JPS6084337A - Flame-retardant resin composition and its use - Google Patents

Abstract

PURPOSE:A flame-retardant resin composition for use in obtaining electronic parts having excellent reliability under high temperature and humidity conditions, comprising antimony oxide particles with their surfaces precoated with a coating material. CONSTITUTION:A flame-retardant resin composition comprising particles of antimony oxide selected from amony Sb2O3, Sb2O4, and Sb2O5, with their surfaces precoated with a coating material composed of an agent for forming a moisture- resistant protective layer (e.g. an epoxy resin) and/or an agent for forming a layer to give an affinity for resin components (e.g. a silane coupling agent). With no difference in flame retardancy from conventional flame retardant compositions, the composition is substantially free of corrosion of a metal sealed in a resin particularly under high temperature and humidity conditions, making it possible to improve reliability; thus serves as a suitable packaging material for electronic parts, etc.

Description

Detailed Description of the Invention [Field of Application of the Invention] The present invention relates to a flame-retardant resin composition for obtaining electronic components with high reliability, particularly reliability under high temperature and high humidity conditions, and sealing with the composition. related to electronic components.

[Background of the invention]

In recent years, economical plastic materials have been widely used for packaging diodes, thyristors, transistors, integrated circuits, large-scale integrated circuits, and electronic components equipped with these various semiconductor devices.

However, since general plastic equipment is flammable, the plastic materials used for the packaging of the electronic components are mixed with various halogenated compounds, phosphorus compounds, antimony oxides, or inorganic hydroxides. It combusts, compromising the safety of combustion. In particular, epoxy resin-based compositions are usually used for packaging semiconductor devices that require a high degree of reliability;
:) FFI is made by using a combination of non-rogenated epoxy resin and antimony oxide, but general semiconductor devices are extremely sensitive to moisture and chemical contamination, especially when aluminum is used in wiring. In semiconductor devices using aluminum alloys or aluminum alloys, the interaction between minute amounts of contaminants contained in the package material and moisture infiltrating from outside the package can cause wiring to thicken, causing disconnections and abnormal leakage currents. This tendency becomes particularly noticeable when a flame retardant resin IX+4 composition is used as the package material.

In order to solve these problems, we have refined various materials to reduce the amount of contaminants, lowered the moisture permeability of Package II to prevent moisture intrusion, and improved the elements.
There are so many things you can do to improve the adhesion or adhesion between lead frames, lead frames, etc. and package materials! However, there is a problem in that the moisture resistance of plastic packaged products is considerably inferior to that of hermetically sealed products.

[Purpose of the invention]

The object of the present invention is to provide a flame-retardant resin composition and an electronic component sealed with the composition, in order to improve the drawbacks of the above-mentioned prior art, and to obtain an electronic component whose reliability is questionable especially under high temperature and high humidity conditions. Our goal is to provide the following.

[Summary of the invention]

To summarize the present invention, the first invention of the present invention is an invention of a flame-retardant resin composition, which is characterized in that it contains antimony oxide particles whose surfaces have been pre-cut with a coating agent. do.

A second invention of the present invention is an invention of an electronic component, which is an electronic component sealed with a flame-retardant composition, wherein the composition is the flame-retardant resin composition of the first invention of the present invention. It is characterized by

In order to achieve the above object, the present inventors investigated various types of materials and found that, in addition to the moisture and pollutants mentioned above, flame retardant components are responsible for the corrosion of metal wood constituting electronic components packaged with plastic materials. One of the headlines is that antimony oxide is used as an intermediary. In other words, water that has entered the plastic package under high temperature and humidity conditions dissolves antimony oxide in the presence of contaminants, and the dissolved antimony is used to dissolve antimony from materials that make up electronic components and which have a greater tendency to ionize than antimony, such as aluminum, chromium, zinc,
The present invention was achieved based on the discovery that the dissolution and corrosion of iron, cobalt, nickel, tin, lead, etc. are significantly accelerated.

The coating agent in the present invention means a moisture-resistant retention agent.

The surface of antimony oxide particles can be coated with a coating agent not only when a moisture-resistant protective layer is provided, but also when a treatment layer is provided to provide affinity with the resin component. Since the wettability with the resin component is improved, the formation of antimony oxide stone chips due to infiltrated moisture and contaminants is prevented, so that the dissolution corrosion of the metal 4 material constituting the electronic parts can be reduced.

