JPS61272262A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent moisture-resistance and heat-resistance and suitable as a resin for the sealing of semiconductor devices, electronic circuit parts, etc., by compounding an epoxy resin with specific amounts of a curing agent, a specific organometallic compound, a petroleum sulfonic acid metal salt and a dithiocarbamic acid metal salt. CONSTITUTION:The objective composition can be produced by compounding (A) an epoxy resin (e.g. glycidyl ether epoxy resin) with (B) a curing agent (e.g. a precondensate of a synthetic resin such as phenolic resin), (C) one or more organometallic compounds selected from organic aluminum compound, organic titanium compound, etc., (D) a petroleum sulfonic acid metal salt of formula I (M is Ca, Ba, etc.; R<1> is paraffinic side chain or an aromatic hydrocarbon residue containing naphthene ring in the molecule) and (E) a dithiocarbamic acid metal salt of formula II (R<2> and R<3> are 1-18C alkyl, etc.; M is Zn, etc.). The amounts of the components C, D and E are 0.01-5(wt)%, 0.1-10% and 0.1-10% based on the component A, respectively.

Description

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

[Conventional technology]

BACKGROUND ART Conventionally, epoxy resin compositions containing acid anhydrides, amines, phenolic resins, etc. as hardeners have been widely used as sealing materials for electrical components such as transistors, diodes, ICs, and LSIs.

This is because epoxy resins are superior to other thermosetting and thermoplastic resin materials in terms of physical properties such as mechanical properties, electrical properties, thermal properties, and moldability. This is because it is superior to hermetic seal systems using metal materials or ceramic materials in terms of performance and economy.

However, in recent years, with the development of the electronics field, epoxy resin compositions have come to be used in a wide variety of applications2.For example, their use outdoors in extremely cold or hot and humid regions, as typified by automobiles, is also increasing. .

Furthermore, as typified by the 256-bit VLSI, electronic circuits are rapidly becoming denser and finer. As a result, cases have frequently been reported in which electrical components suffer catastrophic failures due to the effects of external heat and humidity, especially during practical operation.

Many of these defects are said to be due to the effects of ionic impurities contained in the epoxy resin composition and moisture that has entered from the outside world.

That is, since the molded body of the epoxy resin composition itself has moisture permeability, moisture that has entered the molded body permeates to the surface of the resin-sealed electrical component, causing corrosion and deterioration of metal electrodes such as aluminum. Also.

Along with moisture permeation, moisture also infiltrates from the lead frame interface.
Corrodes as well. Furthermore, water dissolves organic acids and ionic impurities such as Na'' and CI- contained in the epoxy resin, and transports them to the surface of electrical parts to form local batteries, further accelerating corrosion.These epoxy resins Ionic impurities contained in the resin are derived from the synthetic raw material epichlorohydrin and the subsequent alkaline cleaning process, so it is virtually impossible to completely remove them. Epichlorohydrin causes a side reaction and remains as hydrolyzable chlorine in the epoxy resin, and these hydrolyzable chlorines are ionized by the catalytic action of heat and other factors and corrode aluminum electrodes and the like.

Therefore, various proposals have been made to deal with these problems.
1341) No. 2), Selection of Internal Mold Release Agent (Unexamined Japanese Patent Publication No. 58)
-152047), addition of additives to capture ionic impurities in epoxy resin compositions (Japanese Patent Laid-Open No. 58
Although various attempts have been made, such as Japanese Patent Application Laid-open No. 174435 and Japanese Patent Application Laid-open No. 176237/1983, no particularly significant effects have been obtained.

[Problem that the invention seeks to solve]

The present invention was made in view of the above-mentioned problems, and aims to provide an epoxy resin composition having excellent moisture resistance and heat resistance.

