JPS61296019A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To titled composition, obtained by using tetraphenylphosphonium tetraphenylborate and triphenylphosphine as a curing accelerator and epoxysilane and mercaptosilane as a surface treating agent together and having improved moisture resistance, electrical characteristics and thermal stability, etc. CONSTITUTION:An epoxy resin composition obtained by incorporating tetraphenylphosphonium tetraphenylborate and triphenylphosphine preferably at 1:0.3-4.5 weight ratio as a curing accelerator and an epoxysilane and mercaptosilane preferably at 1:0.01-1.0 weight ratio in an epoxy resin composition containing an epoxy resin, curing agent, e.g. acid anhydride based curing agent, curing accelerator and surface treating agent. The amount of the curing accelerator to be used is preferably 0.1-0.5pts.wt. based on 100pts.wt. epoxy resin composition and the amount of the surface treating agent to be used is preferably 0.02-1pts.wt. based on 100pts.wt. epoxy resin composition respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an epoxy resin composition used for plastic encapsulation of electrical parts, electronic parts, or semiconductor devices.

[Conventional technology]

Epoxy resin compositions are widely used as insulating sealing materials for electrical parts, electronic parts, or semiconductor devices because of their good electrical properties, adhesive properties, and moisture resistance. Conventional methods for curing epoxy resins include using acid anhydrides, phenolic compounds, or amines as curing agents, and adding aliphatic tertiary amines, aromatic amines, imidazoles, Techniques using quaternary ammonium salts or organic metal salts are widely known. As the amount of the curing accelerator added increases, the curing properties can be improved, but this is accompanied by a decrease in moisture resistance, electrical properties, and thermal stability.

Therefore, the usual method has been to reduce the amount of curing accelerator added as much as possible and to find a range in which the curing properties do not slow down. However, it has been quite difficult to achieve both of these required characteristics.

In addition, since the semiconductor device itself relies on lead pins for electrical contact between the element and the outside, the adhesiveness of the interface between the material, the lead bin, and the element is as important to reliability as the curing accelerator. It has great influence.

The use of tetraphenylbosphonium tetraphenylborate as a curing accelerator was already reported in Japanese Patent Publication No. 56-45.
The use of l-riphenylphosphine is known in Japanese Patent Publication No. 47-14148, and the combined use of epoxysilane and mercapsilane as a surface treatment agent is known in Japanese Patent Publication No. 5!143062. It is publicly known. However, the epoxy resin composition described herein cannot satisfy the above-mentioned required properties.

[Problem that the invention seeks to solve]

The present invention was made as a result of careful consideration of the combination of a curing accelerator and a surface treatment agent for epoxy resin compositions in order to address the following two circumstances, and it has achieved moisture resistance that could not be achieved with conventional technology. The aim is to satisfy properties such as physical properties, electrical properties, adhesion properties, and curing properties.

[Means for solving problems]

In order to solve the above-mentioned problems, the inventors of the present invention discovered that tetrafluoride, which has extremely high thermal stability and latent curability (does not have a curing accelerating effect unless the temperature exceeds a certain temperature), is used as a curing accelerator for epoxy resins. Phenylphosphonium (tetraphenylbo l/-) and hyaku1n ding 1gyu were used in combination with triphenylbosphine, which has excellent electrical properties.Furthermore, to improve adhesion, epoxysilane and mercap 1- were used as surface treatment agents.
The purpose was achieved by using silane in combination and using these in combination. If the amount of tetraphenylphosbonium te-I, raphenylbore-1, or triphenylbosphine is increased independently, the former has too strong latent curing properties and is used in large amounts, resulting in a decrease in electrical properties, while the latter causes a decrease in electrical properties. Since it has no latent hardening property, it reduces product yield during molding and does not provide stable production during manufacturing, making it unsuitable for practical use.

In the present invention, in addition to incorporating the advantages of tetraphenylbosphonium tetraphenylbore I. By using epoxysilane and mercaptosilane together, new features were discovered that could not be achieved using either alone.

