KR20020079703A - Heat resistant adhesive and adhesive tape for semiconductors - Google Patents

Abstract

PURPOSE: A heat-resistant adhesive and adhesive tape for semiconductor are provided to improve adhesive strength and reduce a thermal stress between a semiconductor chip and a lead frame by controlling glass-transition temperature and the amount of the remaining solvent in a low temperature process by an adhesive. CONSTITUTION: A semiconductor chip(2) is adhered to a lead frame(3) by using an adhering member(1). An LOC(Lead-On-Chip) type semiconductor package by sealing an adhering portions of the semiconductor chip(2) and the lead frame(3) with a sealant(5). A compound adhesive sheet used for the adhering member(1) includes a resin having an imide radical. A heat-resistant adhesive conductive layer is formed on one or more sides of a heat-resistant base film. The heat-resistant adhesive conductive layer has an adhering starting temperature of 230 to 330 degrees centigrade, and the amount of the remaining solvent of 3.0 weight percent and below. The glass-transition temperature of the heat-resistant adhesive is 150 to 200 degrees centigrade.

Description

Heat resistant adhesive and adhesive tape for semiconductors

The present invention is to reduce the thermal process temperature and shorten the thermal process time of the semiconductor package by appropriately adjusting the glass transition temperature (Tg) and the residual solvent content of the adhesive member in the semiconductor package, especially the lead on chip (LOC) structure package The present invention relates to an adhesive member using a heat-resistant adhesive and an adhesive which prevents degradation of a package due to thermal stress and is effective for package crack resistance with low moisture absorption and low residual solvent properties. In other words, with the recent trend of higher capacities of 64M ~ 1G DARM in 4 ~ 16M DRAM in the past, it is essential to shorten the adhesion time and lower the temperature of the adhesion process in the bonding of the chip and the lead frame. In this situation, the adhesive member for bonding the semiconductor and the lead frame can be achieved by controlling the residual solvent amount and controlling the glass transition temperature.

As semiconductor integration increases, miniaturization of semiconductor chip circuits, miniaturization and thinning of packages are required, and thus, main process conditions of the package change. In addition, the required properties of the relevant materials to meet the changed key process conditions and package reliability will require new properties.

LOC stands for 'lead on chip' which is a typical method of mounting a semiconductor package for memory, and when it is literally expressed as a lead on a chip, it significantly reduces the mounting area of the semiconductor package compared to the conventional mounting method. It has the advantage of being reduced to, and is currently used as a typical implementation of the package for memory.

FIG. 1 shows a representative cross section of a LOC package. Each cross section of the LOC tape is bonded to the lead frame and the chip, and serves as a medium for mechanically attaching the lead frame and the chip to each other. It plays a role.

The chip and leadframe are electrically connected by wires, and the leadframe serves as a medium for electrically and mechanically connecting the entire semiconductor chip package to an external circuit such as a printed circuit board (PCB).

The manufacturing process of the LOC package is as follows.

① Lead frame taping process

First, the leadframe company attaches the LOC tape on the leadframe through the taping process.

② die attach process

The taping process attaches the chip to the opposite side of the LOC tape attached to the leadframe.

③ wire bonding process

Connect the chip and leadframe with wires.

④ EMC (epoxy molding compound) process

EMC protects package components from external conditions such as moisture by molding and stacking most components (except the outer lead) such as chips, LOC tapes, wires, and inner leads.

⑤ The semiconductor package chip, which has completed the final EMC above, is shipped after inspection and marking.

The present invention relates to a heat-resistant adhesive and a composite adhesive sheet, in particular bonded to the semiconductor chip to the lead frame.

In particular, the present invention relates to a heat-resistant adhesive and a composite adhesive sheet which are effective in preventing package cracks during soldering after moisture absorption in semiconductor packages, particularly in lead on chip (LOC) structure packages.

The conventional general package structure is a structure in which a chip is mounted on a die pad of a lead frame having the same structure as that of FIG. 3, and the lead frame and the chip are connected with an Au-Si eutectic method, solder or epoxy thermosetting adhesive ( Die bond material).

As the degree of integration increases and the chip grows, the percentage of semiconductor chips in the package increases. For this reason, since a chip mounted on the die pad of the lead frame cannot accommodate the chip, a package having a die padless structure of the same type as shown in Figs. 1 and 2 has been developed. 5,140,404, Japanese Patent Laid-Open No. 61-218199, Copper No. 61-241950, US Patent No. 4,862246, Japanese Patent Laid-Open No. 1-76732, 2-36542, copper 4-318962). Package structures having the same shape as those of FIGS. 1 and 2 are called lead on chip (LOC) and chip on lead (COL), respectively, and a thermosetting adhesive or a heat resistant hot melt adhesive is used to connect the lead frame and the chip.

Recently, in accordance with the demand for fine circuitry due to high integration of semiconductor chips, fine multi-pinning of the lead frame, and high electroconductive properties, thermal stress generated during the packaging process is suppressed to improve semiconductor package process conditions with high reliability. In terms of high integration and high electroconductivity, the lead frame material is also replaced with a nickel alloy from a copper alloy, and has been made thinner and smaller.

In particular, in the case of the LOC tape that bonds the semiconductor chip and the lead frame to each end face, the high integration package reliability is degraded by thermal stress by bonding in the existing high temperature process (near 400 ° C).

As the proportion of semiconductor chips in the package becomes smaller, thinner, or larger, the thickness of the sealing material becomes thinner. If the adhesive or the sealing material absorbs moisture, the moisture absorbed by heat during solder connection (solder reflow) vaporizes and expands. As a result, a lot of cracks occurred in the package.

In order to prevent this phenomenon, examination of the two surfaces of a sealing material and an adhesive agent is performed, and about a sealing material, the low moisture absorption and the improvement of mechanical strength (Japanese Patent Laid-Open No. 5-67708) are examined. On the other hand, as for the adhesive, a technique for reducing moisture absorption or separating the adhesive member into a plurality of small pieces to remove water vapor during reflow and to prevent cracking (see Japanese Patent Laid-Open No. 3-109757) It was.

In addition, from the standpoint of lowering the adhesion temperature, the solvent is intentionally retained, the resin is softened (see Japanese Patent Publication No. 3-64386), or the solvent is left to improve the fluidity and adhesion. It has been described with respect to reducing the leakage current between the inner leads by making enough (see Japanese Patent Application Laid-open No. Hei 2-36542), but the residual solvent evaporates in a high temperature process causing cracks in the package. It may cause problems.

In recent years, the packaging process requires low hygroscopic and low residual solvent properties that can withstand high temperature solder reflow compared to the conventional solder process.

Conventionally, in order to prevent cracking of the package (Korean Patent No. 0243731), the moisture content of the LOC tape and the length of the extruded limit were limited, but the LOC tape adhesive of the extruded length condition defined in the patent has a high glass transition temperature and a high temperature process (400 ° C.). Adhesion in the low-temperature process (below 350 ℃) to reduce thermal stress, resulting in thermal stress on the semiconductor chip and leadframe. Too weak, there is a problem that a heel crack occurs when the reliability evaluation.

In order to solve the problems of the present invention, the adhesive controls the glass transition temperature (Tg) and the residual solvent amount even in a low temperature process (less than 350 ° C.), thereby securing excellent adhesion to the lead frame and the chip, thereby improving the chip and the lead frame. The thermal stress of the hot and hot process can be alleviated to increase the package reliability and production yield. In addition, the LOC tape having low hygroscopicity and low residual solvent characteristics was improved to prevent cracking of the semiconductor package due to rapid evaporation of moisture and residual solvent during the high temperature solder process, thereby improving semiconductor package crack resistance.

In the case of using the existing LOC tape, the lead frame and the semiconductor chip are adhered at a high temperature around 400 ° C., which causes thermal stress on the semiconductor chip and causes package reliability degradation. Accordingly, the present invention has invented an adhesive tape suitable as a LOC tape that can be adhered at a time of adhesion time of less than 1.0 second at a low temperature of less than 350 ℃.

LOC tape of the present invention is first bonded in a form having a flow instantaneously when pressed in a short time of less than 1 second at a low frame condition of the lead frame and 300 ℃, if the flow of adhesive is too low lead When the wetting property of the frame and the wettability is lowered, there is a problem that the adhesive strength is lowered.If the flowability of the adhesive is too large, the amount of adhesive (fillet) pushed by the lead is excessive and the lead is tilted, resulting in a post process wire. It is desirable to have adequate flowability and fillet amount in the bonding process by causing defects in bonding. In the case of the conventional LOC tape to be bonded at a high temperature region of 400 ℃ when the adhesive is bonded at less than 350 ℃ due to the lack of flow of the adhesive has a weak adhesive strength problem. Even when the LOC tape is pressed at a temperature below 350 ° C. with the chip, when the flowability of the adhesive is too low, adhesion characteristics due to wettability with the chip are degraded.