[Means for solving problems]

The epoxy resin composition of the present invention comprises an epoxy resin, a curing agent, and one or more of an organic aluminum compound, an organic titanium compound, an organic zirconium compound, an organic tin compound, an organic lead compound, an organic zinc compound, an organic chromium compound, or It is characterized by comprising an organic metal compound consisting of two or more types and an additive consisting of a petroleum sulfonic acid metal salt and a dithiocarbamate metal salt.

The epoxy resin used in the present invention may have at least two epoxy groups in two molecules, and is not particularly limited to a structure with a molecular weight of 5 molecules. Examples include glycidyl ether-based epoxy resins, phenol novolac-based epoxy resins, cresol novolak-based epoxy resins, alicyclic epoxy resins, glycidyl ester-based epoxy resins, and halogenated epoxy resins.

Therefore, one kind or a mixture of two or more kinds of these epoxy resins are used. Among the above epoxy resins, phenol novolac epoxy resins and cresol novolac epoxy resins are preferred from the viewpoint of electrical properties, heat resistance, etc.
The most excellent characteristics can be obtained. These epoxy resins undergo a curing reaction and are solidified by the following curing agent.

Next, as curing agents, phthalic anhydride, succinic anhydride,
Acid anhydrides such as methylnadic anhydride, aromatic amines such as metaphenylene diamine, diaminodiphenylsulfone, and aromatic amine adducts, aliphatic or alicyclic amines such as polymethylene diamine and menthanediamine, phenolic resins, cresol resins, etc. Examples include, but are not limited to, synthetic resin initial metal bars. As the curing agent, one type or a mixture of two or more types may be used. However, among the above-mentioned curing agents, synthetic resin initial metal bars such as phenol resins and cresol resins are preferred from the viewpoint of electrical properties, heat resistance, and the like.

In the present invention, regarding the compounding ratio of the epoxy resin and the curing agent, the chemical equivalent ratio (number of epoxy groups/number of functional groups) between the number of functional groups in the curing agent and the number of epoxy groups in the epoxy resin is 0.5. Blending so that it is within the range of ~1.5,
Storage stability, curing speed.

It is preferable in terms of curing properties such as thermal and mechanical properties after curing. Furthermore, the excellent curing properties are due to the above chemical equivalent ratio of 0.8 to 1.
It can be obtained when it is within the range of 2.

In addition, in the present invention, when the above-mentioned curing agent is used, a curing accelerator may be used to accelerate the curing speed.
The curing accelerator is not particularly limited, but examples include imidazoles such as 2-methylimidazole, 2-phenylimidazole, and 2,4-dimethylimidazole, triethylamine, diethylaminopropylamine,
Amines such as benzyldimethylamine and N-aminoethylpiperazine, triethylamine, etc. and boron trifluoride (
Examples include complex compounds with BFz). Also.

These curing accelerators may be used alone or in a mixture of two or more. Therefore, when adding this curing accelerator, its amount is generally 0.00% relative to the epoxy resin.
The content is preferably within the range of 5 to 5% by weight.

The additive comprising the organometallic compound, petroleum sulfonic acid metal salt, and dithiocarbamate metal salt according to the present invention improves the moisture resistance of the epoxy resin composition.

It improves heat resistance.

In the present invention, the organometallic compound includes a perforated aluminum compound, an organic titanium compound, an organic zirconium compound, an organic tin compound, an organic lead compound, an organic zinc compound,
One or more organic chromium compounds.

Examples of organoaluminum compounds include those having an alkoxy group such as a methoxy group or a propoxy group, an acyloxy group such as a phenoxy group or an acetoxy group, and a complex compound with acetylacetone.

Specifically, aluminum isopropylate, aluminum butyrate, aluminum S-butyrate, aluminum t-butyrate aluminum diisopropylate
Tomono S-butyrate.

Aluminum isopropylate di-S-butyrate, aluminum octylate, aluminum laurate, aluminum stearate, aluminum oxide isopropylate, aluminum oxide octylate,
Aluminum oxide stearate, aluminum octylate, aluminum oxalate, aluminum benzoate.

