- Maleimidophenoxy) phenyl] fluoromethane, bis [4- (4
-Maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl] ketone, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 1,1,1,
3,3,3-hexafluoro-2,2-bis [4- (4
-Maleimidophenoxy) phenyl] propane, etc.

A radical polymerization agent may be used to accelerate the curing of these imide compounds. Examples of the radical polymerization agent include acetylcyclohexyl sulfonyl peroxide, isobutyryl peroxide, benzoyl peroxide, octanoyl peroxide, acetyl peroxide, dicumyl peroxide, cumene hydroperoxide, and azobisisobutyronitrile. At this time, the amount of the radical polymerization agent used is preferably 0.01 to 1.0 parts by weight with respect to 100 parts by weight of the imide compound.

In the production of the resin paste of the present invention, first, the polyimide resin (A) is dissolved in an organic solvent. The organic solvent that can be used here is not particularly limited as long as it can be uniformly dissolved or kneaded, and examples thereof include dimethylformamide, dimethylacetamide and N 2.
-Methylpyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene, benzene,
There are xylene, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane and the like.

Next, the conductive filler (B) is added, and if necessary, other additives are added and mixed. In this case, the kneading may be carried out by appropriately combining an ordinary stirrer, a raker, a three-roller, a ball mill and other dispersing machines.

The resin paste containing the thermosetting resin (C) is manufactured as follows. First epoxy resin,
Phenol resin and polyimide resin are dissolved in an organic solvent. The organic solvent is not particularly limited as long as it can uniformly dissolve or knead the above materials, and the above-mentioned solvents such as dimethylformamide can be used.

Then, a curing accelerator, a conductive filler and, if necessary, an additive are added, and the mixture is mixed and kneaded in the same manner as described above to form a resin paste.

The resin paste containing the thermosetting resin is characterized in that the shear adhesive strength when heated is high. But,
On the contrary, since the peel adhesive strength when heated decreases, it is advisable to use a resin paste with or without a thermosetting resin depending on the purpose of use.

In a semiconductor device using the resin paste of the present invention, a resin paste is applied to a supporting member such as a lead frame by a dispensing method, a stamping method, a screen printing, etc., and a semiconductor element is pressure-bonded thereto, and then a hot air circulation system is used. A semiconductor device and a supporting member are bonded by heating and curing using a heating device such as a dryer or a heat block, and then a semiconductor device is obtained through a normal wire bonding process and a sealing process.

[0036]

The present invention will be described below with reference to examples. Synthesis Example 1 500 m equipped with a thermometer, stirrer and calcium chloride tube
41 g (0.1 mol) of 2,2-bis (4-aminophenoxyphenyl) propane and 150 g of dimethylacetamide were placed in a 4-necked flask having a volume of 1 and stirred. After dissolution of the diamine, while cooling the flask in an ice bath,
-(Ethylene) bis (trimellitate dianhydride) 41g
(0.1 mol) was added in small portions. After reacting for 3 hours at room temperature, 30 g of xylene was added, and the mixture was heated at 150 ° C. while blowing N ₂ gas to remove xylene azeotropically with water. The reaction solution was poured into water, and the precipitated polymer was collected by filtration and dried to obtain a polyimide resin (A ₁ ).

Synthesis Example 2 500 m equipped with a thermometer, stirrer and calcium chloride tube
43.2 g (0.1 mol) of bis (4- (3-aminophenoxy) phenyl) sulfone and 150 g of N-methyl-2-pyrrolidone were placed in a 4-liter four-necked flask and stirred. After dissolving the diamine, at room temperature, 43.8 g of 1,4- (tetramethylene) bis (trimellitate dianhydride)
(0.1 mol) was added. React at 5 ° C or below for 5 hours,
20.4 g (0.2 mol) of acetic anhydride and pyridine 15.
8 g (0.2 mol) was added and stirred at room temperature for 1 hour. The reaction solution was poured into water, and the precipitated polymer was collected by filtration and dried to obtain a polyimide resin (A ₂ ).