In general, the tape for the LOC package mainly uses an imide-based adhesive, and the adhesive melts instantly at a high temperature to have a flowability, adheres to an adhesive substrate such as a semiconductor chip, and then hardens the adhesive again at room temperature. The adhesion is made in the form of being attached to the substrate.

Therefore, the high temperature flow characteristics of the adhesive play a very important role in the wettability of the adhesive and the adhesion property of the substrate, and by determining the range of the pressed length of the adhesive, the adhesive has the proper flow and adhesion characteristics in the bonding process below 350 ° C. Compared to the adhesion process near 400 ℃, thermal stress during the adhesion process can be alleviated, and at the same time, the low residual solvent amount and proper residual solvent properties can be ensured to ensure the reliability of crack resistance of the semiconductor package. Production yields could be increased.

That is, the present invention

① As a heat-resistant adhesive and a heat-resistant adhesive used for an adhesive member for manufacturing a semiconductor package by bonding a semiconductor chip to the lead frame by an adhesive process of less than 350 ° C. and sealing at least the adhesive portion of the semiconductor chip and the lead frame with a sealing material. Provided is a composite sheet prepared heat-resistant composite sheet in the range of adhesion start temperature 230 ~ 330 ℃, residual solvent amount 0.03 ~ 1.00% by weight, residual solvent amount 3.0% by weight or less.

② A heat-resistant adhesive used in the adhesive member for manufacturing a semiconductor package by sealing the adhesive part with a sealing material, the adhesive starting temperature range 230 ~ 330 ℃, residual solvent amount 0.03 ~ 1.00% by weight, the length of the extruded 2.0 ~ 5.0mm, It provides a heat-resistant adhesive having a residual solvent content of 3% by weight or less and a glass transition temperature of 150 to 200 ° C.

(3) The adhesive member is a composite adhesive sheet formed by installing the heat resistant adhesive coating film on one or both sides of the heat resistant base film, or a heat resistant adhesive.

1 is a cross-sectional view of an example of a resin-encapsulated semiconductor device using the heat resistant adhesive member of the present invention.

2 is a cross-sectional view of another example of the resin-encapsulated semiconductor device in which the present invention uses a heat resistant adhesive member.

3 is a cross-sectional view of still another example of the resin encapsulated semiconductor device using the heat resistant adhesive member of the present invention.

<Description of the symbols for the main parts of the drawings>

1 bonding member 2 semiconductor chip

3: lead frame 4: wire

5: sealing material

The specific heat resistant adhesive used in the present invention may be made of a heat resistant thermoplastic resin or a thermosetting resin, may be made of a thermoplastic and thermosetting blending resin, and has a bonding start temperature of 230 to 330 ° C. and a residual solvent amount of 0.03 to 1.00 weight. It is in the range of%, residual solvent content of 3% by weight or less, and the length of 2.0 to 5.0mm extruded, and there is no particular limitation, but it is preferably a heat resistant adhesive having a glass transition temperature of 150 to 20 ° C., a polyimide adhesive and Preference is given to adhesives in which polyimide and other polymers are blended together.

Here, polyimide includes resin having imide groups such as polyamideimide, polyesterimide, polyetherimide and polyimide. Suitable polymers for blending together include epoxy, bismaleimide and the like.

In the heat-resistant adhesive of the present invention, the adhesion start temperature is 230 to 330 ° C., and the residual solvent amount is in the range of 0.03 to 1.00% by weight, more preferably in the range of 0.1 to 0.5% by weight. The amount of residual solvent affecting the crack resistance of the semiconductor is 3.0% by weight or less, preferably 2.5% by weight or less, more preferably 2.O% by weight or less, and the protruded length is in the range of 2.0 to 5.0 mm, preferably It is in the range of 2.5 to 3.5 mm. In particular, as the heat resistant adhesive of the present invention, it is desired that the glass transition temperature is in the range of 150 to 200 ° C, more preferably in the range of 150 to 180 ° C, in addition to the above characteristics. In particular, it was mentioned that the absorption rate and the residual solvent amount were closely related to the crack resistance of the semiconductor package. The crack resistance of the semiconductor package was related to the sum of the absorption rate and the residual solvent amount, and the sum of the residual solvent amount and the residual solvent amount was determined. It was called 'residual solvent amount'.

Here, the "adhesion start temperature" refers to the adhesive temperature that the adhesive force is 0.5kN / m or more when the adhesion between the heat-resistant composite sheet and the semiconductor chip made of the heat-resistant adhesive and the heat-resistant adhesive and the semiconductor chip under the conditions of 3.0MPa, 0.5 seconds.

In addition, the term "extended length" means that the length of the adhesive that was pushed out when the adhesive film having a thickness of 19 x 50 mm and a thickness of 25 μm was pressed at 350 ° C, 3.0 MPa for 1 minute was measured at the center of the long side direction. Shall be. In the preparation of the film, the polyimide varnish was spread out on a glass plate, dried at 100 ° C. for 10 minutes, then peeled and placed in an iron mold and dried at 250 ° C. for 1 hour to obtain a film. More specifically, the dried film was placed on a glass plate (PTFE) impregnated glass fabric (thickness 150 μm) on a lower plate of a hot press heated to 350 ° C., and then the dried film was placed on the glass fabric. After 30 seconds, the Teflon-impregnated glass fabric was placed on the film and pressed at 3.0 MPa for 1 minute.

In addition, the 'absorption rate' is obtained by applying a film made of a heat-resistant adhesive or a heat-resistant adhesive to a heat-resistant base film and drying the composite heat-resistant sheet at 120 ° C. for 1 hour, after weighing the weight (W), and immersing in distilled water for 24 hours. Weight increase (w) divided by dry weight (W) is the percentage (% by weight).

On the other hand, 'residual solvent amount' is to leave the heat-resistant adhesive or heat-resistant composite sheet in a standard state for 24 hours, then weigh the weight (W1) and then remove the residual solvent and moisture at 300 ℃, 1 hour conditions and weigh (W2) After weighing, the sample is left for 24 hours in a standard state, and then weighed (W3), and the percentage of the value obtained by subtracting W1 from W1 divided by W1 is the residual solvent amount (% by weight). Here, the weight of the W1 heat-resistant adhesive or even the heat-resistant composite sheet is the weight of the adhesive portion of the heat-resistant composite sheet. If the residual solvent content is less than 0.03% by weight, the adhesive strength is reduced, the adhesion process temperature with the chip and lead frame is increased, even if the process temperature is low, there is a problem that can not obtain the adhesive strength to secure the reliability for a short time of less than 1 second. In other words, in the case where the adhesive contains a solvent having a freezing degree, the adhesive strength with the chip can be obtained at a low temperature in a short time of 1 second or more. If it is more than 1.00% by weight, bubbles are generated when the heat-resistant adhesive and the heat-resistant composite sheet are adhered to the lead frame and the chip, resulting in poor adhesion. Usually, when adhesive is adhered to lead frame and chip, it is dried after removing water in 150 ~ 180 ℃ range and 20 ~ 50 seconds, so moisture is removed but residual solvent amount is not removed. It is very important to control the amount of residual solvent. In other words, at the high capacity of 64M ~ 1G DARM in the past 4 ~ 16M DRAM of semiconductors, it is essential to shorten the adhesion time and lower the temperature of the adhesion process when bonding the chip and the lead frame in the manufacture of semiconductor chips. In this situation, this could be achieved by adjusting the residual solvent volume and adjusting the glass transition temperature.

The residual solvent amount is a value obtained by adding the absorption rate and the residual solvent amount. The amount of residual solvent is a very important item in actual low temperature process adhesives and is a factor that affects the crack resistance of a semiconductor package. In conclusion, the crack resistance of the package of the semiconductor was secured when the residual solvent amount, which is the sum of the absorption rate and the residual solvent amount, was 3 wt% or less. Until now, the absorption rate has been an important factor in crack resistance of the semiconductor package, but according to the present invention, the amount of residual solvent, which is the sum of the absorption rate and the residual solvent amount, is an important factor for the crack resistance of the semiconductor according to the recent trend of lowering the temperature of the chip bonding process.

