JPH1135647A - Molding material for sealing electronic part, its molding, electronic part device and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject molding material capable of manifesting the effect on the retardation of gelling and the improvement of preservation stability, etc., and having excellent moldability and reliability by compounding a vinyl ester resin with a specific initiator and an inhibitor. SOLUTION: The molding material consists essentially of (A) a vinyl ester resin, (B) a radical polymerization initiator (e.g. an aromatic peroxide), (C) a polymerization initiator containing at least one N-O bond in the structure (preferably an oxime-based compound, or nitroxide-based compound) and (D) an inorganic filter, and not less than 20 wt.% of the component A is a novolak- based vinyl ester resin. The amounts of the respective compounded ingredients are preferably 0.05-10 pts.wt. component B, 0.001-10 pts.wt. component C and 100-2,000 pts.wt. component D based on 100 pts.wt. component A. A transfer molding method and an injection molding method are desirable as the molding method of the molding material. As a result, high productivity of an electronic part device is expected by using the molding material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding material for sealing electronic parts having excellent mechanical properties, moldability, productivity, environmental resistance and storage stability, and an electronic device having an electronic part sealed with the molding material. The present invention relates to a component device and a method of manufacturing the same.

[0002]

2. Description of the Related Art Organic materials such as epoxy resins, silicone resins, and diallyl phthalate resins are widely used as sealing materials used in electronic component devices such as semiconductor packages for reasons of cost and productivity. Among them, epoxy resin
It has good moldability and dimensional stability, and occupies a high share because good mechanical properties can be obtained not only at room temperature but also at high temperatures during soldering.

[0003] However, the epoxy resin reacts with the amine which is its catalyst at normal temperature, and gels in about several days. For this reason, refrigeration is required for transportation and storage, and costs are incurred. In recent years,
Due to the advanced development of the information society around the world, the production bases of electronic components and molding compounds for their encapsulation and the electronic component equipment manufacturers who are their users are distributed all over the world. Transport costs also tend to increase. Further, for users, slight inadequate handling of temperature control and deterioration of moldability due to progress of gelation during long-term storage cause sudden failures.

In the transfer molding method frequently used in this field, a considerable amount of sprue and cull waste is generated as compared with a molded product. In recent years, disposal of industrial waste has become difficult due to aggravation of environmental problems and an increase in consciousness of residents, and the amount of disposal becomes a problem in a situation where the production of electronic component devices is rapidly increasing. On the other hand, in the injection molding method, there is no problem with the amount of sprue or cull waste, but it must be preheated and melted at a relatively high temperature of about 50 to 100 ° C. lower than the molding temperature before molding. Since it takes several minutes to several tens of minutes from the application of heat to molding, the epoxy resin hardens in the meantime and eventually loses its fluidity. For this reason, injection molding is difficult with an epoxy resin.

On the other hand, in an unsaturated polyester resin or a vinyl ester resin using a radical polymerization initiator, a polymerization reaction proceeds by radicals resulting from decomposition of the polymerization initiator.
Since the activation energy of this polymerization reaction is higher than that of the above-described amine-catalyzed epoxy ring opening reaction, the progress of the reaction at room temperature is very small. Therefore, it can be stored for several months or more. Furthermore, since the activation energy is high, the gelation time at the preheating temperature is 3 to 10 times the gelation time at the molding temperature, which is considerably longer than that of the epoxy resin. Law is applicable. Especially vinyl ester resin,
Excellent corrosion resistance and high temperature stability. As the vinyl ester resin, a novolak vinyl ester resin and a bisphenol vinyl ester resin are well known.

[0006] However, in the radical polymerization, specific impurities, for example, amines and metals have a content of 0.1%. Several% to several p
Some of them show catalytic effect only by mixing pm
Curing may proceed even at room temperature. As a result, there is a problem that gelation occurs in about several days even at room temperature, and the stability is not different from that when an epoxy resin is used.
A great deal of care and effort is required to prevent the contamination of impurities, which causes a cost increase in manufacturing the molding material and a sudden failure.

Japanese Patent Application Laid-Open No. 60-104121 discloses the use of a novolac vinyl ester resin as a molding material for a semiconductor encapsulant. However, there is no description of a guideline for selecting a polymerization initiator or a polymerization inhibitor.