Examples include aluminum trisethyl acetoacetate, aluminum isopropoxyethyl acetoacetate, aluminum dibutoxyacetoacetate, aluminum dibutoxymonoethyl acetate, and the like. Therefore, one or more of these organoaluminum compounds are used.

Examples of organic titanium compounds generally include titanium alkoxides, monomers and polymers of chelate compounds, coordination compounds, and the like.

Specifically, tetraisopropyl titanate tetrabutyl titanate, tetra 2-ethylhexyl titanate,
Tetrastearyl titanate.

Isopropyl tristearyl titanate, tributyl stearyl titanate, butyl titanate dimer, polytripropyl titanate polybutyl titanate polytributyl stearyl titanate, titanium acetylacetonate, titanium ethyl acetoacetate, titanium octylene glycolate, dihydroxybis(lactate)
Titanium.

Tetraoctylene glycol titanium, dipropoxytitanium bis(lactate), polytitanium acetylacetonate, polyhydroxytitanium stearate, isobrobyl tridodecylbenzenesulfonyl titanate, isopropyltris(dioctylpyrophosphate) titanate, tetraisopropylbis(dioctylphosphite) Titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl) bis(di-tridecyl phosphite) titanate, bis(dioctyl pyrophosphate) oxyacedo titanate.

Examples include bis(octyl birophosphate) ethylene titanate. Furthermore, fatty acids (12 to 1 carbon atoms)
8) Titanium, titanium oxalate, titanium benzoate, etc. may be used. Therefore, one or more of these organic titanium compounds are used.

Organic zirconium compounds generally include alkyl groups,
Examples include those having an aromatic group, an alkoxy group, an acyloxy group, etc., and a complex compound of zirconium and acetylacetone.

Specific examples include tetrabutyl zirconate, zirconium stearate, zirconium octylate tetrabutoxyzirconium, zirconium tetrakis (acetylacetate), zirconium acetylacetonate, etc., and one or more of these are used. .

The organic tin compound is generally an alkyltin compound or an alkyltin mercaptide compound.

Alkyltin sulfide compounds, alkyltin unsubstituted -
carboxylic acid salt compounds, alkyltin maleic acid compounds, alkyltin fumaric acid compounds, alkyltin substituted carboxylic acid salt compounds, alkyltin acid compounds, alkyltin inorganic acid salt compounds, bis(alkyltin) oxide compounds, acetyl hydroxytin compounds, acetylalkoxytin compounds compounds, aryltin compounds, ferratetin compounds.

Examples include tin core carboxylic acid compounds, tin side chain carboxylate compounds, tin aliphatic carboxylates, and the like.

More specifically, tetrabutyltin, dibutyltin dilauryl mercaptide, butyltin trisdodecyl mercaptide, dimethyltin sulfide.

Monooctyltin sulfide, tributyltin laurate, tributyltin oleate, dibutyltin dilaurate, dibutyltin distearate.

Dibutyltin laurate maleate Dioctyltin laurate maleate, tributyltin acetate, trimethyltin maleate Tributyltin maleate, tributyltin gluconate.

Dibutyltin oxide, bistributyltin oxide, tetraphenyltin, tributyltin butyl ferrate, tributyl benzoate, triphenyltin benzoate, triphenyltin terephthalate, tributyltin cinnamate, etc., and one or two of these
Use more than one species.

Organic lead compounds generally include lead salts of fatty acids such as lead acetate and lead stearate, lead maleate, lead phthalate, lead salicylate, lead borate, and lead naphthenate.

Lead 2-ethylhexylate, dimethyl isophthalate-5-
Lead sulfonate, lead benzoate, alkyl (1 to 12 carbon atoms)
) Lead benzoate, lead β-resorucinate.

Examples include aromatic compounds such as tetraphenyl lead.

One or more of these may be used.