In the present invention, examples of moisture-resistant d-layer forming agents include epoxy resins, silicone resins, polyimide resins,
Obtained by firing a thermosetting resin selected from unsaturated polyester resins, phenolic resins, and the above-mentioned fluorine-modified resins, thermoplastic resins selected from polyethylene, polypropylene, polystyrene, saran, fluorine resins, etc., or organic silicone resins. Examples include inorganic coatings and inorganic substances such as glass, but thermosetting resins selected from the group consisting of epoxy resins, silicone resins, fluorine-modified resins, and polyimide resins or free silicone compounds are suitable. The normal microencapsulation method is used to form the protective 1ω layer, but among these methods, various non-retentive substances are dissolved in an appropriate solvent, and then antimony oxide is added to this solution and dispersed well. The simplest method is to perform spray drying and further perform post-heating if necessary. In addition, examples of layer-forming agents imparting affinity with the η11 component include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-dalicidoxyprobyltrimethoxysilane, and vinyltris(β-methoxyethoxy)silane. , γ-methacryloxypropyltrimethoxysilane, N-[γ-(dimethoxymethylsilyl)propyl]ethylenediamine, N-[γ-(trimethoxysilyl)propyl]ethylenediamine, isopropyltriisostearoyl titanate, titanate coupling agents such as inglobil tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate,
Aluminum coupling agents such as aluminum inpropylate, mono-5ec-butoxyaluminum diisopropylate-1, aluminum-5ec-butyrate, ethyl acetoacetate aluminum diisobrobylate, aluminum tri(ethylacetoacetate), and various other surfactants and the like. To form the affinity-imparting layer, each of the above compounds is dissolved in an appropriate solvent,
It can be formed by adding antimono oxide therein, dispersing it well, filtering it, and drying it, or by spray drying it in the same manner as described above.

Examples of antimony oxides used in the present invention include diantimony tetroxide and diantimony pentoxide in addition to diantimony trioxide.

The flame-retardant resin composition of the present invention includes an epoxy resin, a vinyl ester resin, and a non-flammable resin containing at least one curing agent selected from the group consisting of generally known phenols, acid anhydrides, and amine compounds. saturated polyester resin,
Thermosetting resins such as silicone resins and polyimide resins and thermoplastic resins such as polyphenylene sulfide and polysulfone are coated with antimony oxide and halogen compounds to enhance the flame retardation effect.
These compositions contain phosphorus compounds, nitrogen compounds, etc., and depending on the purpose, curing accelerators, silica,
Fillers such as alumina and glass fibers, mold release agents, coupling agents, surfactants, pigments, dyes, etc. can also be blended.

) b-11P, l- & l/P-SH-IT j-,
s)z 4! →−a+ +4 μ, L If a large amount of contaminants are present in the materials of electronic parts, even if they are present, the presence of a large amount of contaminants alone will cause corrosion of the metal materials due to the infiltration of moisture. Therefore, it is desirable that the composition containing the above resin composition and various additives contains few contaminants. For example, when the above composition is extracted with pure water, the electrical conductivity is 100 pσ/m or less (
Extraction conditions: > i o o ℃ 7120 h') is desirable.

When using the flame-retardant resin composition obtained in this manner, the reliability of the electronic component is improved, especially under high temperature and high humidity conditions, compared to electronic components sealed with conventional flame-retardant resin compositions. I can do seven.

Examples of these electronic components include resin-sealed rigid semiconductor devices, resin-sealed motors, and small transformers.

[Embodiments of the invention]

Hereinafter, the present invention will be explained in more detail with reference to production examples and examples, but the present invention is not limited thereto. In addition, in each example, the blending amount of each material is expressed as parts 1. There was a lot in the weight section.

First, an example of manufacturing a coating using an antimony oxide coating agent will be shown.

Production Example 1 10 parts of bisphenol-type epoxy resin Ep-1001 (manufactured by Shell Co., Ltd., epoxy equivalent: 475), 2.5 parts of tetrahydrophthalic anhydride (manufactured by Shin Nippon Chemical Co., Ltd., melting point: about 100°C), 2-ethyl-4-methyl Imidazole (Shikoku Kasei M
') [11 parts were dissolved in 125 parts of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., special grade), and 10 parts of diantimony trioxide (manufactured by Nippon Seiko Co., Ltd., purity 995%) was added to this m solution and mixed by stirring. Next, this mixed solution was filtered, the separated nantimony trioxide was air-dried, and then heated at 150°C for 1 hour.
The desired niantimony trioxide having an epoxy resin layer on its surface was obtained.

Production Example 2 10 parts of silicone resin Kn-253 (manufactured by Etsu Kagaku Co., Ltd., nonvolatile content 10%) were mixed with 10 parts of diantimony trioxide. The mixed solution was filtered, the separated diantimony trioxide was air-dried, and then heated at 150° C. for 1 hour to obtain the desired diantimony trioxide having a silicone resin layer on the surface.

Production Example 3 After adding and mixing 2 parts of diantimony trioxide to 100 parts of fluororesin coating agent FC-721 (manufactured by Sumitomo 3M, non-volatile content 2%), spray drying and heating at 150°C for 1 hour This was carried out to obtain the desired diantimony trioxide having a fluororesin layer on the surface.