[Problems to be solved by the invention]

[0008] From the above background, 60 degrees from normal temperature range
There is a strong demand for a molding material for electronic component encapsulation in which the gelation hardly proceeds in a medium temperature range of from 100 ° C to 100 ° C, the storage stability is high, the curability is good at the time of molding, and there is no problem of waste. I have.

[Means for Solving the Problems]

The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, by mixing a vinyl ester resin with a specific polymerization initiator or polymerization inhibitor, suppression of gelation and storage stability have been achieved. A remarkable effect was observed in the improvement of the composition and the like, and it was found that a molding material satisfying the above-mentioned requirements was obtained, and the present invention was completed.

That is, the present invention provides (1) (A) a vinyl ester resin, (B) a radical polymerization initiator, (C) a polymerization inhibitor containing at least one nitrogen-oxygen bond in its structure, and (D) an inorganic inhibitor. A molding material for sealing electronic parts, wherein a filler is an essential component and at least 20% by weight of the vinyl ester resin of the component (A) is a novolac vinyl ester resin; Ester resin 10
The polymerization initiator of the component (B) is added in an amount of 0.05 part by weight to 0 part by weight.
-10 parts by weight, the polymerization inhibitor of component (C)
10 parts by weight, 100 to 200 parts of the inorganic filler (D)
The molding material for electronic parts sealing according to the above (1), which is blended with 0 parts by weight, and (3) the vinyl ester resin of the component (A)
The molding material for sealing electronic components according to the above (1) or (2), wherein 0 to 80% by weight is a bisphenol A-based vinyl ester resin, and the polymerization initiator of the component (4) (B) is an organic peroxide. The molding material for sealing electronic parts according to any one of the above (1) to (3), and the polymerization inhibitor (5) according to any one of the above (1) to (4), wherein the polymerization inhibitor of the component (C) is an oxime compound. The molding material for component sealing, wherein the polymerization inhibitor of component (6) (C) is a compound having at least one unpaired electron (1).
(4) The molding material for sealing electronic parts according to any one of (1) to (4),
(7) The method for molding a molding material for sealing electronic parts according to any one of the above (1) to (6), which uses a transfer molding method, and (8) the above, which uses an injection molding method. (1) The method for molding a molding material for sealing electronic parts according to any one of (1) to (6), (9) a molding temperature of 120 ° C to 24 ° C.
(7) The method of molding an electronic component sealing material according to (7) or (8), wherein the molding material is 0 ° C., (10) sealing with the electronic component encapsulating material according to any one of (1) to (6). (11) The above (1) to (6).
(12) A method for manufacturing an electronic component device, comprising: a step of sealing an electronic component with the molding material for sealing an electronic component according to any one of the above.
(13) The electronic component device according to the above (10), wherein the electronic component is an active element, (13) the above (11), wherein the electronic component is an active element.
A method for manufacturing the electronic component device described above.

[0011]

DETAILED DESCRIPTION OF THE INVENTION (A) used in the present invention
The vinyl ester resin of the component is not particularly limited,
For example, a novolak-based vinyl ester resin, a bisphenol A-based vinyl ester resin and the like can be mentioned. Of these, the compounding amount of the novolak vinyl ester resin is (A)
More than 20% by weight of the components is necessary to meet the requirements of the present invention. The preferred amount of the novolak vinyl ester resin is 40 to 70% by weight of the vinyl ester resin as the component (A). If it is less than 40%, the molded product is too soft to be easily separated from the mold, and if it exceeds 70% by weight, it tends to be hard and low in toughness, and particularly the thermal shock resistance tends to be reduced. The method for synthesizing the novolak vinyl ester resin is not particularly limited. For example, a method of reacting an unsaturated acid with a glycidylated compound of a novolak resin, a method of reacting a glycidylated compound of an unsaturated acid with a novolak resin, and the like are used. Can be. Regardless of the synthesis method, the reaction may be carried out with or without a solvent. If necessary, a catalyst or a compound for inhibiting polymerization as a side reaction can be added to the reaction system.

The glycidylated product of the novolak resin is not particularly limited. Examples thereof include glycidylated products of a novolak resin using phenol, cresol, xylenol, and naphthol as raw materials, and these may be used alone or in combination of two or more. be able to.