Synthesis Example 3 500 ml equipped with a thermometer, stirrer and calcium chloride tube
In a four-necked flask of 2,2-bis (4-aminophenoxyphenyl) propane 32.8 g (0.08 mol),
5.08 g (0.02 mol) of 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane and 100 g of dimethylacetamide were taken and stirred. After dissolution of the diamine, while cooling the flask in an ice bath,
0- (decamethylene) bis (trimellitate dianhydride)
41.8 g (0.08 mol) and 6.44 g (0.02 mol) of benzophenone tetracarboxylic dianhydride were added in small portions. After the addition was completed, the reaction was allowed to proceed for 3 hours in an ice bath and further for 4 hours at room temperature, and then 25.5 g (0.25
Mol) and 19.8 g (0.25 mol) of pyridine, and the mixture was stirred at room temperature for 2 hours. Pour the reaction into water,
The precipitated polymer was taken by filtration, and dried to give a polyimide resin (A _3).

Synthesis Example 4 500 ml equipped with a thermometer, stirrer and calcium chloride tube
Into a four-necked flask of 4 was charged 41.0 g (0.10 mol) of 2,2-bis (4-aminophenoxyphenyl) propane and 100 g of dimethylacetamide and stirred. After dissolution of the diamine, while cooling the flask in an ice bath,
4,1.8 g (0.08 mol) of 1,10- (decamethylene) bis (trimellitate dianhydride) and 6.44 g (0.02 mol) of benzophenone tetracarboxylic acid dianhydride
Was added in small portions. After the addition was completed, the reaction was carried out for 3 hours in an ice bath and then for 4 hours at room temperature. Pour the reaction into water,
The precipitated polymer was taken by filtration and dried to afford polyamic acid resin (A _4).

Example 1 According to the formulation table shown in Table 1 (unit: parts by weight, the same applies hereinafter), kneading was carried out using a raker machine and a triple roll, and three types (No. 1 to No. 3) of homogeneity were obtained. Various resin pastes were prepared.

[0041]

[Table 1] Table 1 Recipe Table ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Material No. 1 No. 2 No. 3 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Resin Polyimide A ₁ Polyimide A ₁ Polyamic acid A ₄ 100 parts 100 copies 100 copies ─────────────────────────────────── Silver powder (TCG-1) 150 copies 67 copies 150 Parts ─────────────────────────────────── Solvent DMAA 300 parts CH 300 parts CH 300 parts ━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ The abbreviations in Table 1 have the following meanings. DMAA: Dimethylacetamide, CH: Cyclohexanone TCG-1: Tokuriki Kagaku, silver dust

Example 2

[Table 2] Table 2 Recipe List ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Material No. 4 5 6 7 8 9 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Epoxy YDCN-702 N-865 ESCN-195 N-865 N-865 YDCN-702 Resin 50 parts 20 parts 10 parts 10 parts 7 parts 50 parts ───────────────────────────── ──────── pheno H-1 H-1 VH-4170 VH-4170 VH-4170 H-1 resin 24 10 6 6 5 24 ──────────────── ───────────────────── Curing acceleration 2P4MHZ TPPK 2MA-0K TPPK TPPK 2P4MHZ agent 0.5 0.4 0.1 0.5 0.7 0.5 ──────────── ──────────────────────── Polyimi A ₁ A ₂ A ₃ A ₁ A ₁ A ₄ Resin 100 100 100 100 100 100 ───── ────────────── ───────────────── Silver powder (TCG-1) 400 200 70 500 67 400 ────────────────────── ─────────────── Solvent DMAA NMP CH CH / DMAA CH / DMAA CH 400 200 100 100 67 400 ━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━

According to the formulation table shown in Table 2, kneading was carried out using a rafting machine and a triple roll to prepare 6 kinds of uniform resin pastes No. 4 to No. 9. In Table 2, various symbols have the following meanings. YDCH-702: Toto Kasei, Cresol Novolac Epoxy
(Epoxy equivalent 220), N-865: Dainippon Ink, bisphenol novolac type epoxy (epoxy equivalent 208), ES
CN-195: Nippon Kayaku, cresol novolac type epoxy (epoxy equivalent 200), H-1: Meiwa Kasei, phenol novolac (OH equivalent 106), VH-4170: Dainippon Ink, bisphenol A novolac (OH equivalent 118), TCG-1: Tokuriki Kagaku, silver powder, DMAA: dimethylacetamide, NMP: N-
Methylpyrrolidone, CH: Cyclohexanone

Example 3 According to the formulation table shown in Table 3, kneading was carried out using a raider and a three-roll mill to prepare 6 kinds of uniform resin pastes No. 10 to No. 15.