The ratio (weight ratio) of the curing accelerator used is preferably tetraphenylphosphonium tetraphenylborate 1.0
For triphenylphosphine, it is 0.3 to 4.5. If the amount of triphenylphosphine is less than 0°3, it will not be effective in shortening the mold cycle, and if it exceeds 4°5,
This is because work stability during manufacturing will be lost.

Further, the curing accelerator of the present invention is preferably used in an amount of 0.1 to 0.5 parts by weight per 100 parts by weight of the epoxy resin composition containing the epoxy resin, curing agent, curing accelerator, and surface treatment agent.

The ratio (weight ratio) of epoxysilane to mercaptosilane is preferably 1 to 1 of epoxysilane to 0.01 to 1.0 of mercaptosilane. Mercaptosilane is 0
．． If it is less than 0.01, there is no effect of improving adhesion, and if it is added in excess of 1.0, the adhesion will not be improved.

The total amount of the surface treatment agent used is preferably 0.02 to 1 part by weight per 100 parts by weight of the epoxy resin composition.

Epoxy resins that can be applied to the present invention include glycidyl ethers of phenols such as bisphenol A1 bisphenol F lusorcinol, phenol novolak, and cresol novolak; glycidyl ethers of alcohols such as butanediol and polyethylene glycol;
Glycidyl-type epoxy resins such as glycidyl esters of carboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidyl-type epoxy resins such as those in which the active hydrogen bonded to the nitrogen atom of aniline and isocyanuric acid is replaced with a glycidyl group; and alicyclic-type epoxy resins. etc. are used.

Further, as the curing agent, a known acid anhydride curing agent, amine curing agent, or novolak type phenol type or cresol type resin curing agent is used.

The epoxy resin composition referred to in the present invention is not only a combination of the above-mentioned epoxy resin, curing agent, curing accelerator, and surface treatment agent, but also contains calcium carbonate, silica,
It also includes those containing fillers such as talc and quartz glass, mold release agents, flame retardants, colorants, and various modifiers.

The epoxy resin composition of the present invention can be produced by kneading the above-mentioned ingredients while heating them with a mixing roll.

〔Example〕

The present invention will be explained in more detail below by showing examples and conventional examples. In addition, parts in each example mean parts by weight.

Example 1 (A) 100 parts of Talesol novolac type epoxy resin (Nippon Kayaku Co., Ltd., trade name EOCN-102) (B) Phenol formaldehyde novolac resin
50 parts (manufactured by Hitachi Chemical, product name 14P-
607N) (C) Silica powder 410
Part CD) Carnauba wax Part 2 (E)
Carbon blank 1 part (F) Epoxy silane 3 parts (manufactured by Shin-Etsu Silicone)
Product name KBM-403) (G) Mercaptosilane
0.2 parts (manufactured by Shin-Etsu Silicone, product name: KBM)
-803) (I+) ) Riphenylbosphine
1 part (1) Tetraphenylphosphonium tetraphenylborate 1 part The above composition was preheated to 75 to 85°C and kneaded with heating for about 8 minutes using a mixing roll to make a homogeneous composition, then cooled to room temperature and pulverized. The desired resin composition was obtained. Table 1 shows the properties of the cured product of the obtained epoxy resin composition.

(Comparative Example 1.2.3.4) In Example 1, each composition of (A) to (G) was made the same, 2 parts of triphenylphosphine (■) was added, and kneaded in the same manner as in Example 1. The composition obtained was designated as Comparative Example 1,
Comparative Example 2 was a composition obtained in the same manner as in Example 1 except that (A) to (G) were the same, except for (11), and 2 parts of (I) tetraphenylphosphonium tetraphenylborate was added. .

Further, in Example 1, (8) to (F) (I+) (
Comparative Example 3, (8) to (E) (+
1) A composition obtained in the same manner as in Example 1 except that (■) was the same, except for (F) and 3 parts of mercaptosilane (G) was added was used as Comparative Example 4.

The curing properties of each composition are also listed in Table 1. In Table 1, the viral flow is EMMI-1-66, and the gel time is JIS.
5906, the hot hardness was measured using a Shore hardness tester type D within 10 seconds after molding. Melt viscosity was measured using Koka type flow tester (manufactured by Shimadzu Corporation), and secondary transition point was measured using TMA.
(manufactured by Rigaku Denki Co., Ltd.), volume resistivity is JIS, 691
1. Water absorption was tested in accordance with JIS 6911.