Organic zinc compounds generally include fatty acid zinc such as zinc stearate and zinc laurate, zinc naphthenate, zinc phthalate, zinc benzoate, aromatic compounds such as zinc alkyltin 1 to 12) penzetyl sulfonate, and diethyl zinc. ,
Zinc 2-ethylhexanoate, zinc ricinoleate, zinc 2-ethylhexoinate, zinc salicylate, zinc octylate, metal complex salts of zinc and acetylacetone, zinc dimethylthiocarbamate cyclohexylamine complex, etc. One or more of these are used.

Organic chromium compounds generally include complex salts of chromium and acetylacetone, chromium and 2-(2-hydroxy-5-
complex salt with nitrophenylthiazoacetoacetanilide),
Examples include chromium salicylate, alkyl (8 to 50 carbon atoms) chromium salicylate, and one or two of them.
Use more than one species.

The above organic aluminum compounds, organic titanium compounds, organic zirconium compounds, and organic tin compounds.

The amount of the organic metal compound consisting of one or more of organic lead compounds, organic zinc compounds, and organic chromium compounds is 0.01 to 5% by weight based on the epoxy resin.
It is desirable to do so. When the amount is less than 0.01% by weight, the moisture resistance and heat resistance effects of the present invention are difficult to be exhibited;
If it exceeds the weight%, although the addition has an effect,
Other properties 1, such as moldability, may be deteriorated.

Petroleum sulfonic acid metal salts are metal salts obtained by neutralizing and refining oil-soluble sulfonic acids obtained by sulfonating petroleum lubricating oil components, and the general chemical formula is (R'SOz).
It is expressed as tM (in this chemical formula).

M is a monovalent metal element such as calcium (Ca), barium (Ba), magnesium (Mg), zinc (Zn), and RI is a monocyclic or bicyclic metal element having a paraffin side chain and a naphthene ring in the molecule. ring aromatic hydrocarbon group, SOI
is a sulfone group and is bonded to an aromatic ring. ■ represents an integer).

Alternatively, a petroleum sulfonic acid metal salt containing a base greater than the theoretical amount may be used. The petroleum sulfonic acid metal salt is not particularly limited, but preferably, the larger the molecular weight and the higher the purity, when used as an additive, exhibit excellent moisture resistance and heat resistance. Among these, even more excellent properties can be obtained when a metal salt of mahogany acid obtained from a long-chain alkylaryl monosulfonic acid is used.

In the present invention, one or more of the above petroleum sulfonic acid metal salts are used.

The amount of the above petroleum sulfonic acid metal salt is as follows.

It is desirable that the amount is 0.1-10% by weight based on the epoxy resin. When the content is less than 0.1% by weight, the moisture and heat resistance effects of the present invention are difficult to be exhibited.On the other hand, when it is more than 10% by weight, the effects are improved by addition, but rather other properties such as moldability are impaired. There is a risk of lowering the Even better moisture resistance.

Heat resistance is obtained when the above-mentioned amount is within the range of 1 to 6 f [% by weight].

The above-mentioned dithiocarbamate metal salt generally has the following chemical formula [
Examples of zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, and zinc di-n-propyldithiocarbamate include, but are not limited to, those represented by A).

Zinc di-n-butyldithiocarbamate, zinc di-n-amyldithiocarbamate, zinc di-1so-amyldithiocarbamate, zinc di-n-octyldithiocarbamate, zinc di-2-ethylhexyldithiocarbamate, N-ethyl-N-phenyl Zinc dithiocarbamate, zinc N-pentamethylene dithiocarbamate, copper dimethyldithiocarbamate, copper diethyldithiocarbamate.

Examples include lead N-pentamethylene dithiocarbamate, lead N-pentamethylene dithiocarbamate, and ferric N-pentamethylene dithiocarbamate. In the present invention, one or more of these dithiocarbamic acid metal salts are used.