The unsaturated acid is not particularly restricted but includes, for example, acrylic acid, oleic acid, maleic acid, mesaconic acid, citraconic acid, methacrylic acid, itaconic acid, cinnamic acid, fumaric acid, aconitic acid, crotonic acid, Sorbic acid, docosahexaenoic acid and the like.

Known catalysts can be used, for example, amine catalysts such as triethylamine and imidazole,
Phosphorus compounds such as diethylphosphine and triphenylphosphine can be used, but the present invention is not limited to these. In particular, phosphorus-based catalysts are preferred in that they suppress side reactions such as polymerization of unsaturated groups that occur in addition to the intended esterification reaction.

Examples of the compound for inhibiting the polymerization as a side reaction include phenol compounds such as phenol, catechol, resorcin, pyrogallol, hydroquinone and naphthol; quinone compounds such as benzoquinone and naphthoquinone; and para-benzoquinone dioxime. , Oximes such as diethyl ketone oxime, dinitrobenzene, nitrotoluene, 2,2-diphenyl-picryl-
Examples thereof include, but are not limited to, nitro compounds such as hydrazyl, N-nitrosophenylhydroxylamine ammonium salts, and nitroso compounds such as nitrosotoluene.

In the present invention, as the vinyl ester resin as the component (A), a bisphenol A vinyl ester resin can be added in addition to the novolak vinyl ester resin. Bisphenol A used in the present invention
Although the vinyl ester resin is not particularly limited, for example, it can be commercially obtained from Showa Polymer Co., Ltd. under the trade name Lipoxy R-802. It can also be obtained by reacting an unsaturated acid with a glycidylated product of bisphenol A. The glycidylation product of bisphenol A is not particularly limited, and for example, those sold by Yuka Shell Co., Ltd. under the trade names of Epicoat 828 and Epicoat 1001 can be used. Further, the bisphenol A-based vinyl ester resin can be synthesized by the same method as the novolak-based vinyl ester.

The amount of the bisphenol A-based vinyl ester resin is 20 to 8 of the vinyl ester resin as the component (A).
It is preferably set to 0% by weight. If the amount of bisphenol A-based vinyl ester resin is large, the molded product tends to be hard and low in toughness, and if it exceeds 80% by weight, the hardness of the molded product may be lower than the level required as a material for sealing electronic parts. When the molded product is taken out, it is difficult to separate from the mold. If it is less than 20% by weight, on the contrary, the toughness is increased and the adhesive strength is also improved, but it tends to be too soft. From the viewpoint of thermal shock resistance, it is more preferable to set the blending amount of the bisphenol A-based vinyl ester resin to 40 to 80% by weight of the vinyl ester resin as the component (A).

In the present invention, a conventionally known thermosetting resin or thermoplastic resin can be added, if necessary, in addition to the vinyl ester resin as the component (A). The thermosetting resin is not particularly limited, and examples thereof include an unsaturated polyester resin, an epoxy resin, a phenol resin, a polyurethane resin, a polyimide resin, a melamine resin, a benzoguanamine resin, a furan resin, and a diallyl phthalate resin. Examples of the thermoplastic resin, polystyrene resin, polyacrylic resin, polymethacrylic acid resin,
Polyvinyl chloride resin, silicone resin, polybutadiene resin, indene-cumarone resin, polyvinyl acetate resin,
Examples include, but are not limited to, polyamide resins and polycarbonate resins. These resins can be appropriately added alone or in combination of two or more to improve mechanical properties, appearance, weather resistance, radiation resistance, heat conductivity, printability, and the like.

The radical polymerization initiator of the component (B) used in the present invention is not particularly limited, and is generally known as a polymerization initiator which generates a radical by thermal decomposition, and conventionally known ones can be used. For example, organic peroxides such as peroxyketal compounds, peroxyester compounds, dialkyl peroxide compounds, and hydroperoxide compounds, and 2,2′-azobisisobutyronitrile, 1,1′- Azobis (cyclohexane-1-
Azo-based polymerization initiators such as carbonitrile).
Among them, organic peroxides are preferable, and those classified into the category of medium to high temperature initiators are more preferable. Here, the medium temperature initiator is a temperature at which the peroxide decomposes and the amount of active oxygen is reduced to half of the initial amount in one minute (hereinafter, referred to as a half temperature).
C. to 100.degree. C., and a high-temperature initiator is one having a half-life temperature exceeding 100.degree. An appropriate polymerization initiator can be selected depending on the desired molding temperature and molding time. These polymerization initiators can be used alone or in combination of two or more. Perbutyl O manufactured by NOF Corporation, Kayakumil D and Kayahexa AD manufactured by Kasei Akzo Co., Ltd., and Perhexin 25B manufactured by NOF Co., Ltd. are commercially available as high temperature initiators. However, the present invention is not limited to these.

