JPS6084321A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin composition excellent in moisture resistance, rust prevention, and adhesiveness, by mixing an epoxy resin with a curing agent, lanolin or its derivative, and a petroleum-derived lubricating oil. CONSTITUTION:An epoxy resin is mixed with a curing agent, and an additive comprising lanolin and/or its derivative and a petroleum-derived lubricating oil. If desired, an inorganic filler is added to improve dimensional stability, thermal properties, workability, etc. Desirable epoxy resins are phenol novolak epoxy resin or cresol novolak epoxy resin from the viewpoint of electrical properties, heat resistance, etc. Part of the above additive, such as lanolin, reacts with neither the epoxy resin nor the curing agent, and exudes from the resin when or after the epoxy resin composition is applied to an electrical part for its sealing. This component of the additive reaches the surface of the sealed electrical part to form a rust-preventive film, so that the electrical part can be protected.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an epoxy resin composition used as a sealing resin for semiconductor devices and other electronic circuit components.

Generally, epoxy resins are made of amines or acid anhydrides.

When cured using a curing agent such as phenolic resin, a product with excellent electrical, mechanical, and thermal properties can be obtained.
It is used as a sealing resin to protect semiconductor devices and other electronic circuit components from external air and mechanical shock. Furthermore, resin sealing using epoxy resin has many advantages in terms of productivity and economy compared to sealing using ceramic or metal, and is therefore widely used.

By the way, the recent increase in the density of semiconductor devices, 1! Due to changes in the usage environment due to the diversification of applications for sub-circuit components, high temperatures,
Epoxy resin compositions are required to be reliable in maintaining the functionality of electrical components under high humidity conditions. However, conventional compositions have fundamental problems, including the high temperatures required.

It was difficult to satisfy all electrical properties under high humidity.

In other words, the low moisture resistance and low corrosion resistance of resin sealing with conventional epoxy resin compositions are due to the direct contact between the resin and electrical components and the fact that resin sealing is not airtight. Therefore, its improvement is extremely difficult and rare. Epoxy resin absorbs or permeates moisture due to the polar groups remaining in the cured product. Furthermore, epoxy resins contain ionic impurities such as chlorine produced from epichlorohydrin used as a raw material during synthesis or sodium derived from sodium hydroxide used for dechlorination, and large amounts of these impurities are present in the raw materials. Contains ionic impurities. However, due to the interaction between the absorbed or permeated water and ionic impurities, the functionality of resin-sealed electrical parts deteriorates, such as a decline in insulation and an increase in leakage current. This damages the aluminum wiring and electrical 4M used in the parts, eventually leading to wire breakage.

In addition, at high temperatures, ionic impurities and other polar substances contained in the resin become more mobile due to activation of thermal motion, and when an electric field is generated in parts such as elements, the field between the resin and parts such as elements increases. ”, these ionic impurities are further activated, locally reducing the electrical properties, and if moisture is present, the maturation will progress rapidly.

Adversely affect.

In order to deal with these problems, recent proposals have been made to reduce the ionic impurities in epoxy resins and to improve the adhesiveness between electrical parts and resins to block moisture infiltration. There is.

However, it is still difficult to completely remove ionic impurities from the resin, and furthermore, problems with mold releasability during resin sealing arise due to improved adhesion between electrical components and the resin.

In view of the above-mentioned shortcomings, the inventors of the present invention have conducted intensive studies and found that the epoxy resin composition contains a component that forms an anti-rust film that prevents the infiltration of moisture and ionic impurities. During or after resin sealing, the anti-conjunctiva-forming component is exuded.

The idea was to form an anti-rust film on the surface of electrical parts.

The present invention has been accomplished.

The object of the present invention is to provide an epoxy resin composition with excellent moisture resistance and rust prevention properties.

That is, the epoxy resin composition of the present invention is characterized by comprising an epoxy resin, a curing agent, and an additive consisting of one or both of lanolin and a lanolin derivative and a petroleum-based lubricating oil.

According to the present invention, it is possible to provide an epoxy resin composition having excellent moisture resistance, rust prevention, and adhesiveness.