In order to examine the working stability of Example 1 and Comparative Examples 1 and 2, the relationships among heating temperature, kneading time, and fluidity (spiral flow) are shown in FIGS. 1 and 2. From FIG. 1 and FIG. 2, it can be seen that the stability during production of Example 1 of the present invention is almost the same as that of Comparative Example 2, and is not easily affected by kneading time and kneading temperature. Normally, Example 1, which is a combination system of Comparative Examples 1 and 2, should be at an intermediate level between Comparative Examples 1 and 2, but the result is actually closer to that of Comparative Example 2, which has thermal stability. It is thought that the thermal stability was improved due to the interaction.

Next, when comparing the physical property data in Table 1, it is found that the volume resistivity value, which is a guideline for electrical properties, is located at an intermediate level between Comparative Examples 1 and 2 in the case of Example 1 of the present invention. Recognize.

Table 1 also shows the results of examining the curability of each of these compositions using a mounting mold. The mold used was IC16 Bin DTP.
(Dual in-line) type 84 holes and 40 pin D
It has an IP rating of 80, and the hardenability is expressed by the time it takes to reach Shore hardness of 80 or higher. The number of defects occurring at that time was also tested. It can be seen that Example 1 of the present invention had a small number of defects and a good molding yield.

After assembling the device into Test 1 and using the DTP16 bottle mold described above, samples for evaluation of moisture resistance in Presso Shark Socates 1-1 were prepared using each composition. The test device size used was (i x 4. mm, aluminum wiring 1) 10 μm, and the device did not have an inorganic protective film, and its wiring pattern is shown in FIG. 3. These results are also listed in Table 1. The present invention Example 1: Preso Shark Soca Test 3
It can be seen that even at 000h, no defects were observed due to aluminum disconnection, showing good results. An analysis of the phenomenon in which defects occurred in Comparative Examples 1 to 4 revealed that all of them were disconnections due to corrosion of the aluminum wiring.

The difference between Comparative Examples 1 and 2 is due to the curing accelerator itself, and it was confirmed that the former caused corrosion in a part of the corner of the element, and the latter caused corrosion in the entire element. The reason for this is that in the case of Comparative Example 1, due to the lack of thermal stability, distortion due to rapid curing was concentrated in a part of the corner of the element, weakening the adhesiveness between the material and the element.

Furthermore, the reason why Comparative Example 3 is weak is due to the low adhesive strength. Comparative Example 4 is generally good except for Example 1, but since it does not use epoxy silane (51), the adhesion (wettability) between the filler and the epoxy resin decreases, so the present invention It seems that the reliability was inferior to that of Example 1.

The adhesion shown in Table 1 was determined by placing each molded product, Zumble, in methanol in which red dye had been dissolved, applying 5 atm and leaving it for 6 hours, cutting the interface with the lead pin, and determining the penetration level. ◎ indicates almost no infiltration, and △ indicates almost half infiltration.

[Effects of the Invention] According to the present invention, a good epoxy resin composition that is compatible with moisture resistance, electrical properties, adhesiveness, thermal stability, and curability was obtained.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the relationship between kneading time and fluidity of the materials of Examples and Comparative Examples, and FIG. 2 is a diagram showing the relationship between kneading temperature and fluidity. FIG. 3 is a schematic diagram of the test element used to evaluate moisture resistance. Explanation of symbols 1 Gold wire bonding pad 2 Aluminum wiring 3 Silicon] 1 training time (minutes) Fig. 1 General Tokodo ('C) Fig. 2

Claims (1)

[Claims] 1. In an epoxy resin composition containing an epoxy resin, a curing agent, a curing accelerator, and a surface treatment agent, tetraphenylphosphonium tetraphenylborate and triphenylphosphine are used as the curing accelerator, and epoxysilane and mercaptosilane are used as the surface treatment agent. An epoxy resin composition characterized in that it is used in combination.