The amount of the radical polymerization initiator (B) is not particularly limited, but is preferably 0.05 to 10 parts by weight based on 100 parts by weight of the vinyl ester resin (A). Preferably it is 0.2 to 5 parts by weight. If the amount is less than 0.05 part by weight, it is difficult to cure and molding failure is likely to occur. If it exceeds 10 parts by weight, the gelation time becomes extremely short, and the gel tends to harden before flowing in the cavity, which tends to cause unfilling.

The polymerization inhibitor having at least one nitrogen-oxygen bond in the structure of the component (C) used in the present invention is not particularly limited. Examples thereof include oximes such as para-benzoquinone dioxime and diethyl ketone oxime. Nitro compounds such as dinitrobenzene, nitrotoluene, 2,2-diphenyl-picryl-hydrazyl,
2,6,6, -tetramethyl-1-piperidinyloxy, 4,4-dimethyl-3-oxazolinyloxy,
2,2,5,5-tetramethyl-1-pyrrolidinyloxy, 5,5-dimethyl-1-pyrroline-N-oxide,
2,5,5-trimethyl-1-pyrroline, N-tert-butyl-α-phenylnitrone, α- (4-pyridyl-1-oxide) -N-tert-butylnitrone,
-Methyl-2-nitrosopropane, 2-hydroxymethyl-2-nitrosopropane, 2,4,6, -tri-tert-butyl-nitrosobenzene, nitrosodulene,
Examples include nitroxide compounds such as pyridine-N-oxide. Among them, compounds having unpaired electrons are preferable from the viewpoint of molding latitude. For example, 2,2,6,6,-
Examples thereof include tetramethyl-1-piperidinyloxy, 4,4-dimethyl-3-oxazolinyloxy, and 2,2,5,5-tetramethyl-1-pyrrolidinyloxy.
Oxime compounds and nitroxide compounds are preferred from the viewpoint of safety and toxicity. These polymerization inhibitors can be used alone or in combination of two or more.

The compounding amount of the polymerization inhibitor (C) is
The amount is preferably 0.001 to 10 parts by weight based on 100 parts by weight of the vinyl ester resin as the component (A). When the compounding ratio of the polymerization inhibitor is less than 0.001 part by weight,
Gelation time is too short, there is no molding tolerance, voids called voids inside the molded product due to unfilled,
The function as a sealing material is impaired, and the gelation in the temperature range from room temperature to medium temperature progresses, and storage stability tends to decrease.
Here, the medium temperature range is defined as a temperature range of 60C to 100C. If the compounding amount of the polymerization inhibitor exceeds 10 parts by weight, the hardness of the molded product is reduced and the molded product is damaged when being removed from the mold, or the mechanical strength is reduced, and the function as a sealing material is impaired. Easy to do. A more preferred compounding range is 0.01 to 2 parts by weight based on 100 parts by weight of the vinyl ester resin as the component (A).

In the present invention, a known polymerization inhibitor having no nitrogen-oxygen bond in the structure may be used in combination with the polymerization inhibitor of the component (C). The polymerization inhibitor having no nitrogen-oxygen bond is not particularly limited. Examples thereof include quinone-based compounds such as benzoquinone and naphthoquinone, and phenol-based compounds such as hydroquinone, catechol and pyrogallol.