In the adhesive of the present invention, when the bonding start temperature with the chip or lead frame is lower than 230 ° C, the wire bonding property is rapidly deteriorated. In particular, in recent years, due to the development of technology, the wire bonding temperature is continuously lowered to be carried out at 200 ° C or lower. However, when bonding start temperature is less than 230 degreeC, there exists a tendency for wire bonding property to deteriorate rapidly. In this case, it is desirable to increase the hardness of the adhesive by containing an epoxy component in terms of the length and wire bonding extruded.

The heat resistant adhesive of the present invention is basically synthesized from diamine (A) or diisocyanate (A '), acid anhydride (B) and / or dicarboxylic acid or an amide modified derivative thereof (C), The above-mentioned predetermined characteristics, namely the adhesion start temperature range 230 ~ 330 ℃, residual solvent amount 0.03 ~ 1.00% by weight, residual solvent content 3% by weight or less, the length of the length 2.0 ~ 5.0mm extruded, glass transition temperature 150 ~ 200 ℃ It can be manufactured easily by combining the said reactive component so that it may have a range, and adjusting the reaction ratio, reaction conditions, molecular weight, presence or absence of an additive, its kind, additive resin, such as an epoxy resin, etc. in various ways.

As diamine (A) used for this invention, alkylenediamine, such as hexamethylenediamine, octamethylenediamine, dodecamethylenediamine, paraphenylenediamine, metaphenylenedaamine, 2, 4- diaminotoluene, etc., for example Arylenediamine, 4,4'-diaminodiphenylether (DDE), 4,4'-diaminophenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone , Diaminodiphenyl derivatives such as 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzanilide, 1,4-bis [1- (4-amino Phenyl) -1-methylethyl] benzene (BAP), 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis (3-aminophenoxy) benzene, 1 , 4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), 2,2'-bis [4 (3-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] sulfone (m-APPS), bis [4- (4-aminophenoxy) Phenyl] And the like phone, 2,2'-bis [4- (4-aminophenoxy) phenyl] siloxane diamine of the diamine and the following hexafluoropropane, and the following general formula (1) Formula (2).

(One)

In the above formula, Y is an amino group, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently hydrogen or an alkyl or alkoxy group having 1 to 4 carbon atoms, at least two or more of which are alkyl or alcohol groups, X is -CH _2- . -C (CH ₃ ) _2- , -O-, -SO _2- , -C0- or -NHCO- group.

As the compound of the general formula (1), for example, 4.4'-diamino-3,3 ', 5,5'-tetramethyldiphenylmethane, 4,4'-diamino-3,3', 5,5 '-Tetraethyldiphenylmethane, 4,4'-diamino-3,3', 5,5'-tetra (n-propyl) diphenylmethane, 4,4'-diamino-3,3 ', 5 , 5'- tetraisopropyldiphenylmethane,

4,4'-diamino-3,3 ', 5,5'-tetrabutyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-diethyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-diisopropyldiphenylmethane, 4,4'-diamino-3,3'-diethyl-5,5'-diiso Propyldiphenylmethane, 4,4'-diamino-3,5-dimethyl-3 ', 5'-diethyldiphenylmethane, 4,4'-diamino-3,5-dimethyl-3', 5 ' -Diisopropyldiphenylmethane, 4,4'-diamino-3,5-diethyl-3 ', 5'-diisopropyldiphenylmethane, 4,4'-diamino-3,5-diethyl -3 ', 5'-dibutyldiphenylmethane, 4,4'-diamino-3,5-diisopropyl-3', 5'-dibutyldiphenyl methane, 4,4'-diamino-3 , 3'-diisopropyl-5,5'-dibutyldiphenyl methane, 4,4'-diamino-3,3'-dimethyl-5,5'-dibutyldiphenylmethane, 4,4'- Diamino-3,3'-diethyl-5,5'-dibutyldiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3, 3'-diethyldiphenylmethane, 4,4'-diamino-3,3'-di (n-propyl) diphenylmethane, 4,4'-diamino-3,3'- Isopropyldiphenylmethane, 4,4'-diamino-3,3'-dibutyldiphenylmethane, 4,4'-diamino-3,3 ', 5-trimethyldiphenylmethane, 4,4'- Diamino-3,3 ', 5-triethyldiphenylmethane, 4,4'-diamino-3,3', 5-tri (n-propyl) diphenylmethane, 4,4'-diamino-3 , 3 ', 5-triisopropyldiphenylmethane, 4,4'-diamino-3,3', 5-tributyldiphenylmethane, 4,4'-diamino-3-methyl-3'-ethyl Diphenylmethane, 4,4'-diamino-3-methyl-3'-isopropyldiphenylmethane, 4,4'-diamino-3-ethyl-3'-isopropyldiphenylmethane, 4,4 ' -Diamino-3-ethyl-3'-butyldiphenylmethane, 4,4'-diamino-3-0 | sopropyl-3'-butyldiphenylmethane, 2,2'-bis (4-amino- 3,5-dimethylphenyl) propane, 2,2'-bis (4-amino-3,5-diethylphenyl) propane, 2,2'-bis [4-amino-3,5-di (n-propyl ) Phenyl] propane, 2,2'-bis (4-amino-3,5-diisopropylphenyl) propane, 2,2'-bis (4-amino-3,5-dibutylphenyl) propane, 4, 4'-diamino-3,3 ', 5,5'-tetramethyldipe Ether, 4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylether, 4,4'-diamino-3,3', 5,5'-tetra (n-propyl) Diphenyl ether, 4,4'-diamino-3,3 ', 5,5'-tetraisopropyldiphenyl ether, 4,4'-diamino-3,3', 5,5'-tetrabutyldi Phenylether, 4,4'-diamino-3.3 ', 5,5'-tetramethyldiphenylsulfone, 4.4'-diamino-3,3', 5,5'-tetriethyldiphenylsulfone, 4, 4'-diamino-3,3 ', 5,5'-tetra (n-propyl) diphenylsulfone, 4,4'-diamino-3,3', 5,5'-tetraisopropyldiphenylsulfone , 4,4'-diamino-3,3 ', 5,5'-tetrabutyldiphenylsulfone, 4,4'-diamino-3,3', 5,5'-tetramethyldiphenylketone, 4 , 4'-diamino-3,3 ', 5,5'-tetraethyldiphenylketone, 4,4'-diamino-3,3', 5,5'-tetra (n-propyl) diphenylketone , 4,4'-diamino-3,3 ', 5,5'-tetraisopropyldiphenylketone, 4,4'-diamino-3,3', 5,5'-tetrabutyldiphenylketone, 4,4'-diamino-3,3 ', 5,5'-tetramethylbenzanilide, 4,4'-diamino-3,3' , 5,5'-tetramethylbenzanilide, 4,4'-diamino-3,3 ', 5,5'-tetra (n-propyl) benzanilide, 4,4'-diamino-3,3' , 5,5'-tetraisopropylbenzanilide, 4,4'-diamino-3,3 ', 5,5'-tetrabutylbenzanilide, and the like.

(2)

In said formula, R <^15> and R <^18> is a divalent organic group, R <^16> and R <^17> is a monovalent organic group, m is an integer of 1-100000.

Examples of the general formula (2) R ¹⁵ and R ¹⁸ in each independently represents a trimethylene group - (CH _{2) 3} -, a tetramethylene group - (CH _{2) 4} -, toluyl include a group and a phenylene group, etc., and , as the R ¹⁶ and R ^17, there may be mentioned a methyl group, an ethyl group, a phenyl group, each independently, of R ¹⁶ and a plurality of R ¹⁷ are a plurality, each may be independently same or different.

In the siloxanediamine of general formula (2), when any one of R <^15> and R <^18> is a trimethylene group and any one of R <^16> and R <^17> is a methyl group, m is 1, the average is about 10O, and the average It is sold by Shin-Etsu (Tokyo, Japan) and Dow Coated Toray Silicone (Tokyo, Japan) by molecular weight.

As diisocyanate (A ') used for this invention, what substituted the amino group by the isocyanate group in the diamine illustrated above is mentioned as an example.

As the acid anhydride (B) used in the present invention, trimellitic anhydride, pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, Bis (3,4-dicarboxyphenyl) sulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfon dianhydride, 2,2-bis [4 (3,4-dicarboxy Phenoxy) phenyl] propane dianhydride, ethylene glycol bistritellate dianhydride (EBTA), decamethylene glycol bistrimellitate dianhydride (DBTA), bisphenol A bistrimellitate dianhydride (BABT), 2,2-bis [4 -(3,4-dicarboxybenzoyloxy) phenyl] hexafluoropropane dianhydride, 1,4-bis [1-methyl-1- [4- (3,4 (dicarboxybenzoyloxy) phenyl] ethyl] benzene Dianhydride, maleic anhydride, methylmaleic anhydride Sunnamic acid, allyl anhydride, methylnamic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, etc. are mentioned.