[0045]

[Table 3] Table 3 Recipe List ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Material No. 10 11 12 13 14 15 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Polyimide A ₁ A ₂ A ₃ A ₁ A ₁ A ₄ 100 parts resin 100 parts 100 parts 100 parts 100 parts 100 parts ─────────────────────────────────── ─ Imide BMDADPM BMDADPM BMPPP BMPPP BMDADPE BMDADPM Compound 20 50 10 50 30 20 ──────────────────────────────────── ─ Silver powder 500 50 100 800 100 500 ──────────────────────────────────── Solvent DMAA CH / DMAA NMP CH / DMAA DMAA CH ──────────────────────────────────── Other B PO DCPO BPO CHPO DCPO BPO 0.1 0.2 0.01 0.003 0.1 0.1 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

However, the symbols in Table 3 have the following meanings. BMDADPM: 4,4'-Bismaleimidodiaminodiphenylmethane BMPPP: 2,2-Bis (4- (4-maleimidophenoxy) phenyl) propane BMDADPE: 4,4'-Bismaleimidodiaminodiphenyl ether DMAA: Dimethylacetamide NMP: N-methyl Pyrrolidone DMF: Dimethylformamide BPO: Benzoyl peroxide DCPO: Dicumyl peroxide CHPO: Cumene hydroperoxide

Test Example 1 Shear Adhesive Strength of Resin Paste (Part 1) The shear adhesive strength of the resin paste obtained in Example 1 was measured and is as shown in Table 4. The test method was as follows. A resin paste was used to press-bond a 4 × 4 mm silicon chip and a silver-plated lead frame to cure at 180 ° C. for 1 hour, and then a push-pull gauge was used at room temperature and at 350 ° C. The shear adhesive strength was measured at the time of heating after heating for 20 seconds at 0 ° C.

[0048]

[Table 4] Table 4 Shear adhesive strength of resin paste ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Item No. ． 1 No. 2 No. 3 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Shear adhesive strength (kgf / chip) Room temperature 15.0 14. 5 12.5 350 ℃ 0.5 0.4 0.4 0.4 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Test Example 2 Shear Adhesion of Resin Paste (Part 2) Shear adhesion of the resin paste obtained in Example 2 was measured and the results are shown in Table 5. The test method was as follows. A resin chip was used to press-bond a 4 × 4 mm silicon chip and a silver-plated lead frame, and the resin was cured at 180 ° C. for 1 hour. Then, a push-pull gauge was used to heat at room temperature and 350 ° C. Shear adhesion was measured when heated 20 seconds later.

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[Table 5] Table 5 Shear adhesive strength of resin paste ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Item No. .4 5 6 7 8 9 9 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Shear adhesive strength Room temperature 11.0 10.5 12.3 9.8 13.4 10.2 (kgf / chip) 350 ° C 2.0 2.5 3.0 1.8 2.1 2.2 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Comparing Table 4 and Table 5, the resin paste containing the thermosetting resin (No. 4 to 9) is shear bonded at 350 ° C. more than the resin paste containing the thermosetting resin (No. 1 to 3). You can see that the power is high.

Test Example 3 Shear adhesive strength of resin paste (Part 3)

[Table 6] Table 6 Shear adhesive strength of resin paste ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Item No. .10 11 12 13 13 14 15 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Shear adhesive strength Room temperature 10.7 12.3 17.5 15.7 11.3 11.0 (kgf / chip) 350 ° C 1.5 3.3 2.8 2.3 2.8 2.1 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ When the shear adhesive force of the conductive resin plate obtained in Example 3 was measured, it was as shown in Table 6. The test method is the same as the method described in Test Example 2.

Test Example 4 Peel Adhesive Strength of Resin Paste The peel adhesive strength of the resin pastes obtained in Example 1 and Example 2 was measured and the results are shown in Table 7. In addition,
Peel adhesion is obtained by crimping a 8 × 8 mm silicon chip and a silver-plated lead frame using resin paste,
After curing at 180 ° C. for 1 hour, measurement was performed at 250 ° C. for 20 seconds.