The inorganic filler of the component (D) in the present invention is not particularly limited and conventionally known ones can be used. Examples thereof include fused silica, crystalline silica, alumina, zircon,
Powders of calcium silicate, calcium carbonate, silicon carbide, aluminum oxide, copper oxide, tin oxide, nickel oxide, titanium oxide, beryllium oxide, aluminum nitride, boron nitride, beryllia, zirconia, or spherical beads of these, titanium One or more kinds of single crystal fibers such as potassium acid, silicon carbide, silicon nitride, and alumina, glass fibers, and the like can be used in combination. Further, examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate and the like, and these can be used alone or in combination. Among the above-mentioned inorganic fillers, silica is preferable in terms of balance between availability, hygroscopicity, insulating properties, and thermal stability, and in particular, from the viewpoint of reducing the linear expansion coefficient, fused silica is preferred from the viewpoint of high thermal conductivity. Alumina is preferred. Known inorganic fillers include monoclinic, triclinic, orthorhombic, cubic, and tetragonal crystalline forms, amorphous prismatic forms, spherical forms, and the like. Any shape can be used. Also, a single kind of shape or a mixture of two or more different shapes of inorganic fillers may be used.
Also, any particle size and distribution of the inorganic filler can be used.

The amount of the inorganic filler (D) is from 100 to 2 parts by weight per 100 parts by weight of the vinyl ester resin (A).
Preferably, the amount is 000 parts by weight. If the compounding amount is less than 100 parts by weight, the package may be warped or cracked in the cooling process after molding due to large heat shrinkage,
Due to the large amount of moisture absorption, reliability is likely to decrease due to corrosion of internal wiring and the like. If it exceeds 2,000 parts by weight, the fluidity decreases, and unfilling occurs during molding,
Insufficient amount of resin combined with filler,
Chipping or brittle fracture of the molded product is likely to occur. More preferred compounding amount is the vinyl ester resin 10 of the component (A).
The inorganic filler is 200 to 1000 parts by weight with respect to 0 parts by weight.

In order to improve workability, a conventionally known mold release agent may be added to the molding material for sealing electronic parts of the present invention, if necessary. Examples of the release agent include stearic acid, carnauba wax, ethylene oligomer, Teflon oligomer, low polymerization degree polyethylene, silicone oil, oxidized or non-oxidized polyolefin, and the like.

In the present invention, a conventionally known organic or inorganic colorant can be added as needed. Examples of colorants include, but are not limited to, phthalocyanine pigments, quinacdrine pigments, carbon black, cadmium yellow, perylene pigments, azo pigments, and the like.

Other additives include conventionally known coupling agents, flame retardants such as brominated epoxy resins, antimony trioxide, phosphate esters, nitrogen-containing compounds such as red phosphorus and melamine resins, and natural waxes. , Synthetic wax, stress relief agent such as silicone oil and silicone rubber powder, ion trapping agent such as hydrotalcite and antimony-bismuth, fluidity regulator, antioxidant, ultraviolet absorber, antistatic agent, anti-crystallization agent A fungicide, a water-producing agent, a flexible agent and the like can be used as required.

The molding material in the present invention can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed. As a general method, a predetermined amount of raw materials are sufficiently mixed by a mixer or the like. After mixing, melt-kneading with a mixing roll, extruder, etc., cooling,
A pulverizing method can be used. Tablets may be formed in a size and weight suitable for molding conditions.

A support member such as a lead frame, a wired tape carrier, a wiring board, glass, or a silicon wafer is provided with a memory IC, a central processing processor (CPU) LS
I, digital general-purpose processing elements, digital signal processing processor (DSP) LSI, communication control elements, semiconductor chips such as analog processing elements, silicon-based materials, germanium-based materials, gallium arsenide in junction-type, mesa-type, planar-type, etc. processes PNP type, NPN fabricated using base materials
Types such as bipolar transistors, field effect type MOS transistors, tunnel diodes, zener diodes, diodes such as variable capacitance diodes, thyristors,
Active parts such as thyristors such as gate turn-off thyristors, thermistors, varistors, etc., electronic parts such as capacitors, resistors, coils, and passive elements such as transformers, and / or electronic parts such as switches and connectors are mounted. The electronic component device can be manufactured by sealing with the sealing molding material of the present invention. Examples of such an electronic component device include a QFP in which a chip mounted on a copper lead frame is sealed with a molding material of the present invention, and a semiconductor chip connected to a tape carrier with a bump using a molding material of the present invention. Can be mentioned. Also, active elements such as semiconductor chips, transistors, diodes, thyristors, and / or passive elements such as capacitors, resistors, and coils are connected to wiring formed on a wiring board or glass by wire bonding, flip chip bonding, soldering, or the like. Is sealed with the molding material of the present invention.
A B module, a hybrid IC, a multi-chip module, and the like can be given.