In addition, a part of diamine (A) and dicarboxylic acid (C) can be substituted by aminocarboxylic acid, such as aminobenzoic acid.

Preferably, the heat resistant adhesive of the present invention is (A) diamine as alkylenediamine, metaphenylenediamine, 2,4-diaminotoluene, 4,4'-diaminodiphenylether (DDE), 4,4 '-Diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 1,4-bis (4-aminophenyl Isopropyl) benzene (BisAP), 1,3-bis (4-aminophenylisopropyl) benzene (BisAM), 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy Benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2'-bis [4- (4-aminophenoxy) phenyl] Propane (BAPP), bis [4- (3-aminophenoxy) phenyl] sulfone (m-APPS or BAPSM), bis [4- (4-aminophenoxy) phenyl] sulfone (BAPS), 2,2'- Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylmethane, 4,4'-diamino- 3,3 '5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3', 5 , 5'- tetraisopropyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-diethyldiphenylmethane, 4,4'-diamino-3,3'- Dimethyl-5,5'-diisopropyldiphenylmethane, 4,4'-diamino-3,3'-diethyl-5,5'-diisopropyldiphenylmethane, 4,4'-diamino- 3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diamino-3,3'-diisopropyldiphenylmethane, also Bis (γ-aminopropyl) tetramethyldisiloxane (GAPD), bis (γ-aminopropyl) polydimethyldisiloxane (PSX 480 (weight average molecular weight = 480), PSX750 (weight average) in the siloxane diamine of general formula (2) Molecular weight = 750) and the like can be preferably used.

Preferably, as the (B) acid anhydride, trimellitic anhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 2,2'-bis (3,4- Dicarboxyphenyl) hexafluoropropane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfon dianhydride, 4,4'-bis (3,4-di Carboxyphenoxy) diphenylsulfone dianhydride, 2,2'-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, ethylene glycol bistrimulitate dianhydride (EBTA), decamethylene glycol bis Trimellitate dianhydride (DBTA), bisphenol A bistrimellitate dianhydride (BABT), 1, 4-bis [1-methyl-1- [4- (3,4-dicarboxybenzoyloxy) phenyl] ethyl] benzene Ruled anhydride, maleic anhydride, anhydride anhydride and allyl dianhydride can be preferably used.

In this invention, it is good to select a monomer suitably so that the glass transition temperature of resin manufactured by combining these diamine (A), acid anhydride (B), and dicarboxylic acid (C) suitably may be in the range of 150-200 degreeC. .

When the polyimide and the polyamide are mixed in order to produce a heat resistant adhesive according to the specific characteristics of the present invention, the glass transition temperature of the adhesive after mixing is preferably in the range of 150 to 200 ° C.

The adhesive member in which the adhesive of the present invention is used has a shape and properties suitable for bonding a semiconductor chip to a lead frame in the structure of a sealed semiconductor package, and is particularly suitable for the manufacture of a semiconductor package having a LOC structure. That is, the adhesive member in which the adhesive of the present invention is used is used to bond a semiconductor chip of a sealed semiconductor package of a structure without a top (bonding pad) on which the wire bonding connecting the semiconductor chip and the lead frame is on the semiconductor chip. It has a shape and properties that are particularly suitable for use.

As a heat resistant adhesive agent of this invention, it is not limited to said polyimide and polyamide, Polymaleimide and polyallyl naimide can also be used similarly. Polyimide is obtained by the heat ring or chemical ring of polyamic acid. Although the polyamide used for this invention does not need to be imidated 100% in half, it is preferable that it is fully imidized.

The heat resistant adhesive of the present invention may be polyimide or polyamide alone, or may be used by adding a mixture of polyimide and polyamide, or further adding an epoxy resin, a curing agent, a polyamine compound, a curing accelerator, or the like.

In this case, by appropriately mixing the following additives, such as epoxy resins, additive resins, polyamines, coupling agents, and the like, the residual solvent amount and the length to be extruded even if the glass transition temperature of the heat-resistant adhesive to be used is 150 ° C or less. It was found that it could be adjusted to fall within.

The epoxy resin that can be mixed with the specific polyimide heat-resistant adhesive of the present invention has an average of two or more epoxy groups per molecule, and there is no particular limitation, but for example, diglycidyl ether of bisphenol A, bisphenol F Diglycidyl ether, phenol novolak type epoxy resin, polyglycidyl ester of polyglycidyl ester polybasic acid of polyhydric acid, alicyclic epoxy resin, hydantoin type epoxy resin, etc. are mentioned.

Moreover, fillers and coupling agents, such as ceramic powder, glass powder, silver powder, and copper powder, can be added to the heat resistant adhesive agent of this invention. Moreover, it can also be used by making it into the base sheet, such as a heat resistant adhesive agent, a glass fabric, an aramid fabric, a carbon fiber fabric, of this invention.

As said polyamino compound, the following are mentioned specifically as polyfunctional polyamino. 3,3 ', 4,4'-tetraaminodiphenyl iscer, 3,3', 4,4'-tetraaminodiphenyl, 3,3 ', 4,4'-tetraaminodiphenylmethane, 3,3 ', 4,4'-tetraaminobenzophenone, 3,3', 4,4'-tetraaminodiphenyl sulfone, 3,3 ', 4,4'-tetraaminobiphenyl, 1,2,4,5 -Tetraaminobenzene, 3,3 ', 4-thyriaminodiphenyl, 3,3', 4-triaminodiphenylmethane, 3,3 ', 4-triaminobenzophenone, 3,3', 4-tri 3,3 which is a mono-, di-, tri- or tetra-acid salt of aminodiphenylsulfone, 3,3 ', 4-triaminodibiphenyl, 1,2,4-triaminobenzene and the like ', 4,4'-tetraaminodiphenyl iscer tetrahydrochloride, 3,3', 4,4'-tetraaminodiphenylmethane tetrahydrochloride, 3,3 ', 4,4'-tetraaminobenzophenone tetra Hydrochloride, 3,3 ', 4,4'-tetraaminodiphenyl sulfone tetrahydrochloride, 3,3', 4,4'-tetraaminobiphenyl tetrahydrochloride , 1,2,4,5-tetraaminobenzene tetrahydrochloride, 3,3 ', 4-thyriaminodiphenyl trihydrochloride, 3,3', 4-triaminodiphenylmethane trihydrochloride, 3,3 ', 4-triaminobenzophenone trihydrochloride, 3,3', 4-triaminodiphenylsulfone trihydrochloride, 3,3 ', 4-triaminodibiphenyl trihydrochloride, 1,2,4-tri Aminobenzene dihydrochloride and the like. The above polyfunctional polyamino compounds can be used 1 type or in mixture of 2 or more types. The polyfunctional polyamino compound is an important additive that can solve both parts of low temperature adhesiveness and wire bonding stability by adding a small amount and crosslinking. In the present invention, by adding the polyamino compound in the range of 0.01 to 5% by weight, low temperature adhesiveness and wire bonding properties were secured. In case of 0.01 wt% or less, the wire bonding property was deteriorated, and in the case of 5 wt% or more, the adhesion process temperature was high.

Examples of the coupling agent include vinyl silanes such as vinyltrimethoxysilane, vinyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiene. Ethoxysilane of the oxysilane, (beta)-(3, 4- methoxy cyclohexyl) ethyl trimethoxysilane; mercaptosilanes, such as aminosilanes, such as v-aminopropyl triethoxysilane, (gamma) -aminopropyl trimethoxysilane, and N-phenyl- (gamma) -aminopropyl trimethoxysilane, and (gamma)-mercaptopropyl trimethoxysilane; Although coupling agents, such as titanate, aluminate, and zirco aluminate, can be used, it is preferable to use a silane coupling agent, and an epoxy silane coupling agent is especially preferable.

As the solvent used in the present invention, N-methyl-2-pyrrolidone (NMP), NN-dimethyl formamide (DMF), NN-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), sulfolane, hexamethyl Aprotic polar solvents, such as a phosphate triamide and 1, 3- dimethyl- 2-imidazolidone, phenol type solvents, such as a phenol, cresol, xylphenol, and p-chlorophenol, etc. are mentioned. If necessary, ether solvents such as diethylene glycol and dimethyl ether, aromatic solvents such as benzene, toluene, and xylene are used. In addition, methyl ethyl ketone, acetone, tetrahydrofuran, dioxane, monoglyme, Solvents such as diglyme, methylcellosolve, cellosolve acetate, methanol, ethanol, isopropanol, methylene chloride, chloroform, trichloroethylene, nitrobenzene and tertiary amines such as pyridine can also be used. It is also possible to use one or more of the above solvents simultaneously. The solvent used for the LOC tape is preferably in the range of 0.01 to 1.0% by weight, more preferably in the range of 0.1 to 0.5% by weight.