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[Table 7] Table 7 Peel adhesion of resin paste ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Item No. .1 2 3 4 5 6 7 7 9 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Peel adhesion 250 ℃> 3 ＞ 3 1.9 1.5 1.7 1.0 2.5 2.0 (kgf / chip) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Resin paste containing thermosetting resin (No. 4
~ 9) resin paste containing no thermosetting resin (N
It can be seen from the results of Table 7 that the peel adhesion at 250 ° C. is higher in o.1 to 3).

Test Example 5 Solder Reflow Crack Test The following lead frame and silicon chip were used in Examples 1-3.
The resin paste obtained in 1. was used for adhesion under the following curing conditions. Then, it was sealed with an epoxy sealing material CEL-4620 (Hitachi Chemical Co., Ltd.) to obtain a solder reflow test package. The package has a temperature and humidity of 85
It was allowed to absorb moisture for 48 hours in a thermo-hygrostat set to 85 ° C. and 85%. After that, solder reflow was performed under a reflow condition of 215 ° C./90 seconds, and the number of external cracks generated in the package was observed with a microscope (magnification: 15 times). Table 8 shows the number of cracked samples when 5 samples were tested. The test results of two types of comparative examples conducted in parallel are also shown.

[Curing conditions] Chip size: 8 mm x 10 mm Package: QFP, 14 mm x 20 mm x 2 mm Frame: 42 alloy Temperature conditions: Temperature rising to 180 ° C in 30 minutes, curing at 180 ° C for 1 hour

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[Table 8]

Two kinds of resin pastes as comparative examples were prepared as follows. Comparative Example 1 To 30 parts by weight of YDCN-702S (cresol novolac resin, Tohto Kasei Co., Ltd.), 10 parts by weight of H-1 (phenol novolak type resin, Meiwa Kasei Co., Ltd.) and 10 parts by weight of butyl cellosolve acetate were added and heated to 80 ° C. And stirred for 1 hour to obtain a varnish. Then cool down to 23 ℃ ~ 25 ℃,
Curesol 2P4MHZ (Imidasole, Shikoku Kasei) 0.5 part by weight and silver powder TCG-1 (Tokuriki Chemical Co., Ltd.) 80 parts by weight were mixed by a raker machine to obtain a resin paste.

Comparative Example 2 To 35 parts by weight of Epicoat 1001 (bis A type epoxy resin, oiled shell epoxy), 10 parts by weight of H-1 (phenol novolak type resin, Meiwa Kasei Co., Ltd.) and 10 parts by weight of butyl cellosolve acetate were added, It heated at 80 degreeC and stirred for 1 hour, and obtained the varnish. Then, the mixture was cooled to 23 ° C to 25 ° C, 0.5 parts by weight of Curezol 2P4MHZ (Imidasole, Shikoku Chemicals), silver powder TCG-1 (Tokuriki Kagaku) 8
The resin paste was obtained by mixing 0 parts by weight with a raker.

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EFFECTS OF THE INVENTION The resin pastes according to claims 1 to 4 are excellent in adhesive strength to various substrate surfaces and do not cause reflow cracks during reflow soldering. The semiconductor device according to claim 5 is highly reliable because it does not cause reflow cracks.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuo Miyadera 48, Wadai, Tsukuba, Ibaraki Hitachi Chemical Co., Ltd. Tsukuba Development Laboratory

Claims (5)

[Claims] (A) Formula (I): (However, n represents an integer of 2 to 20 and R represents a divalent organic group.) Or, the compound represented by the formula (II): (However, n represents an integer of 2 to 20, R represents a divalent organic group, and R ′ represents hydrogen or a monovalent organic group.) A resin paste containing a polyimide-based resin containing 70 mol% or more of the total of repeating units of the resin, and (B) a conductive filler. 2. The resin paste according to claim 1, which comprises (C) a thermosetting resin in addition to (A) a polyimide resin and (B) a conductive filler. 3. The resin paste according to claim 1, which comprises (A) a polyimide resin; 100 parts by weight, and (B) a conductive filler; 1 to 8000 parts by weight. 4. A resin containing (A) a polyimide resin; 100 parts by weight, and (B) a conductive filler; 1 to 8000 parts by weight, and (C) a thermosetting resin; 0 to 200 parts by weight. The resin paste according to claim 2, wherein 5. A semiconductor device in which a semiconductor element and a substrate are bonded with the resin paste according to any one of claims 1 to 4 and sealed.