The method for sealing the electronic component, that is, the method for molding the molding material for electronic component sealing of the present invention is not particularly limited.
A compression molding method and the like can be mentioned. Among them, the transfer molding method and the injection molding method are preferable. The molding temperature is not particularly limited, but is preferably from 120C to 240C. If the temperature is lower than 120 ° C., the reliability tends to decrease, and if the temperature exceeds 240 ° C., the work tends to be difficult. A more preferred range is 140
C. to 200C. The molding pressure is not particularly limited, but is preferably set in a range of 50 to 300 kg / cm ² . If it is less than 50 kg / cm ² , unfilled portions and internal voids are likely to be generated, and if it is more than 300 kg / cm ² , there is a possibility that internal elements and the like may be damaged. In the preheating step of the injection molding, it is preferable that the increase in the viscosity from the initial viscosity at 100 ° C. or less within one hour is 20% or less.

[0032]

EXAMPLES Next, examples of the present invention will be described, but the scope of the present invention is not limited to these examples.

Synthesis Example 1 (Synthesis of cresol novolak vinyl ester resin) Orthocresol novolak type epoxy resin (EOCN103 manufactured by Nippon Kayaku Co., Ltd., softening point 82 ° C., epoxy equivalent 22)
0), 200 parts by weight of methacrylic acid, and 0.5 part by weight of a triphenylphosphine catalyst were charged into a reaction vessel, and the mixture was stirred at 100 ° C. to 120 ° C. until the reaction was saturated, and reacted to obtain a softening point of 72. A novolak-based vinyl ester resin at a temperature of ° C was obtained. The acid value of this resin is KOH / g
It was 6 mg in conversion.

Synthesis Example 2 (Synthesis of bisphenol A-based vinyl ester resin) 400 parts by weight of bisphenol A-based epoxy resin (Epicoat 828, Yuka Shell Co., softening point 65 ° C, epoxy equivalent 470), 70 parts by weight of methacrylic acid, Further, 1.0 part by weight of a triphenylphosphine catalyst was charged into a reaction vessel, and stirred at 100 ° C. to 120 ° C. until the reaction was saturated,
The reaction was performed to obtain a bisphenol A-based vinyl ester resin having a softening point of 85 ° C.

Examples 1 to 23 and Comparative Examples 1 to 7 Each material was preliminarily mixed (dry-blended) with the composition shown in Tables 1 to 3, and then a pre-roll temperature of 60 was obtained using a 10-inch diameter mixing roll. ℃, after roll temperature 90 ℃,
Front roll rotation speed 22 rpm, rear roll rotation speed 18 rpm
Was wound around a front roll and kneaded for 5 minutes according to a conventional method. The obtained sheet-like material was pulverized to obtain the molding materials for sealing electronic parts of Examples 1 to 23 and Comparative Examples 1 to 7. The novolak-based vinyl ester resin is the resin obtained in Synthesis Example 1, the bisphenol A-based vinyl ester resin is the resin obtained in Synthesis Example 2, and the polymerization initiator is dicumyl peroxide (DCP manufactured by Mitsui Petrochemical Co., Ltd.). ), SCOX-31 manufactured by Micron Co., Ltd. as an inorganic filler, and carbana wax as a release agent. Examples 1 to 13 and Comparative Example 1 of Polymerization Inhibitors were 2,2 manufactured by Sigma-Aldrich. , 6,6, -Tetramethyl-1-piperidinyloxy, Examples 14-18 were para-benzoquinone-dioximes, Examples 19-23 were 2,2-diphenyl-picryl-hydrazyl, Comparative Examples 3-7 were Hydroquinone was used.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

[Table 3]

Comparative Example 8 Orthocresol novolak epoxy resin (EOCN103 manufactured by Nippon Kayaku Co., Ltd., softening point 82 ° C., epoxy equivalent 22
0) 100 parts by weight, 47 parts by weight of phenol novolak resin (HP-208 manufactured by Hitachi Chemical Co., Ltd.), imidazole C17
Z (manufactured by Shikoku Chemicals Co., Ltd.), 2 parts by weight of SCOX-31 manufactured by Micron Corporation as an inorganic filler, 1 part by weight of carbon black, 1 part by weight of carbana wax, and 1 part by weight of epoxysilane were blended. Roll kneading was performed in the same manner as in Example 1 to obtain an epoxy-based molding material for electronic component sealing (Comparative Example 8).