The heat resistant adhesive used for the adhesive member of the present invention may be used alone, or may be applied by coating or impregnating onto a base film or sheet. In addition, when using a heat resistant adhesive agent alone, it can apply | coat directly to a to-be-adhered body, such as a semiconductor chip and a lead frame, and can also be used, previously applied to a to-be-adhered body on a sheet, and thermocompression-bonding.

When the heat-resistant adhesive of the present invention is applied on a base film (or sheet) and used as a composite adhesive sheet, the composite adhesive sheet may be bonded to one or both sides of a heat-resistant base film, preferably a surface-treated heat-resistant base film 230 to Apply a heat-resistant adhesive or varnish thereof in a range of 330 ° C., a residual solvent amount of 0.03 to 1.00% by weight or less, a residual solvent amount of 3.0% by weight or less, an extended length of 2.0 to 5.0 mm, and preferably a glass transition temperature of 150 to 200 ° C. After that, it is obtained by heating.

As a heat resistant base film used as a base film in this invention, films, such as engineering plastics, such as a polyimide, a polyamide, a polysulfone, a polyphenylene sulfide, a polyether ether ketone, and a polyarylate, are mentioned.

The glass transition temperature (glass transition temperature) of a heat resistant base film is higher than the glass transition temperature of the heat resistant adhesive agent of this invention, Preferably it is 20 degreeC or more, More preferably, 250 degreeC or more is used. The water absorption of the heat resistant base film is 3.0% by weight or less, preferably 2.5% by weight or less.

Therefore, as a heat resistant base film used for this invention, a polyimide film is preferable from a glass transition temperature, a water absorption rate, and a thermal expansion coefficient. Particularly preferred are films having physical properties of glass transition temperature of 200 ° C. or higher, water absorption of 3.0% by weight or less, and thermal expansion coefficient of 30 ppm / ° C. or lower.

Heat-resistant base film is preferably subjected to a surface treatment to increase the adhesion with the adhesive. As the surface treatment method, chemical treatment such as alkali treatment, silane coupling treatment, physical treatment such as sand blast, plasma treatment, corona treatment, and the like can be used, but it is preferable to use a treatment most suitable according to the type of adhesive. When the heat resistant adhesive of the present invention is applied, chemical treatment or plasma treatment is particularly suitable as the surface treatment to be applied to the heat resistant base film.

The method of forming the adhesive layer on the base film is not particularly limited, and examples of suitable methods include a method of applying an adhesive varnish to the base film and drying and removing the solvent. The method of applying the adhesive varnish to the base film is not particularly limited, and a coater of comma form, reverse form, and die form may be used. Of these, die-type coaters are the most preferred. Application can also be performed by immersing the base film in an adhesive varnish, but it can be difficult to control the thickness of the adhesive layer.

In the case of the polyamic acid varnish, a temperature higher than the glass transition temperature is required for imidization, but in the case of the polyimide varnish, any temperature can be used to remove the solvent. In order to improve the adhesive strength of the adhesive and the heat-resistant base film, it is preferable to heat-treat at a temperature of 250 ℃ or more.

In the present invention, in the case of the composite adhesive heat-resistant sheet provided with a heat-resistant adhesive coating film on both the outer and inner surfaces of the heat-resistant base film, the outer and inner adhesives may be the same or different.

The adhesive member using the heat resistant adhesive roll of the present invention is particularly favorable for adhesion between the lead frame and the semiconductor chip in the semiconductor package having the LOC structure shown in FIG.

The lead on chip (LOC) structure package of FIG. 1 differs from the chip on lead (COL) package of FIG. 2 and the ratio of semiconductor chips in the entire package as compared to the package of FIG. 3. The package of FIG. In the package of FIG. 2, wire bonding is performed laterally of the semiconductor chip, whereas the package of FIG. 1 is wire bonded on the semiconductor chip, and the package of FIG. Is not required otherwise.

Therefore, in the package of FIG. 1, since the ratio of the semiconductor chip which occupies for the whole package can be enlarged, the sealing material which occupies the whole package inevitably becomes thin, and the influence of the adhesive agent on the package crack generation and the reliability of a semiconductor becomes large.

In the package of FIG. 1, the occurrence of a package crack increases rapidly compared with the package of FIG. 2, and a countermeasure is desired. The adhesive of the present invention is particularly effective for preventing the occurrence of package cracking in the package of FIG.

When using the adhesive agent of this invention for connection of a semiconductor chip and a lead frame, there is no restriction | limiting in particular in the method, It can connect by the method most suitable for each package.

For example, (1) First, the composite adhesive sheet coated with both sides of the heat resistant adhesive of the present invention is thermocompression-bonded to a lead frame, and then the semiconductor chip is thermocompression-bonded to the surface of the heat-resistant adhesive of the opposite invention.

(2) A sheet coated with the heat-resistant adhesive of the present invention on one side is first thermally pressed on a lead frame, and then the same or different adhesive paste of the present invention is applied on the opposite side to press the semiconductor chip.

(3) The heat-resistant adhesive single film of the present invention is sandwiched between the semiconductor chip and the lead frame and thermocompressed.

(4) Various methods can be used, such as applying the heat resistant adhesive of the present invention to a semiconductor chip or lead frame, and thermocompression bonding with the lead frame or semiconductor chip.

A specific method of adhering a semiconductor chip to a lead frame using the adhesive member using the heat resistant adhesive of the present invention is illustrated by FIGS. 1 to 2 is a semiconductor package manufactured by bonding a semiconductor chip to a lead frame by means of an adhesive member using the heat resistant adhesive of the present invention, and sealing the adhesive portion between the semiconductor chip, the semiconductor chip and the lead frame as a sealing material. It is a figure which shows the adhesion state in the case where the lead frame shape and the position of the semiconductor chip adhere | attached with a lead frame differ.

The adhesive member using the heat resistant adhesive of the present invention is effective for connecting the semiconductor chip and the lead frame, but is not limited thereto, and can be effectively applied to adherends such as ceramic plates, metal plates, metal foils, plastic films, plastic plates, and laminates. Can be.

In this case, the adherend can be adhered to another object by applying it on the adherend or in the case of a sheet, by sandwiching between the adherend and heating and pressing at a temperature equal to or higher than the softening temperature of the adhesive.

EXAMPLE

Although an Example demonstrates this invention in detail below, this invention is not limited to these range.

Example 1

4.63 g (9 mmol) 1,3-bis (3-aminophenoxy) benzene and 0.25 g (1 mmol) GAPD N, N-dimethyl in a four-necked flask equipped with a stirrer, thermometer, nitrogen gas introduction tube and salt calcium tube 28.3 g of formamide (DMF) was added to dissolve it. Then, 3,3'4,4'- oxydiphthalic anhydride (ODPA) 3.10 g (10 mmol) was added little by little while cooling not to exceed 5 ° C, followed by cooling for 1 hour while cooling not to exceed 5 ° C, followed by 6 hours at room temperature. By reacting, polyamic acid was synthesized. 2.55 g of acetic anhydride and 1.98 g of pyridine were added to the reaction solution containing the obtained polyamic acid, followed by reaction at room temperature for 3 hours to synthesize polyimide.

The obtained polyimide roll-containing reaction solution was poured into water, and the precipitate obtained was separated, pulverized and dried to obtain a polyimide powder.

The polyimide powder was dissolved in DMF at a concentration of 0.1 g / dl, and the reduced viscosity when measured at 30 ° C. was 0.71 dl / g. The polyimide powder was added to various organic solvents so as to have a concentration of 5% by weight, and the solubility was observed at room temperature to test the solubility. As a result, this polyimide powder was dissolved in DMF, N-methylpyrrolidone (NMP) and DMAc.

And the varnish obtained by dissolving this polyimide powder in NMP was made to flow on the glass plate. After drying for 10 minutes at 10O &lt; 0 &gt; C, it was peeled off and placed in an iron mold and dried at 250C for 1 hour to obtain a film.

Thus, the glass transition temperature of the polyimide was 182 degreeC in the film obtained by measuring the temperature increase rate of 10 degree-C / min with the differential calorimeter. Pyrolysis temperature was 405 degreeC.

