JP3300134B2 - Thermosetting resin composition cured product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cured thermosetting resin composition having excellent releasability at the time of molding, less mold contamination, and excellent marking characteristics, and sealing with the cured product. The present invention relates to a semiconductor device that is manufactured.

[0002]

2. Description of the Related Art Semiconductor devices such as ICs and LSIs are usually sealed with a ceramic package or a plastic package. Ceramic packages have excellent heat resistance and moisture resistance and can be sealed with high reliability without damage to the semiconductor elements inside the package. In recent years, resin sealing using a plastic package has become mainstream due to the disadvantage of poor mass productivity. Above all, resin molding performed by transfer molding with an epoxy resin composition has obtained good results in terms of workability during molding, mass productivity, and reliability after molding.

[0003] Usually, using this epoxy resin composition,
When the semiconductor element is sealed by transfer molding, a mold release agent such as carnauba wax or polyethylene wax is internally added to the epoxy resin composition in order to improve mold releasability from a mold.

[0004]

Since the release agent is developed by blooming the release agent from the resin composition to the surface of the mold at the time of molding, the release agent is compatible with the resin. No material is used.

In addition, when transfer molding an epoxy resin composition, in order to improve the releasability from a mold,
Often a relatively large amount of release agent is required. But,
When a large amount of the release agent is blended, blooming of the release agent on the surface of the molded product becomes intense, and the release property is improved.
Unless these steps are removed, it is difficult to perform printing or stamping (marking). In addition, as the amount of the release agent increases, the resin leaks from the minute space of the mold increases, resulting in a disadvantage that moldability such as mold contamination deteriorates.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been made of a thermosetting resin composition cured product having excellent releasability, less mold stains, and excellent marking characteristics.
And a semiconductor device encapsulated thereby.

[0007]

Means for Solving the Problems In order to achieve the above-mentioned object, a cured product of the thermosetting resin composition of the present invention contains particles containing a component imparting releasability at the time of molding in the cured product. A)
Are substantially uniformly dispersed, and the particles (A)
Some of them have a structure in which fine particles (B) containing a component more hydrophilic than the particles are dispersed.

[0008]

In other words, the present inventors attempted to obtain a cured product of a thermosetting resin composition having a good mold release property, a small amount of mold stains, and an excellent marking property, so that a small amount of a mold release agent was used. The study was repeated on the structure of the cured thermosetting resin composition when was added. As a result, first, two or more release agents having different HLB values were mixed, and then added to the thermosetting resin composition. Thereby, particles (A) containing a component that imparts release properties in the cured product (hereinafter abbreviated as “release agent (A)”) and release agent (A) in release agent (A)
A thermosetting resin composition cured product having a three- or more-phase structure in which fine particles (B) containing a more hydrophilic component (hereinafter abbreviated as “release agent (B)”) are dispersed has a releasability. Was found to be excellent and the marking characteristics were also excellent, and the present invention was achieved.

Next, the present invention will be described in detail.

[0010] The cured product of the thermosetting resin composition used in the present invention comprises a thermosetting resin, a curing agent and a specific release agent,
It is obtained by curing using a curing accelerator as necessary. An example thereof will be described with reference to FIG. 1. (X) is a cured composition, (A) is a mold release agent having an HLB value of 2 or more and less than 20, and (B) is a specific (A) actually used. )
A release agent having an HLB value greater than that of the release agent. The difference in HLB value is preferably 0.5 to 10.0.

As the thermosetting resin, epoxy resin, urea resin, melamine resin, phenol resin, polyester, urethane resin, imide resin and the like are used. Further, as the epoxy resin, a modified epoxy resin obtained by a reaction with a silicone resin can be used.

As the curing agent used together with the thermosetting resin, for example, in the case of epoxy resin, amines, phenol resin, acid anhydride, polyamide, polymercaptan and the like are used. In the case of urea resins, melamine resins and phenol resins, aldehydes such as formaldehyde and hexamethylenetetramine, in the case of polyesters and urethane resins, in the case of polyvalent alcohols and in the case of imide resins,
Polyamines and amides are used.