For a total of 31 types of molding materials produced, a 64-pin QFP (14 mm × 20 mm × 2.7 m) mounted with a silicon chip of 4 mm × 4 mm size was used.
m) Using a mold, a test chip was molded with a low-pressure transfer molding machine under the conditions of a mold temperature of 150 ° C., a molding pressure of 70 kgf / cm ² , and a curing time of 120 seconds. Was evaluated for release properties, changes in appearance during the subsequent cooling process, and storage stability as follows. (1) Hot hardness The hardness of the molded product immediately after opening the mold was measured using a Shore-D hardness meter. (2) Releasability "Good" refers to the state in which the molded article can be released without any defect, "slightly bad" refers to the state in which the corners of the molded article are partially adhered to the mold, and the molded article remains in the mold even in the flat part. The state of adhesion is "bad",
A state in which the molded product could not be taken out without being destroyed was judged as "extremely bad". "Bad" and "extremely bad"
In the case of, it is practically difficult. (3) Package cracking Package cracking is a phenomenon in which a molded product is subjected to excessive stress due to molding distortion, curing shrinkage, etc., while being left to cool to room temperature after the molded product is removed from the mold, causing cracks in the molded product. State. The evaluation of package cracking was made based on the presence or absence of cracks visually. (4) Number of thermal shock cycles After cooling, post-curing was performed at 170 ° C for 6 hours, and a thermal shock test (alternate cycle of 150 ° C for 2 minutes and -196 ° C for 2 minutes)
Was performed, and the number of tests until a crack was formed in the molded product was examined. (5) Spiral flow retention The storage stability was evaluated by the spiral flow retention. The measurement of the spiral flow was performed by molding using a mold for measuring spiral flow according to EMMI-1-66, and determining the flow distance. The flow distance 30 days after storage at 40 ° C. was measured, and the rate of change was determined as the spiral flow retention rate retention rate. (6) Rate of change in viscosity Temperature stability was also evaluated based on the rate of change in viscosity. 10
5 g of a molding material for sealing electronic components was placed in a test tube (inner diameter 12 mm, length 25 cm) kept in an oil bath controlled at a temperature of 0 ± 3 ° C., and kept warm for 10, 30, and 60 minutes. After the heat retention, the molding material was taken out and the viscosity was measured, and the rate of change in viscosity with respect to the viscosity of the untreated molding material (the viscosity of the molding material after the heat treatment / the viscosity of the untreated molding material × 100) was determined. The closer the viscosity change rate is to 100%, the smaller the change in viscosity and the better the temperature stability. In addition, what gelatinized during the heat retention period was described as gelation in the evaluation result table. The gelled product has poor temperature stability because the viscosity after the heat treatment is infinite. The evaluation results are shown in Tables 4 to 6.

[0041]

[Table 4]

[0042]

[Table 5]

[0043]

[Table 6]

In Comparative Example 1 containing no novolak vinyl ester resin in the component (A) in the present invention, the releasability was poor. In Comparative Example 2 containing no polymerization inhibitor, the filling property and the temperature stability were poor, and the storage stability was significantly poor. (C) in the present invention, although containing a polymerization inhibitor
In Comparative Examples 3 to 7, which do not contain the polymerization inhibitor as a component, the filling property or the releasability is poor, and in Comparative Examples 3 to 5, in which the inhibitor concentration is low, the temperature stability is also poor. Further, in the present invention, (A)
In Comparative Example 8, which did not contain the component, the component (B) and the component (C), the gel was completely formed in 30 days, and the fluidity was lost. Since the same storage stability evaluation as other molding materials was not possible, Table 6 shows the evaluation results of the fluidity after 7 days (spiral flow retention).

On the other hand, in the examples containing all of the components (A) to (D), the hardness at the time of heating, the filling property, and the appearance were all good, and the releasability was practically satisfactory. In addition, the storage stability and the temperature stability were all excellent in all Examples including the Example in which the concentration of the polymerization inhibitor was low.