NMP varnishes of polyimide were applied on a plasma-treated polyimide film (trade name: UPILEX-SGA, manufactured by Ube Industries, Ltd.), followed by drying at 10OOOC and 10O0 at 270 ° C for composite adhesion. A sheet was obtained. The residual solvent amount of this composite adhesive sheet was 0.13 wt%, the residual solvent amount was 1.7 wt%, and the adhesion start temperature with the chip (PIX3400 coating) was 300 ° C.

Packages a thin small out-line package (TSOP) type semiconductor chip by bonding the lead frame and the semiconductor chip to which the composite adhesive sheet is attached and the bonding conditions at a temperature of 3 MPa, 0.5 seconds, and 10 ° C. higher than the initiation temperature. After soaking for 48 hours at 85 ° C. and 85% RH, the solution was immersed in a solder bath at 260 ° C., but no cracking occurred, and the final yield of the semiconductor was 99.97%.

Example 2

3.22 g (10 mmol) of 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3.46 g (8 mmol) of bis [4- (3-aminophenoxy) phenyl] sulfone (m-APPS or BAPSM) ) And PSX750 1.5 g (2 mmol) were used in the same manner as in Example 1 to obtain a polyamic acid varnish. It carried out similarly to Example 1 from this polyamic-acid varnish, and obtained the polyimide powder. Its reduced viscosity was 1.21 dl / g, glass transition temperature was 190 ° C, and pyrolysis temperature was 410 ° C.

A composite sheet was obtained in the same manner as in Example 1 except that the drying conditions were adjusted so that the residual solvent amount of the composite sheet was 0.42 wt% using the polyamic acid varnish. The adhesion start temperature of the composite sheet was 280 ℃ and the residual solvent amount was 1.7% by weight. In the same manner as in Example 1, the TSOP semiconductor package obtained by bonding at 290 ° C. (temperature 10 ° C. higher than the adhesion start temperature) did not generate cracks due to soldering after moisture absorption, and the final yield of the semiconductor was 99.98%.

Example 3

3,3'4,4'-oxydiphthalic dianhydride (ODPA) 1.55 g (5 mmol), 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride 1.61 g (5 mmol) instead of DMF A pulley amic acid varnish was obtained in the same manner as in Example 1 except that NMP 20.6 g was used. 10 g of xylene was added to the varnish and heated at 180 ° C. for 5 hours to obtain a polyimide varnish. The reduced viscosity was 0.48 dl / g, the glass transition temperature was 187 ° C, and the pyrolysis temperature was 405 ° C.

Plasma-treated polyimide film (trade name: APICAL-AH, Kaneka Industries, Ltd.) after applying the polyimide varnish and dried, the adhesion start temperature 305 ℃, residual solvent amount 0.08% by weight, residual solvent amount 2.4% The composite adhesive sheet which is% was obtained.The TSOP type semiconductor package obtained by carrying out similarly to Example 1 did not produce the crack by the soldering process after moisture absorption, and the final product yield of the semiconductor package was 99.97%.

Example 4

2.29 g (8 mmol) of DAnMG and 0.50 g (2 mmol) of GAPD were dissolved in 24.5 g of DMF, 2.02 g (10 mmol) of isophthalic acid chloride was cooled to below 5 ° C. after adding 2.02 g (20 mmol) of triethylamine. Was added little by little. After reacting at 5 degrees C or less for 5 hours, it carried out similarly to Example 1, and obtained polyamide powder. The reduced viscosity was 0.45 dl / g, the glass transition temperature was 160 ° C, and the pyrolysis temperature was 395 ° C.

60 wt% of polyimide and 40 wt% of the polyamide obtained in the same manner as in Example 1 were applied on a plasma-treated APICAL-AH film, and then dried to obtain a glass transition temperature of 172 ° C, adhesion start temperature of 270 ° C, A composite adhesive sheet having a residual solvent amount of 0.10% by weight and a residual solvent amount of 2.3% by weight was obtained. The TSOP type semiconductor package obtained in the same manner as in Example 1 did not produce cracks due to the soldering process after moisture absorption, and the final production yield of the semiconductor package was 99.99%.

Example 5

Polyimide powder in the same manner as in Example 3 except for 3.10 g (10 mmol) of 3,3'4,4'-oxydiphthalic anhydride (ODPA), 2.87 g (7 mmol) of BAPP, and 2.25 g (3 mmol) of PSX750. Got. The reduced viscosity was 0.62 dl / g, the glass transition temperature was 161 占 폚, and the pyrolysis temperature was 395 占 폚.

The DMAc varnish of the polyimide was applied on a polyimide film (trade name: NPI, Kaneka Industries, Ltd.) and dried, followed by an adhesion start temperature of 270 ° C., residual solvent amount of 0.14% by weight, and residual solvent amount of 2.5% by weight. Phosphorus composite adhesive sheet was obtained. The TSOP type semiconductor package obtained in the same manner as in Example 1 did not produce cracks due to the soldering process after moisture absorption, and the final production yield of the semiconductor package was 99.99%.

Example 6

3,3'4,4'-oxydiphthalic anhydride (ODPA) 3.10 g (10 mmol), 1,3-bis (4-aminophenylisopropyl) benzene (BisAM) 2.75 g (8 mmol), PSX750 1.5 A polyimide powder was obtained in the same manner as in Example 1 except that g (2 mmol) was used. The reduced viscosity was 0.61 dl / g, the glass transition temperature was 155 ° C, and the pyrolysis temperature was 415 ° C.

The NMP varnish of the polyimide was applied to a plasma-treated polyimide film (trade name: UPILEX-SGA, Ube Industries, Ltd.), dried, and then dried at an adhesion start temperature of 270 ° C., a residual solvent amount of 0.10% by weight, and a residual solvent. A composite adhesive sheet having an amount of 1.8% by weight was obtained. The TSOP type semiconductor package obtained in the same manner as in Example 1 did not produce cracks due to the soldering process after moisture absorption, and the final production yield of the semiconductor package was 99.99%.

Example 7

BAPB, 2.58 g (7 mmol), PSX480 1.44 g (3 mmol) is dissolved in DMF 20 g, and 2.02 g (20 mmol) of triethylamine is added, followed by cooling to below 5 ° C. 10 mmol) was added in portions. After reacting at 5 degrees C or less for 5 hours, it carried out similarly to Example 1, and obtained polyamide powder. The reduced viscosity was 0.88 dl / g, the glass transition temperature was 185 ° C, and the pyrolysis temperature was 385 ° C.

An NMP varnish containing 6% by weight of polyimide of Example 1 and 4% by weight of polyamide was applied and dried to obtain a composite adhesive sheet having an adhesion start temperature of 270 ° C., a residual solvent amount of 0.19% by weight, and a residual solvent amount of 1.9% by weight. . The TSOP type semiconductor package obtained in the same manner as in Example 1 did not produce cracks due to the soldering process after moisture absorption, and the final production yield of the semiconductor package was 99.99%.

Example 8

BAPB, 3.69 g (10 mmol) was dissolved in DMF 2Og, 1.23 g (3 mmol) of ethylene glycol bistrimultate dianhydride (EBTA) and 0.30 g (3 mmol) of triethylamine were added and then cooled to 5 ° C. or lower. 2.O3 g (2.17 mmol) of oxyphthalic anhydride was added little by little. After reacting for 5 hours or less at 5 ° C, acetic anhydride and pyridine were added to carry out in the same manner as in Example 1 to obtain a polyamideimide. The reduced viscosity was 0.88 dl / g, the glass transition temperature was 165 ° C, and the pyrolysis temperature was 385 ° C.

After the alkali treatment, apply the varnish in which the polyamideimide was dissolved in DMAc to the silane coupling-treated NPI film, and then dry it. Got. The TSOP type semiconductor package obtained in the same manner as in Example 1 did not produce cracks due to the soldering process after moisture absorption, and the final production yield of the semiconductor package was 99.99%.

Example 9

Polyimide powder was obtained in the same manner as in Example 1 except that 4.10 g (10 mmol) of ethylene glycol bistrimultate dianhydride (EBTA) and 3.44 g (10 mmol) of BisAM were used. The reduced viscosity was 0.65 dl / g, the glass transition temperature was 176 ° C, and the pyrolysis temperature was 396 ° C.

The NMP varnish of the polyimide was applied and dried on a plasma-treated UPILEX-SGA film to obtain a composite adhesive sheet having a bonding start temperature of 285 ° C., a residual solvent amount of 0.05% by weight, and a residual solvent amount of 2.1% by weight. The TSOP semiconductor package obtained in the same manner as in Example 1 did not generate cracks due to the soldering treatment after moisture absorption, and the final production yield of the semiconductor package was 99.98%.