In the present invention, such effects can be obtained when an additive consisting of one or both of lanolin or lanolin derivatives mixed with an epoxy resin and petroleum-based lubricating oil is used as an all-resin sealant in an epoxy resin composition. It is thought that this is because it is present between the composition and the object to be coated, and exerts its full effect of preventing external moisture and ionic impurities from penetrating into the surface of the object to be coated. As described above, the resin composition of the present invention prevents moisture and onic impurities from penetrating into the interface with the object to be coated, and thus exhibits moisture resistance and Q11 resistance.

It has excellent adhesive properties.

Furthermore, since the epoxy resin composition of the present invention has the above-mentioned effects, it can also be used in applications other than resins for sealing electrical parts.

It can also be used in paints, adhesives, etc.

Next, when the resin composition of the present invention is used as a sealant for electrical parts, the additives such as lanolin can be prevented from forming at the interface between the surface of the electrical parts and the epoxy resin during or after the resin sealing. It is thought that a rust film is completely formed. As a result, moisture from the outside and ionic impurities in the epoxy resin are blocked from penetrating into the surface of the electronic component, thereby preventing a decrease in the insulation properties of the electrical component or a decrease in functionality such as an increase in leakage current. This means that the number of electrical components can be expanded.

Further, since the above-mentioned additives as anti-rust film forming components are embedded in the epoxy resin composition, there is no need for the step of applying a rust-preventive film to the surface of the electrical component.

Epoxy resins that can be used in the present invention are commonly known ones and are not particularly limited. Examples include glycidyl ether type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, dalicidyl ester thread epoxy resin, linear aliphatic epoxy persimmon fat, halogenated epoxy resin, and the like.

These epoxy resins may be used alone or in a mixture of two or more. Among the above epoxy resins, phenol novolak epoxy resins and cresol novolac epoxy resins are preferred from the viewpoint of electrical properties, heat resistance, etc., and can provide the most excellent properties. These epoxy resins.

The following curing agent causes a curing reaction and solidifies.Curing 111J includes acid anhydrides such as phthalic anhydride, succinic anhydride, and methylnadic anhydride, metaphenylene diamine, diaminodiphenyl nulpon, and aromatic amines. Examples include aromatic amines such as adducts, aliphatic or aliphatic amines such as polymethylene diamine and menthanediamine, and initial condensation products of synthetic resins such as phenol resins and cresol resins, but are not limited to iF&. However, among the above-mentioned curing agents, phenolic resins, cresol resins, and other early stage rice compounds are preferred from the viewpoint of electrical properties, heat resistance, and the like.

In the present invention, the fjd combination ratio of the epoxy resin and the curing agent is such that the chemical equivalent ratio between the number of functional groups in the curing agent and the number of epoxy groups in the epoxy resin is within the range of 0.5 to 1.5. In terms of curing properties such as storage stability, properties, curing speed, and thermal/mechanical properties after curing, it is preferable to incorporate the curing agent into a curing agent. Furthermore, excellent curing properties can be obtained when the chemical equivalent ratio is within the range of 0.8 to 1.2.

Furthermore, in the present invention, when the above curing agent is used, a curing accelerator may be used to accelerate the curing speed.

The curing accelerator is not particularly limited, but examples thereof include imidazole, 2-methylimidazole, and 2-phenylimidazole.

2. Imidazoles such as 4-dimethylimidazole, triethylamine, diethylaminoprobylamine, N-
Examples include amines such as aminoethylpiperazine, and complex compounds of triethylamine and B F x. Also,
These curing accelerators may be used alone or in a mixture of two or more. However, the blending ratio of this curing accelerator may generally be within the range of 0.05 to 5 parts by weight per 100 parts by weight of the epoxy resin.

Some of the lanolin, lanolin derivatives, and petroleum-based lubricating oil additives according to the present invention do not react with epoxy resins and curing agents, and are used in resins during or after resin sealing of electrical components with epoxy resin compositions. It seeps out to the outside. The components of this additive reach the surface of the sealed electrical component and completely form a rust-preventing film. The anticorrosive film has excellent moisture resistance, prevents the infiltration of ionic impurities, and can protect all electrical components.