(However, in the above formula, R2 and R2 have 1 to 1 carbon atoms.
Represents 8 alkyl groups, aryl groups, alkenyl groups, aralkyl groups, which may be the same or different, and further RZ,
R3 may form one ring. M is zinc (Zn)
, molybdenum (Mo), iron (Fe), nickel (Ni)
, copper (Cu), lead (Pb), tellurium (Te), and other metal elements, m and n each represent an integer. ) The amount of the dithiocarbamate metal salt blended is preferably 0.1 to 10% by weight based on the epoxy resin, and is less than 0.1% by weight.

On the other hand, the moisture resistance and heat resistance effects of the present invention are difficult to exhibit.

When the amount exceeds 10% by weight, the effect of addition is improved, but other properties such as moldability may be deteriorated. Even better moisture resistance and heat resistance can be obtained when the above-mentioned amount is within the range of 1 to 6% by weight.

When one of the above additives is used as petroleum sulfonate metal salt such as petroleum zinc sulfonate, or as dithiocarbamate metal salt such as dithiocarbamate zinc salt or dithiocarbamate lead salt, it can also be used as the organometallic compound. .

However, in the present invention, the three additives of organometallic compound, petroleum sulfonic acid metal salt and dithiocarbamate metal salt synergistically improve moisture resistance and heat resistance. Preferably heterogeneous.

The present invention focuses on the above component, namely (a) an epoxy resin.

(b) a curing agent; (C) it may be composed only of an additive consisting of the above-mentioned organometallic compound; however, if necessary, the above-mentioned curing accelerator, crystalline silica, fused silica, talc, calcium silicate, alumina.

Inorganic fillers such as calcium carbonate, barium carbonate, glass fiber, natural waxes, synthetic waxes, internal mold release agents such as fatty acid metal salts, fatty acid amides, fatty acid esters, chlorinated paraffins, brominated epoxy resins, brominated substances, etc. fuel,
Silane coupling agent.

A surface treatment agent such as a titanium coupling agent, a 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 the above-mentioned raw material components using 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.

〔Effect of the invention〕

According to the present invention, it is possible to provide an epoxy resin composition that has excellent moisture resistance and heat resistance. Therefore 2
When the epoxy resin composition of the present invention is used for sealing electrical parts, sufficient credibility can be obtained.

Although the effect of obtaining the above effect is not clear, it is estimated to be first-order.

That is, ionic impurities contained in the epoxy resin, active substances produced during curing, active substances produced by the action of heat, moisture, etc. are captured by the additives. In addition, some of the petroleum sulfonic acid metal salts and dithiocarbamate metal salts in the additives seep into the interface between the object to be coated and the resin composition during molding or use of the epoxy resin composition, resulting in rust prevention and Forms a water-repellent protective film. These make them moisture resistant.

It is thought that heat resistance will be improved. These effects are brought about by the synergistic action of the organometallic compound, the petroleum sulfonic acid metal salt, and the dithiocarbamate metal salt (see Examples).

When the epoxy resin composition of the present invention is used as a sealant for electrical parts, it is possible to prevent functional deterioration such as a decline in the insulation properties of the electrical parts or an increase in leakage current, thereby extending the life of the parts. .

Furthermore, since the epoxy resin composition of the present invention has the above-mentioned effects, it can be used not only as a resin for sealing electrical parts but also as a paint, a sealant, and the like.

〔Example〕

The present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples.

In the following examples, all % means weight %.