Example 1O

Polyimide powder was obtained in the same manner as in Example 1 except that 4.10 g (10 mmol) of ethylene glycol bistrimultate dianhydride (EBTA), 3.10 g (9 mmol) of BisAM, and 0.25 g (1 mmol) of GAPD were obtained. . The reduced viscosity was 0.87 dl / g, the glass transition temperature was 163 占 폚, and the pyrolysis temperature was 400 占 폚.

The NMP varnish of the polyimide was applied onto a plasma-treated UPILEX-SGA film, and then dried to obtain a composite adhesive sheet having a bonding start temperature of 260 ° C., a residual solvent amount of 0.08% by weight, and a residual solvent amount of 2.2% by weight. The TSOP type semiconductor package obtained in the same manner as in Example 1 did not produce cracks due to the soldering process after moisture absorption, and the final production yield of the semiconductor package was 99.99%.

Example 11

Using the polyimide of Example 2, the same procedure as in Example 1 was carried out to produce a film of an adhesive alone having a bonding start temperature of 280 ° C., a residual solvent amount of 0.10% by weight, a residual solvent amount of 0.8% by weight, and an extended length of 2.5 mm.

The TSOP semiconductor package obtained in the same manner as in Example 1 did not generate cracks due to the soldering treatment after moisture absorption, and the final production yield of the semiconductor package was 99.98%.

Example 12

An NMP varnish of polyamideimide of Example 8 was used to form an adhesive layer on a semiconductor chip to prepare an adhesive layer having an adhesion start temperature of 250 ° C., a residual solvent amount of 0.92% by weight, a residual solvent amount of 2.2% by weight, and an extruding length of 2.3 mm. It was.

The TSOP type semiconductor package obtained in the same manner as in Example 1 did not produce cracks due to the soldering process after moisture absorption, and the final production yield of the semiconductor package was 99.99%.

Example 13

Except for using 4.10 g (10 mmol) of ethylene glycol bistrimultate dianhydride (EBTA), 2.04 g (7 mmol) of 1,3-bis (3-aminophenoxy) benzene, and 0.74 g (3 mmol) of GAPD, In the same manner as in Example 1, a polyimide powder was obtained. The reduced viscosity was 0.87 dl / g, the glass transition temperature was 135 ° C, and the pyrolysis temperature was 380 ° C.

The varnish obtained by dissolving 100 g of the polyimide powder and 3 g of v-glycidoxypropyltrimethoxysilane in DMF 4OOg was applied on a polyimide film (APICAL AH film), dried, and then dried to obtain a glass transition temperature of 143 ° C. and an adhesion start temperature of 300 ° C. And the composite adhesive sheet which is 0.15 weight% of residual solvents, and 2.9 weight% of residual solvents was obtained. The TSOP semiconductor package obtained in the same manner as in Example 1 did not produce cracks due to the soldering process after moisture absorption, and the final production yield of the semiconductor package was 99.97%.

Example 14

Except for using 4.10 g (10 mmol) of ethylene glycol bistrimultate dianhydride (EBTA), 2.04 g (7 mmol) of 1,4-bis (4-aminophenoxy) benzene, and 0.74 g (3 mmol) GAPD, In the same manner as in Example 1, a polyimide powder was obtained. The reduced viscosity was 0.87 dl / g, the glass transition temperature was 145 ° C, and the pyrolysis temperature was 380 ° C.

A glass transition temperature of 148 ° C., adhesion start temperature of 290 ° C., and residual solvent amount of 0.11 were carried out in the same manner as in Example 13 using a varnish in which 100 g of the polyimide powder and 5 g of γ-glycidoxypropyl methyldiethoxysilane were dissolved in DMF 4OOg. A composite adhesive sheet having a weight% and residual solvent amount of 2.8 weight% was obtained. The TSOP semiconductor package obtained in the same manner as in Example 1 did not produce cracks due to the soldering treatment after moisture absorption, and the final production yield of the semiconductor package was 99.97%.

Example 15

Ethylene glycol bistrimultate dianhydride (EBTA) 4.10 g (10 mmol), 1,4-bis (4-aminophenoxy) benzene 2.04g (7 mmol), PSX 750 2.25g (3 mmol) In the same manner as in Example 1, a polyimide powder was obtained. The reduced viscosity was 0.85 dl / g, the glass transition temperature was 137 ° C, and the pyrolysis temperature was 395 ° C.

Varnish obtained by dissolving 100 g of polyimide powder and 10 g of γ-glycidoxypropyltrimethoxysilane in NMP 4OOg was applied to both sides of a polyimide film (trade name: UPlLEX-S, manufactured by Ube Industries, Ltd.) It dried and obtained the composite adhesive sheet which is 141 degreeC of glass transition temperature, 290 degreeC of adhesion start temperatures, 0.10 weight% of residual solvents, and 1.0 weight% of residual solvents. The TSOP semiconductor package obtained in the same manner as in Example 1 did not generate cracks due to the soldering treatment after moisture absorption, and the final production yield of the semiconductor package was 99.98%.

Example 16

4.10 g (10 mmol) of ethylene glycol bistrimultate dianhydride (EBTA), 2.04 g (7 mmol) of 1,4-bis (4-aminophenoxy) benzene, and 2.22 g (3 mmol) of PSX 750 were used to Got it.

When the adhesive was formed into a film, the glass transition temperature was 137 ° C. and the thermal decomposition temperature was 395 ° C. 0.1 g (0.5 mmol) of 3,3 ', 4,4'-tetraaminodiphenyl was used as the polyamine acid. Polyimide powder was obtained in the same manner as in Example 1. The reduced viscosity was 0.90 dl / g, the glass transition temperature was 151 占 폚, and the pyrolysis temperature was 395 占 폚.

Varnish obtained by dissolving 100 g of polyimide powder in NMP 4OOg was coated on both sides of a polyimide film (trade name: UPILEX-SGA, manufactured by Ube Industries, Ltd.), dried, and then bonded at an initiation temperature of 270 ° C. and a residual solvent amount of 0.06 weight. % And a residual adhesive amount 0.6 wt% were obtained. The TSOP type semiconductor package obtained in the same manner as in Example 1 did not produce cracks due to the soldering process after moisture absorption, and the final production yield of the semiconductor package was 99.99%.

Example 17

Polyimide powder was obtained in the same manner as in Example 1 except that 3.22 g (10 mmol) of BTDA, 3.27 g (9.5 mmol) of BisAM, and 0.12 g (0.5 mmol) of GAPD were used. The ring viscosity was 0.44 dl / g, the glass transition temperature was 210 ° C, and the pyrolysis temperature was 398 ° C.

The polyimide varnish was applied to both sides and dried to obtain a composite adhesive sheet having a bonding start temperature of 320 ° C., a residual solvent amount of 0.53% by weight, and a residual solvent amount of 2.4% by weight. The TSOP semiconductor package obtained in the same manner as in Example 1 did not generate cracks due to the soldering treatment after moisture absorption, and the final yield of the semiconductor package was 99.96%.

Comparative Example 1

2.11 g (8.5 mmol) of DDS, 0.62 g (1.5 mmol) of BAPP are dissolved in 20 g of DMF, and 2.02 g (20 mmol) of triethylamine is added, followed by cooling to 5 ° C or less, and 2.O3 g (10 mmol) of isophthalic acid chloride. ) Was added little by little. After reacting at 5 degrees C or less for 5 hours, it carried out similarly to Example 1, and obtained polyamide powder. The reduced viscosity was 0.45 dl / g, the glass transition temperature was 280 ° C, and the pyrolysis temperature was 430 ° C.

After the alkali treatment, the polyamide varnish was applied to the APICAL-AH film treated with the cylinder coupling and dried to obtain a composite adhesive sheet having an adhesion start temperature of 430 ° C., a residual solvent amount of 0.05% by weight, and a residual solvent amount of 3.6% by weight. The TSOP semiconductor package obtained in the same manner as in Example 1 did not generate cracks due to the soldering treatment after moisture absorption, but the final yield of the semiconductor package was 94.47%.

Comparative Example 2

In the same manner as in Example 6, a polyimide powder having a reduced viscosity of 0.35 dl / g was obtained. The glass transition temperature was 175 ° C and the pyrolysis temperature was 410 ° C. In addition, the amount of residual solvent was 0.6% by weight, and the length that was pushed out was 6.1mm.