Lanolin as an additive mentioned above refers to wool fat.

IJW is an ester of fatty acid and monohydric higher alcohol.

The type thereof is not particularly limited, but in order to form a rust-preventing film containing no impurities, it is preferable to use RI-forming such as deodorization, dehydration, and decolorization.

In addition, the lanolin derivatives in Episode 9 include lanolin fatty acids obtained by removing the alcohol content from lanolin, barium lanophosphate, magnesium lanophosphate,
Examples include lanolin fatty acid metal salts such as zinc lanophosphate, aluminum lanophosphate, calcium lanophosphate, and sodium lanophosphate.

In the present invention, one or both of lanolin and lanolin derivatives are used.

The amount of lanolin or lanolin mold 44 to be blended is preferably 0.1 to 10 parts by weight per 100 parts by weight of the epoxy resin. When the amount is less than 0.1 part by weight, the moisture resistance and rust prevention effects of the present invention are difficult to be exhibited;
If it becomes more than 0 times origin.

Although the effect of the addition is improved, there is a risk that other properties of the composition, such as adhesion, may deteriorate.

Also, the above petroleum lIE lt? Oil is a complex mixture whose main components are hydrocarbons with a single molecular weight. The petroleum-based 71
As for 1 mountain in 7 months, there are 4 temples and 4 temples, but 1 in 1 is not covered.

For example, mendre 710, cold %? Examples include i oil, engine oil, cylinder oil, gear oil, nitrogen lubricating oil, and liquid paraffin. In this invention, one or more of the following petroleum oils are used.

” The blending amount of petroleum-based lubricating oil is epoxy &lI
It is desirable to set it as 0.1 to 10 feet per 100 fingers. On the other hand, if the amount is less than 0.1 part by weight, the moisture-proofing and rust-preventing effects of the present invention are difficult to exhibit.

If the amount exceeds 10 parts by weight, the effect of addition will be improved, but there is a risk that other properties such as adhesion may be completely degraded. Even better moisture resistance and rust prevention properties can be obtained when the above-mentioned amount is within the range of 1 to 6 parts by weight.

The present invention focuses on the above components, namely (8) epoxy resin, (/I)
Although the curing agent may be composed of additives such as iron, it is possible to create an epoxy with improved dimensional stability, thermal properties, workability, etc. by adding an inorganic filler. The entire resin composition can be written.

Examples of inorganic fillers include zirconia, alumina, talc, clay, magnesia + RF4tM silica.

Crystalline silica, calcium silicate, ash 11υ calcium.

Barium sulfate, glass fiber, milled phyno-t-
can be mentioned. Among these, fused silica and crystalline silica are most preferred.

In addition, the epoxy resin composition according to the present invention may optionally be used with 1 release agents such as natural waxes, 9 synthetic waxes, metal salts of linear fatty acids, acid amides, esters, or mixtures thereof, and chlorinated Nozeta rough fin, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin.

Flame retardants such as bromotoluene, hexabromobenzene, antimony trioxide, and silane coupling agents.

A surface treatment agent such as a titanium coupling agent, a d coloring agent such as carbon black, etc. may be appropriately added and blended.

A general method for producing the epoxy resin composition according to the present invention is to thoroughly mix all of the above raw materials in a mixer such as a Henschel mixer.

Melt and knead with a kneader such as a hot roll machine or a kneader,
There is a method of cooling and crushing.

Next, the present invention will be explained in detail.

Examples Ortho-cresol novolak epoxy resin as epoxy resin, purified lanolin as lanolin or calcium lanophosphate as lanophosphate metal salt, and nuvindol oil and liquid paraffin as petroleum-based lubricating oil.
In addition to mixing in the proportions shown in the table (all numerical values for blending amounts represent parts), 50* parts of phenol novolak as a hardening agent, 1) 2- parts as a curing accelerator, Adding 3 parts by weight of phenylimidazole, 350 parts by weight of fused silica as an inorganic filler, 2 parts by weight of epoxysilane as a surface treatment agent, and 2 parts by weight of Karuna 4 as an IT type agent, Mixed.