Production example 4 Inorganic coating agent KOLKO) TSB-'4200
(manufactured by Colcourt, nonvolatile content 45%) was dissolved in 100 parts of tetrahydrofuran, 10 parts of diantimony trioxide was added thereto, mixed, filtered, air-dried, and heated at 200°C for 30 minutes to remove inorganic substances on the surface. The desired diantimony trioxide having a coating layer was obtained.

Production Examples 5 to 7 As coupling agents, γ-(2-aminoethyl)aminopropyltrimethoxysilane IBM-606 (manufactured by Shin-Etsu Chemical Co., Ltd.) [Production Example 5], isopropyl tris (dioctyl pyrophosphate) titanate xR-xss (Ajinomoto (manufactured by Yoken Fine Chemical Co., Ltd.) [Production Example 6], aluminum trisethyl acetate 7'cetate ALCM-TR (manufactured by Yoken Fine Chemical Co., Ltd.) [Production Example 7] 1 part each was dissolved in 100 parts of isopropyl alcohol, and diantimony dioxide was dissolved in the solution. After adding 10 parts of the mixture, mixing, filtering, and air drying, the mixture was heated at 1°C for 30 minutes to obtain pJ of B HrM type nantimony trioxide having a coupling agent layer on the surface.

Examples 1 to 7, Comparative Examples Using each of the above production examples 1 to 7 and untreated diantimony trioxide as a comparative example, eight types of molded materials A with the compositions shown in Table 1 were made. Created. During production, each material is drape-irended in advance, and then 80%
Melt mixing was performed for about 10 minutes using a mixer roll heated to around 10°C.

Table 1 Next, a semiconductor device and a semiconductor device in which a -aluminum zigzag wiring pattern with a thickness of about 1 μm and a width of 'Oppn was formed on a thermal oxide film of a silicon wafer using each of the above-mentioned molding materials.
27 x 12.7 x 1.5 mm flame retardant test,
The specimen was molded using a transfer molding machine. Molding was carried out at 180°C for 1.5 minutes, followed by post-curing at 180°C for 5 hours.

The above resin-sealed semiconductor device was left in water vapor at 120°C and 2 atm, and the aluminum wiring corroded [leading to the i-line].
The time taken to move was measured. For the flame retardant test pieces, a combustion test 15 (according to UL-94) was conducted.The results are shown in Table 2.The tests were conducted on 10 samples, and the corrosion breakage start time is indicated by the time when the first wire breakage occurred.

Table 2 As is clear from Table 2, surface treatment with diantimony trioxide does not change the flame retardant effect of molded products, but it takes 2 to 5 times longer for aluminum wiring to corrode and break. It has become.

〔Effect of the invention〕

As is clear from the above explanation, the flame retardant resin composition of the present invention has no difference in flammability compared to conventional compositions, and moreover, when this composition is used, it can be used particularly under high temperature and high humidity conditions. Since the metal parts are sealed in resin, corrosion is less likely to occur, and reliability can be improved.

Patent applicant Hitachi Seisakusho Co., Ltd.7. ! 11 Agent Hiroshi Nakamoto Continued from page 1 0 Inventor Noriyuki Kaneshiro Hitachi City Saiwai-cho 3 Office

Claims (1)

[Scope of Claims] 1. A flame-retardant resin composition characterized by containing antimony oxide particles whose surfaces are coated with a coating agent in advance. 2. Claim 1, wherein the antimony oxide is at least one selected from the group consisting of diantimony trioxide, diantimony tetroxide, and diantimony pentoxide.
The flame-retardant resin composition described in . 3. The coating agent contains a moisture-resistant protective layer forming agent and/or
The G-IL flammable resin composition according to claim 1 or 2, which is a layer-forming agent that imparts affinity with a resin component. 4. The flame-retardant resin composition according to item 3, wherein the moisture-resistant coercive layer forming agent is a thermosetting resin selected from the group consisting of epoxy resins, silicone resins, fluorine-modified resins, and polyimide resins. 5. The affinity imparting layer forming agent with the resin component is silane-based,
The flame-retardant resin composition according to claim 3, which is a titanate-based or aluminum-based coupling agent. 6. A patent in which the composition is an epoxy resin composition containing the coated antimony oxide particles and at least one curing agent selected from the group consisting of phenols, carboxylic anhydrides, and amine compounds. A flame-retardant resin composition according to any one of claims 1 to 5. 7. An electronic component sealed with a flame-retardant resin composition, characterized in that the composition is a flame-retardant resin composition containing antimony oxide particles whose surfaces are coated in advance with a coating agent. electronic components. 8. The electronic component has aluminum wiring or Q-1! 8. The electronic component according to claim 7, which is a semiconductor device using the alloy.