The mixing ratio between the thermosetting resin and the curing agent is preferably set in the range of 30 to 150 parts by weight of the curing agent per 100 parts by weight of the thermosetting resin (hereinafter abbreviated as "part"). Particularly, in an epoxy resin, the equivalent ratio of the reactive functional group in the curing agent to the epoxy group of the epoxy resin (epoxy group / reactive functional group) is usually 1 / 0.4 to 1/1.
2, preferably in the range of 1 / 0.8 to 1 / 1.1, from the viewpoint of heat resistance and moisture resistance of the semiconductor device.

The release agent (A) used in the present invention is specified as a surfactant having an HLB value which is a measure of hydrophilicity / lipophilicity of a substance of 2 or more and less than 20. Not. Examples thereof include aliphatic alcohols, aromatic alcohols, fatty acids, fatty acid esters, fatty acid metal salts, aliphatic sulfoxide polyethers, aliphatic amines and aliphatic amides. Preferably, a surfactant having an HLB value of 2 or more and less than 15 is preferable, and examples thereof include fatty acids and aliphatic esters. The particle size of the release agent (A) in the cured product is 0.01 to 10 μm.
m is preferably set, and more preferably 0.01 to 1 μm.

Release agent (B) formed in release agent (A)
As the component, a surfactant having an HLB value of 3 or more and 20 or less is preferable, and a surfactant having an HLB value of 10 or more and 20 or less is more preferable. If the HLB value is higher than that of the component (A), it is not specified. Examples of such surfactants include aliphatic metal salts, aliphatic sulfoxides and aliphatic amides. The particle size of the release agent (B) in the cured product is preferably set to 0.005 to 0.5 μm, more preferably 0.005 to 0.5 μm.
０．１0.1 μm.

The amount of the component forming the release agent (B) is 100 parts by weight of the component forming the release agent (A) with respect to the component forming the release agent (A). B) Component is 5
100 parts is preferable, and it is more preferable to set it to 5 to 50 parts. That is, if the compounding amount of the release agent (B) component is 5 parts or less, there is a tendency that problems are caused in the markability and reliability.

Further, the total amount of these release agents, that is, the compounding amount of the release agent (A) and the release agent (B) is in the range of 0.01 to 10 parts of the whole cured thermosetting resin composition. It is preferable to set as follows. That is, if the compounding amount of the release agent is less than 0.01 part, a problem tends to occur in the release agent, and if it exceeds 10 parts, the marking property tends to be inferior.

If necessary, the curing accelerator used in the present invention is a usual catalyst and is not particularly limited. Specific examples include, for example, in the case of an epoxy resin, nitrogen atom-containing compounds such as tertiary amines, imidazoles, imidazolines, diazabicycloalkenes, aliphatic amines and aromatic amines, and triarylphosphine. Phosphonium salts such as monoalkyl diallyl phosphine and tetraaryl phosphonium tetraallyl borate; phosphorus compounds such as triaryl phosphine triaryl boron complex; aluminum triacetate acetonate;
And metal complexes such as In the case of phenol resins, inorganic acids such as triethylamine and boric acid, organic acids and alkalis, and in the case of polyesters, metal organic compounds such as tetrabutyl zirconate and tetrabutyl titanate, and urethane. In the case of a resin, an organic tin, a tertiary amine, or the like is used.

The cured thermosetting resin composition used in the present invention may further comprise, if necessary, other than the above-mentioned components.
After blending various things, it is obtained by curing. For example,
It is a filler, a surface treating agent for treating the surface of the filler, a flame retardant, a coloring agent and a flexible additive.

The filler is not particularly limited. For example, crystalline silica powder, fusible silica powder, quartz glass powder,
Examples thereof include talc, calcium silicate powder, zirconia silicate powder, and calcium carbonate powder, and a silica-based powder is preferable. The compounding ratio of the filler is preferably from 0 to 90% by weight based on the entire resin composition. That is, if the compounding amount of the filler exceeds 90% by weight, the fluidity of the resin composition decreases, and molding becomes difficult.

Examples of the surface treating agent include known silane coupling agents and the like, examples of the flame retardant include antimony trioxide, antimony pentoxide, phosphate and bromide, and examples of the flexible additive include: , Silicone resin and butadiene-acrylonitrile rubber. However, it is not limited to these.