Next, this material was melt-kneaded in a roll mill for /θ minutes at a total temperature of 90°C, and immediately cooled and assimilated.

Thereafter, the pulverized product was molded into tablets to prepare five types of epoxy resin compositions (sample floors 1 to 5 in Table 1) according to the present invention.

For comparison, as shown in Table 1, only lanolin or calcium lanophosphate was used as an additive, or only the above petroleum-based lubricating oil, and no additives were used.
Other than that, all comparative epoxy resin compositions (Samples C1 to C5) were prepared under the same conditions as in Section 2, using the same ingredients and the same amount.

Aluminum wiring using the above 10 types of epoxy resin compositions! 175°C for a model element with poles;
Complete sealing was performed in 5 minutes by transfer molding, and the resin was further cured by heating at 165° C. for 8 hours to complete resin sealing.

To fully test the performance of these sealed samples, these samples were heated to 121°C+28. A Gresochar cooker test was conducted with a bias voltage of 12V applied in saturated steam at tB. Accordingly, the average lifespan of each sample was measured, and its moisture resistance was fully evaluated.

The results are shown in Table 2. ζWhat is the average lifespan?

This is the time it takes for aluminum wiring or electrodes to wear out and lose their electrical conductivity.

As is clear from Table 2, when the epoxy resin composition according to the present invention is used, the average life is significantly improved compared to the comparative composition even under high temperature and high humidity. It has been found that the resin composition of the present invention is also extremely useful as a sealing resin for electrical parts.

Table 1 Table 2 Procedural amendment (voluntary) Commissioner of the Patent Office 1, Indication of the case 1988 Patent Application No. 198065
No. 2, Title of the invention Epoxy resin composition 3, Relationship with the case of the person making the amendment Patent applicant 41-1 Aki Aza Yokodori, Oaza Ai, Nagakute-machi, Aichi-gun, Aichi Prefecture (
860) Shiho U Co., Ltd.] Central Research Institute Representative Director Noboru Komatsu 4, Agent Aichi Prefecture Aichi? ltl Nagakute-machi Oaza Nagashinaji Yokodori 41-15, Subject of amendment Column 6 of "Detailed Description of the Invention" of the specification, Contents of the amendment The description in the specification is amended as follows.

(1) On page 18, line 16, the term epoxy resin is defined as 100-ffl parts of epoxy resin.

(2) On page 18, line 18, “Try, spindle oil.”
Let's say this is spindle oil.

Claims (6)

[Claims] (1) An epoxy resin composition comprising an epoxy resin, a curing agent, and an additive consisting of one or both of lanolin or a lanolin derivative and a petroleum-based lubricating oil. (2) Epoxy resins include glycidyl ether thread epoxy resin, phenol novolac thread epoxy resin, cresol novolak epoxy resin, alicyclic epoxy resin,
The epoxy resin composition according to claim (1), comprising at least one of a grindyl ester epoxy resin, a linear aliphatic epoxy resin, and a non-logenated epoxy resin. (3) The epoxy resin composition according to claim (1), wherein the lanolin derivative is at least one of lanolin fatty acids and lanolin fatty acid metal salts. (4) Lanolin fatty acid metal salts include barium lanophosphate, magnesium lanophosphate, and lanolin ¥2 zinc. Aluminum lanophosphate, calcium lanophosphate. The epoxy resin composition according to claim (3), which is sodium lanophosphate. (5) One or both of lanolin and lanolin derivatives is added in an amount of 0.1 to 10% per 100 parts of epoxy resin.
The epoxy resin composition according to claim (1), wherein the epoxy resin composition is arranged in a sub-site. (6) The epoxy resin composition according to claim (1), wherein the petroleum-based lubricating oil is blended in an amount of 0.1 to 10 parts per 100 units of epoxy horse chestnut resin.