The composite adhesive sheet obtained in the same manner as in Example 6 obtained a composite adhesive sheet having a bonding start temperature of 270 ° C., a residual solvent amount of 0.12% by weight, and a residual solvent amount of 1.9% by weight. The TSOP semiconductor package obtained in the same manner as in Example 1 had a final production yield of 99.99%, but cracks occurred due to soldering treatment after moisture absorption.

Comparative Example 3

Polyimide powder was obtained in the same manner as in Example 1 except that 3.22 g (10 mmol) of BTDA, 3.27 g (9.5 mmol) of BisAM, and 0.12 g (0.5 mmol) of GAPD were used. The reduced viscosity was 0.44 dl / g, the glass transition temperature was 210 ° C, and the pyrolysis temperature was 398 ° C.

Varnish obtained by dissolving 100 g of polyimide powder in NMP 4OOg was applied to both sides of a polyimide film (trade name: UPILEX-SGA, manufactured by Ube Industries, Ltd.), dried, and then bonded to a starting temperature of 370 ° C. and a residual solvent amount of 0.11 weight. %, A composite adhesive sheet having a residual solvent amount of 2.0% by weight. The TSOP semiconductor package obtained in the same manner as in Example 1 did not generate cracks due to the soldering treatment after moisture absorption, and the final production yield of the semiconductor package was 94.89%.

Comparative Example 4

3.10 g (10 mmol) ODPA, 1.60 g (7 mmol) 1,3-bis (4-aminophenoxy) benzene, 0.54 g (2.7 mmol) 3,4'-oxydianiline (ODA), 0.07 g GAPD ( 0.3 mmol) was carried out in the same manner as in Example 1 to obtain a polyimide powder. The reduced viscosity was 0.44 dl / g, the glass transition temperature was 215 ° C, and the pyrolysis temperature was 398 ° C.

Varnish, in which 100 g of polyimide powder was dissolved in NMP 4OOg, was coated on both sides of a polyimide film (trade name: UPILEX-SGA, manufactured by Ube Industries, Ltd.), dried, and then bonded at an initiation temperature of 380 ° C. and a residual solvent amount of 0.15 weight. % And a residual adhesive amount 0.9 weight% of the composite adhesive sheet were obtained. The TSOP semiconductor package obtained in the same manner as in Example 1 did not produce cracks due to the soldering process after moisture absorption, and the final production yield of the semiconductor package was 94.83%.

Comparative Example 5

In the same manner as in Example 1, a polyimide powder was obtained. The reduced viscosity was 0.71 dl / g, the glass transition temperature was 182 ° C, and the pyrolysis temperature was 405 ° C.

The NMP varnish of polyimide was applied on a plasma-treated polyimide film (trade name: UPILEX-SGA, manufactured by Ube Industries, Ltd.), dried, and then bonded at an initiation temperature of 240 ° C., a residual solvent amount of 0.80% by weight, and residual. A composite adhesive sheet having a solvent amount of 3.2% by weight was obtained. Final production yield of the TSOP semiconductor package obtained in the same manner as in Example 1 was 99.99%, but cracks occurred due to soldering treatment after moisture absorption.

Comparative Example 6

Using the same polyimide as in Example 2, except that the reduced viscosity was 0.35 dl / g, the adhesion start temperature was 280 ° C., residual solvent amount 0.40 wt%, residual solvent amount 1.7 wt%, and extruded. A film of adhesive alone having a length of 5.5 mm was produced.

The TSOP semiconductor package obtained in the same manner as in Example 1 had a final yield of 99.98% of the semiconductor package, but cracks occurred due to the soldering treatment after moisture absorption.

Comparative Example 7

In Example 5, the polyimide powder obtained by adjusting the reducing viscosity to 0.30 dl / g had a glass transition temperature of 161 ° C., a thermal decomposition temperature of 395 ° C., and an extended length of 5.4 mm.

The DMF varnish of polyimide was carried out in the same manner as in Example 1 to obtain a composite adhesive sheet having an adhesion start temperature of 260 ° C., a residual solvent amount of 0.10% by weight, and a residual solvent amount of 1.6% by weight. The TSOP semiconductor package obtained in the same manner as in Example 1 had a final production yield of 99.99%, but cracks occurred due to soldering treatment after moisture absorption.

The results of the above examples are given in Table 1 below.

Tg (℃) Reduced viscosity (dl / g) Adhesive Opening Temperature (℃) Residual Solvent Amount (wt%) Residual solvent amount (% by weight) Semiconductor chip crack Semiconductor production yield (%) Example 1 182 0.71 300 0.13 1.7 Not Occurred 99.97 Example 2 190 1.21 280 0.42 1.7 Not Occurred 99.98 Example 3 187 0.48 305 0.08 2.4 Not Occurred 99.97 Example 4 172 - 270 0.10 2.3 Not Occurred 99.99 Example 5 161 0.62 270 0.14 2.5 Not Occurred 99.99 Example 6 155 0.61 270 0.10 1.8 Not Occurred 99.99 Example 7 185 0.88 260 0.19 1.9 Not Occurred 99.99 Example 8 165 0.88 260 0.51 2.8 Not Occurred 99.99 Example 9 176 0.65 285 0.05 2.1 Not Occurred 99.98 Example 10 163 0.87 260 0.08 2.2 Not Occurred 99.99 Example 11 190 1.21 280 0.10 0.8 Not Occurred 99.98 Example 12 165 0.88 250 0.92 2.2 Not Occurred 99.99 Example 13 143 - 300 0.15 2.9 Not Occurred 99.97 Example 14 148 - 290 0.11 2.8 Not Occurred 99.97 Example 15 141 - 290 0.10 1.0 Not Occurred 99.98 Example 16 151 - 270 0.06 0.6 Not Occurred 99.99 Example 17 210 0.44 320 0.53 2.4 Not Occurred 99.96 Comparative Example 1 280 0.45 430 0.05 3.6 Occur 94.47 Comparative Example 2 175 0.35 270 0.12 1.9 Occur* 99.99 Comparative Example 3 210 0.44 370 0.11 2.0 Not Occurred 94.89 Comparative Example 4 215 0.44 380 0.15 0.9 Not Occurred 94.83 Comparative Example 5 182 0.71 240 0.80 3.2 Occur 99.99 Comparative Example 6 190 0.35 280 0.40 1.7 Occur* 99.98 Comparative Example 7 161 0.30 260 0.10 1.6 Occur* 99.99

In Table 1, the cracks in the semiconductor chips of Comparative Examples 2, 6, and 7 occurred because the extruded length of the heat resistant adhesive was 5.0 mm or more.

As is apparent from the above Examples and Comparative Examples, when the heat resistant adhesive and the composite adhesive sheet of the present invention were used, a semiconductor package having excellent crack resistance and semiconductor production yield could be manufactured.

Claims (7)

Already used in the adhesive member for manufacturing the lead-on chip (LOC) type semiconductor package by bonding the semiconductor chip to the lead frame with an adhesive member and sealing at least the semiconductor chip and the adhesive portion of the semiconductor chip and the lead frame with a sealing material. A heat-resistant adhesive coating film containing a resin having a deg, having a bonding start temperature in the range of 230 to 330 ° C., a residual solvent in a range of 0.03 to 1.00% by weight, and a residual solvent in an amount of 3.0% by weight or less, Consisting of composite adhesive sheet. The composite adhesive sheet according to claim 1, wherein the glass transition temperature of the heat resistant adhesive is in the range of 150 to 200 ° C. The composite adhesive sheet according to claim 1, wherein a polyamino compound having three or more amine groups such as triamine and tetraamine is in the range of 0.01 to 5.0% by weight in the heat resistant adhesive. The composite adhesive sheet according to claim 1, wherein the extruded length of the heat resistant adhesive is in the range of 2.0 to 5.0 mm. Already used in the adhesive member for manufacturing the lead-on chip (LOC) type semiconductor package by bonding the semiconductor chip to the lead frame with an adhesive member and sealing at least the semiconductor chip and the adhesive portion of the semiconductor chip and the lead frame with a sealing material. It includes a resin having a rare group, the adhesion start temperature is 230 ~ 330 ℃ range, the residual solvent amount is 0.03 ~ 1.00% by weight, the residual solvent amount is 3.0% by weight or less, the extruded length is 2.0 ~ 5.0mm range Heat-resistant adhesive consisting only of adhesive. The heat resistant adhesive according to claim 2, wherein the glass transition temperature of the heat resistant adhesive is in the range of 150 to 200 ° C. The heat resistant adhesive according to claim 2, wherein the heat resistant adhesive has a polyamino compound having three or more amine groups such as triamine and tetraamine in the range of 0.01 to 5% by weight.