Such a thermosetting resin composition can be produced, for example, as follows. That is,
To the above-mentioned thermosetting resin and curing agent, the one in which the release agent (A) and the release agent (B) are previously blended is added, and if necessary, a curing accelerator and other additives are appropriately blended. After pre-mixing, the mixture is kneaded at a predetermined temperature by a kneader and melt-mixed. After cooling to room temperature, if it is a solid, it is pulverized by a known means, and if necessary, tableted into a tablet, whereby a thermosetting resin composition can be produced. In the case of a liquid, a thermosetting resin composition can be obtained only by mixing.

The cured thermosetting resin composition of the present invention can be obtained by subjecting the thus obtained thermosetting resin composition to a known molding method such as casting or transfer molding.

The cured product of the thermosetting resin composition thus obtained is excellent in mold releasability at the time of molding due to the effect that the specific release agent contained in the composition takes a specific structure, and has a high performance. -Extremely excellent in kingability and reliability. In addition, a specific structure, that is, a three-phase structure, can be observed with a transmission electron microscope.

[0025]

As described above, in the cured thermosetting resin of the present invention, the specific release agent has a specific structure in the cured product. That is, since the cured product has a three-phase structure like the release agent (A) in the cured body and the release agent (B) in the release agent (A), excellent release with a smaller amount of the release agent. With excellent marking characteristics. Therefore, compared to the conventional
The molding efficiency is remarkably improved, and the reliability when used as a sealing material for a semiconductor device becomes extremely high.

[0026]

Next, examples will be described together with comparative examples. Example 1 100 parts of a bisphenol A type epoxy resin (solid resin) having an epoxy equivalent of 650, 100 parts of tetrahydrophthalic anhydride as a curing agent, and 2-part as a curing catalyst
0.3 parts of ethyl-4-methylimidazole, 1.5 parts of n-butyl behenate (HLB value 5.2) as a releasing agent (A) and zinc stearate as a releasing agent (B) in advance (HLB value: 13.0) 0.5 part of the compounded mixture was added, melted and mixed at 90 to 120 ° C, cooled, pulverized, and the powder was tabletted into tablets. A cured product was prepared by transfer molding.

Examples 2 to 8 and Comparative Examples 1 to 8
The types and amounts of the release agents (A) and (B) shown in Table 1, Table 2, Table 3, Table 4, and Table 5 described below, and otherwise the same as in Example 1 The desired cured product was obtained.

Example 9 100 parts of bisphenol A type epoxy resin (liquid resin) having an epoxy equivalent of 180 were mixed with 100 parts of methylhexahydrophthalic anhydride, and 0.2% of 2-ethyl-4-methylimidazole was used as a curing catalyst. In 3 parts, n-butyl behenate 1.5 was previously used as a release agent (A).
And 0.5 parts of zinc stearate as a mold release agent (B) were added and mixed, and the ten-separation mold agent was dispersed in the resin. 16 at ° C
After curing for a time, a cured product was prepared.

Example 10 o- having an epoxy equivalent of 195
Cresol novolak type epoxy resin (solid resin) 10
0 parts, 60 parts of a novolak phenol resin (phenol equivalent: 106), and 2-ethylimidazo- as a curing catalyst.
To 0.3 part of a mixture, previously added 1.5 parts of n-butyl behenate as a release agent (A) and 0.5 part of zinc stearate as a release agent (B), 90-1
After melt-mixing at 20 ° C. and cooling, the mixture was pulverized, the powder was tabletted, and then a cured product was prepared at 150 ° C. by transfer molding.

Example 11 o- having an epoxy equivalent of 195
Cresol novolak type epoxy resin (solid resin) 10
To 0 parts, 12 parts of a dimethyl silicone having amino groups at both ends (molecular weight: 4000) were mixed in advance, and reacted at 100 ° C. for 5 hours, 60 parts of a novolak-type phenol resin (phenol equivalent: 106), 0.3 parts of 2-methylimidazole as a curing catalyst, 1.5 parts of n-butyl behenate as a release agent (A) and 0.5 parts of zinc stearate as a release agent (B) are previously mixed. The resulting mixture was added, melted and mixed at 90 to 120 ° C., cooled, pulverized, and the powder was tabletted into tablets, followed by transfer molding at 150 ° C. to produce a cured product.