Ortho-cresol novolak epoxy resin as epoxy resin (epoxy equivalent: 212. Softening point: 75°C) 19.
0%, 9.3% of phenol novolac resin (softening point 80°C) as a hardening agent, and aluminum acetylacetonate, butyl titanate as organometallic compounds.
Zirconium stearate, dioctyltin distearate, lead phthalate, zinc chromium acetylacetonal octylate, and calcium sulfonate as petroleum sulfonate metal salt (calcium sulfonate content 45%, average molecular weight 1000), barium sulfonate (barium sulfonate content 31) %, average molecular weight 1)00) and di-n-butyldithiocarbamate zinc and copper diethyldithiocarbamate as dithiocarbamate metal salts.
Mix at the blending ratio shown in the table (all blending ratio numbers represent percentages), and add 0.3% of 2-phenylimidazole as a curing accelerator and 70% of fused silica as an inorganic filler. 1 0.2% epoxy silane as a surface treatment agent, 0.2% carnauba wax as a mold release agent.
4% was added and mixed. Next.

This material was melt-kneaded using a roll machine for 5 minutes at a temperature of 90 to 95°C, immediately cooled to solidify, and pulverized.

Thereafter, this pulverized product was molded into a tablet shape, and one of the eight types of epoxy resin compositions according to the present invention (sample block 1 in Table 1) was prepared.
-8) were prepared.

In addition, for comparison, Table 2 (all blending ratio figures are %)
represents. ), C1) without additives, dithiocarbamic acid metal salts as additives only (C2), organometallic compounds only (C3, C4), petroleum sulfonic acid metal salts only (C5), organometallic compounds and dithiocarbamic acid Nine types of comparative epoxy resin compositions were prepared in the same manner as above, using only metal salts (C6°C7) and those using only organometallic compounds and petroleum sulfonic acid metal salts (CB, C9). In addition, the orthocresol novolac epoxy resin as the epoxy resin has a content of 19.8% in 1lhc1,
19.6% in NIC2, 1 in patients C3-C5
9.5%, 19°3% in C6 and C7, C8,
C9 was blended at 19.2%, and other curing agents, curing accelerators, inorganic fillers 1 surface treatment agents, and mold release agents were blended in the same components and proportions as above.

Using the above 17 types of epoxy resin compositions, a model element having aluminum wiring and electrodes was heated at 175°C.
Sealing was performed using a transfer molding machine for 3 minutes, and the resin was further heated at 165° C. for 8 hours for post-curing to perform resin sealing. To test the performance of these sealed samples.

These samples were heated at 12V in an atmosphere of 85°C and 85% relative humidity.
A high-temperature high-temperature energization test was conducted with a bias of . This allows us to measure the average lifespan of each sample.

Its moisture resistance was evaluated. The results are shown in Table 3.

Here, average life is the average time (h) until aluminum wiring or electrodes become corroded and lose their electrical conductivity.
r, 50% average for multiple samples).

As is clear from Table 3, when the epoxy resin composition according to the present invention is used, even under high temperature and high humidity, compared to the conventional comparative composition.

It can be seen that the average life is significantly improved, and the resin composition of the present invention is extremely useful as a resin for sealing electrical parts.

Table 1

Claims (5)

[Claims] (1) An organic compound consisting of an epoxy resin, a curing agent, and one or more of the following: an organic aluminum compound, an organic titanium compound, an organic zirconium compound, an organic tin compound, an organic lead compound, an organic zinc compound, and an organic chromium compound. An epoxy resin composition comprising a metal compound and an additive consisting of a petroleum sulfonic acid metal salt and a dithiocarbamate metal salt. (2) A patent in which the epoxy resin is at least one of glycidyl ether-based epoxy resin, phenol novolac-based epoxy resin, cresol novolac-based epoxy resin, alicyclic epoxy resin, glycidyl ester-based epoxy resin, and halogenated epoxy resin. An epoxy resin composition according to claim (1). (3) The above organometallic compound has a zero
．． Claim No. (1) consisting of 01 to 5% by weight
The epoxy resin composition described in . (4) The epoxy resin composition according to claim (1), wherein the petroleum sulfonic acid metal salt is blended in an amount of 0.1 to 10% by weight based on the epoxy resin. (5) The epoxy resin composition according to claim (1), wherein the dithiocarbamate metal salt is blended in an amount of 0.1 to 10% by weight based on the epoxy resin.