The gelling time of the molding materials for sealing electronic parts of Examples 1 to 5, Examples 14 to 18, Examples 19 to 23 and Comparative Examples 3 to 7 was measured using a JSR type curastometer. . The results are shown in FIG.

FIG. 1 shows that hydroquinone having no nitrogen-oxygen bond in the structure was used as a polymerization inhibitor, and Comparative Examples 3 to 7, which did not contain the component (C) of the present invention, contained the polymerization inhibitor. Even if the amount is increased, the gel time hardly changes, and it is clear that the gel time cannot be controlled. On the other hand, in the embodiment using the polymerization inhibitor containing at least one nitrogen-oxygen bond in the structure of the component (C), the gelation time is prolonged with an increase in the amount of the polymerization inhibitor. Time control is easy.

[0048]

As described in the above Examples, the molding material for sealing electronic parts of the present invention has excellent storage stability and thermal shock resistance of molded products, and can control the rate of polymerization reaction (control of gelation time). )
The molding tolerance is wide due to the ease of molding. Further, at 60 ° C. to 10
It is understood that the composition is excellent in stability in a medium temperature range of about 0 ° C., so that it is optimal not only for transfer molding but also for injection molding. As described above, the molding material for electronic component encapsulation obtained by the present invention is excellent in reliability such as moldability and stability, and therefore has a large industrial value and contributes to high productivity of electronic component devices. it can.

[Brief description of the drawings]

FIG. 1 is a diagram showing the relationship between the gelation time of a molding material and the concentration of a polymerization inhibitor.

[Explanation of symbols]

Δ: 2,2,6,6-tetramethyl as a polymerization inhibitor
Graphs showing dependency of inhibitor concentration in Examples 1 to 5 using -1-piperidinyloxy…: Graph showing dependency of concentration of inhibitors in Examples 14 to 18 using para-benzoquinone-dioxime as a polymerization inhibitor □… Prohibition of polymerization 2,2-diphenyl-picryl-
Inhibitor concentration dependence graphs of Examples 19 to 23 using hydrazyl X: Inhibitor concentration dependence graphs of Comparative Examples 3 to 7 using hydroquinone as a polymerization inhibitor

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H01L 23/31 (72) Inventor Takao Hirayama 5-1 Sunayama, Hazaki-cho, Kashima-gun, Ibaraki Pref. Kashima Plant, Hitachi Chemical Co., Ltd.

Claims (13)

[Claims] (1) a vinyl ester resin, (B) a radical polymerization initiator, and (C) at least one nitrogen-containing compound in the structure.
A polymerization inhibitor containing an oxygen bond, (D) an inorganic filler as an essential component, and 20% by weight of the vinyl ester resin (A)
A molding material for sealing electronic parts, characterized in that the above is a novolac vinyl ester resin. 2. The polymerization initiator of component (B) is used in an amount of 0.05 to 1 based on 100 parts by weight of the vinyl ester resin of component (A).
0 parts by weight, 0.001 to 10
2. The molding material for sealing electronic parts according to claim 1, wherein 100 to 2,000 parts by weight of the inorganic filler of the component (D) is blended. 3. The vinyl ester resin of component (A)
3. The molding material for sealing electronic parts according to claim 1, wherein 80% by weight is a bisphenol A-based vinyl ester resin. 4. The molding material for sealing electronic parts according to claim 1, wherein the polymerization initiator of the component (B) is an organic peroxide. 5. The molding material for sealing electronic parts according to claim 1, wherein the polymerization inhibitor as the component (C) is an oxime compound. 6. The molding material for sealing electronic parts according to claim 1, wherein the polymerization inhibitor (C) is a compound having at least one unpaired electron. 7. The method for molding a molding material for sealing electronic parts according to claim 1, wherein a transfer molding method is used. 8. The method for molding a molding material for electronic parts according to claim 1, wherein an injection molding method is used. 9. The method for molding a molding material for sealing electronic parts according to claim 7, wherein the molding temperature is 120 ° C. to 240 ° C. 10. An electronic component device comprising an electronic component sealed with the electronic component sealing molding material according to claim 1. 11. A method for manufacturing an electronic component device, comprising a step of sealing an electronic component with the molding material for sealing an electronic component according to claim 1. 12. The electronic component device according to claim 10, wherein the electronic component is an active element. 13. The method according to claim 11, wherein the electronic component is an active element.