[0031]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

Next, the releasability from the mold, the marking property on the surface of the cured product, and the phase of the release agent in the cured product were obtained by molding the cured products obtained in the above Examples and Comparative Examples. The structure was evaluated. The results are shown in Tables 4, 5 and 6 below.

[Releasability] The releasability was evaluated in five steps by measuring the release load immediately after molding using a mold for releasability evaluation. 5, 4, 3, 2, and 1 in order from the one having good releasability. [Marking characteristics] The marking characteristics are based on YAG laser.
(Energy density 0.3 joules / cm ² )
The cured product was irradiated and evaluated for the sharpness of the marking under a relatively dark atmosphere. In this case, the degree of sharpness was visually evaluated in five stages. 5,4,
3, 2, and 1. [Phase Structure of Release Agent] The phase structure of the release agent was determined by TEM observation (observation with a transmission electron microscope). The ultra-thin section method was used for TEM observation,
It was shaved to a thickness of 0.1 μm with a microscope and observed with the above microscope. The case where the cured body sample had a three-phase structure including the cured body was evaluated as ○, the case where the two-phase structure was observed, and the case where there was no phase structure as X.

[0034]

[Table 6]

[Table 7]

From the results in Tables 6 and 7, Comparative Example 1 shows that
Since the release agent (A) and the release agent (B) are not incorporated at all, the releasability is very poor, and the surface smoothness of the cured product is also poor, so that the marking property is also poor. In Comparative Example 2, only the release agent (A) was used, and only the release agent (A) was compatible with the resin composition, so that almost no release property was exhibited. In Comparative Example 3, only the release agent (B) was used, and the polarity was high, so that the release property was good. However, since the release agent had many bleeds, the marking property was very poor. Comparative Examples 4 and 5 have a three-phase structure and good dispersibility, but have poor release properties due to a small amount of the polar release agent (B). Comparative Example 6 has a three-phase structure, but the release agent (B) is different from the release agent (A).
Since the amount of the release agent is larger than that of the above, the release agent has a large amount of bleed, and the releasability is good, but the marking characteristics are poor.
Comparative Example 7 also has a three-phase structure, but the release agent (A) and the release agent (B) have a large total amount.
And the releasability is good, but the marking characteristics are poor. Furthermore, in Comparative Example 8, all the release agents are compatible with the resin composition, so that the release properties are poor. On the contrary,
It can be seen that all of the examples have a three-phase structure, exhibit good releasability from the mold during molding, and have excellent marking characteristics.

[0036]

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing that a cured resin composition has a three-phase structure.

[Explanation of symbols]

 (X) Cured composition (A) Release agent (A) (B) Release agent (B)

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ identification code FI H01L 23/31 (58) Field surveyed (Int.Cl. ⁷ , DB name) C08J 5/00 C08L 1/00-101/16

Claims (7)

(57) [Claims] The particles (A) containing a component imparting releasability during molding are substantially uniformly dispersed in the cured product, and the particles (A) contain the particles (A). A cured thermosetting resin composition in which fine particles (B) containing a component more hydrophilic than the particles are dispersed. 2. The cured thermosetting resin composition according to claim 1, wherein the HLB value of the particles (A) is 2 or more and less than 20. 3. The cured thermosetting resin composition according to claim 1, wherein the HLB value of the particles (B) is 3 or more and 20 or less. 4. The cured thermosetting resin composition according to claim 1, wherein the size of the particles (A) in the cured product is 0.01 to 10 μm. 5. The cured thermosetting resin composition according to claim 1, wherein the total content of the particles (A) and the particles (B) is 0.01 to 10 parts by weight based on 100 parts by weight of the cured body. . 6. The cured thermosetting resin composition according to claim 1, wherein the component (A) is a fatty acid or an aliphatic ester, and the component (B) is an aliphatic metal salt. 7. A semiconductor device covered with the cured thermosetting resin composition according to any one of claims 1 to 6.