JP2006182801A - Mold release restoring resin composition and method for producing semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which can restore mold release even when used in a small amount, does not cause oil exudation and stain on the surface of a semiconductor device molded just after mold release is restored thereby, can impart sustained mold release, and can well restore release from a semiconductor-sealing mold. <P>SOLUTION: The resin composition for restoring release from a semiconductor sealing mold is a resin composition essentially consisting of (A) an epoxy resin, (B) a phenolic resin, (C) a cure accelerator, (D) an inorganic filler, and (E) a fluoroalkyl group-containing organopolysiloxane having a specific structure, wherein the fluoroalkyl group-containing organopolysiloxane having a specified structure is contained in an amount of 0.1 to 10 wt.% based on the entire epoxy resin composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a mold release recovery resin composition for sealing a semiconductor used for recovering the mold release property of a mold for sealing used in the manufacture of a resin sealed semiconductor device, and a semiconductor device using the same It is related with the manufacturing method.

  Epoxy resin composition for semiconductor encapsulation as the integration of semiconductor elements progresses year by year and the surface mounting of semiconductor devices is promoted in the market trend of downsizing, weight reduction and high performance of electronic devices in recent years. The demand for things has become increasingly severe. Epoxy resin compositions for semiconductor encapsulation using various resins and additives that meet this requirement are prone to mold fouling during continuous molding, and mold defects such as unfilling are likely to occur. Therefore, it has become normal to periodically clean the mold surface.

  Conventionally, a semiconductor sealing mold cleaning material consists of a resin having a high molding shrinkage such as an amino resin and a filler having high hardness such as crystal-crushed silica and glass fiber. The main thing was scraping off the dirt on the mold surface. After using the cleaning material, the mold surface will be clean, but the mold release agent will also be removed, so the cured resin of the semiconductor device molded immediately after cleaning is extremely releasable. There was a problem of getting worse. Therefore, after using the cleaning material, it is necessary to mold the mold release recovery resin composition, transfer the mold release agent in the mold release recovery resin composition to the mold surface, and apply it to recover the release properties. is there.

The function of the mold release recovery resin composition is to transfer and apply the release agent to the mold surface, and to quickly recover the release property, but if a large amount of release agent is transferred, After that, there is a problem of causing oil floating or dirt on the surface of the cured resin of the molded semiconductor device. If the release agent cannot be transferred sufficiently, the release property cannot be recovered, and a large amount of the release recovery resin composition is required. There arises a problem that it is necessary to use it. Furthermore, when the releasability after recovery of releasability cannot be sustained for a long time, it is necessary to frequently use a releasability recovery resin composition, and productivity is lowered.
For this reason, a technique for improving mold release sustainability by adding an antioxidant to a montanic acid ester wax or oxidized or non-oxidized polyethylene wax as a mold release agent is disclosed (for example, see Patent Document 1). ). Although this method improves mold release sustainability, since the main chain of the mold release agent is a carbon chain, it is relatively compatible with the epoxy resin composition for semiconductor encapsulation, and is formed on the surface of the molded semiconductor device. The problem of causing oil floating and dirt could not be solved sufficiently.

JP-A-4-259513 (2-5 pages)

  The present invention relates to a mold release recovery resin composition for semiconductor encapsulation used for recovering the mold release property of a mold for encapsulation used in the production of a resin-encapsulated semiconductor device. Mold release recovery resin composition for semiconductor encapsulation, which can maintain mold release characteristics without recovering oil floatation and dirt on the surface of the semiconductor device immediately after mold release recovery, and molding using the same It is an object of the present invention to provide a method for manufacturing a resin-encapsulated semiconductor device that recovers mold releasability.

The present invention
[1] (A) epoxy resin, (B) phenol resin, (C) curing accelerator, (D) inorganic filler, (E) organopolysiloxane represented by general formula (1) as essential components, A mold release recovery resin composition for semiconductor encapsulation, characterized in that the organopolysiloxane represented by the formula (1) is contained in the total epoxy resin composition in an amount of 0.1 to 10% by weight,

（式中、Ｒ_１は水素、又は炭素数３０以下のフルオロアルキル基、フェニル基若しくはメチル基から選ばれる有機基であり、互いに同一であっても異なっていてもよいが、少なくとも１方は炭素数３０以下のフルオロアルキル基である。Ｒ_２は水素、又はフェニル基、若しくはメチル基から選ばれる有機基であり、互いに同一であっても異なっていてもよい。ｍは平均値で０〜５０の正数であり、ｎは平均値で１〜５０の正数である。）

(In the formula, R ₁ is hydrogen or an organic group selected from a fluoroalkyl group having 30 or less carbon atoms, a phenyl group or a methyl group, which may be the same or different, but at least one of them is carbon. It is a fluoroalkyl group having a number of 30 or less, R ₂ is an organic group selected from hydrogen, a phenyl group, or a methyl group, and may be the same or different, and m is an average value of 0 to 50. And n is an average value of 1 to 50 positive numbers.)

[2] In a method for producing a resin-encapsulated semiconductor device in which a semiconductor element is molded and encapsulated using a resin composition for encapsulating a semiconductor, a mold-release recovery resin composition for encapsulating a semiconductor according to item [1] A method for manufacturing a resin-encapsulated semiconductor device, wherein the mold release property of the molding die is restored using
It is.

  The mold release recovery resin composition for semiconductor encapsulation of the present invention can recover the mold release property by molding a few times, and oil is applied to the surface of the semiconductor device in the semiconductor seal molding immediately after the mold release recovery. It is industrially useful because it contributes to the improvement of productivity in the manufacture of semiconductor devices, because it can maintain a good release property for a long time without causing floating and dirt.

The present invention provides a mold using a mold release recovery resin composition containing an epoxy resin, a phenol resin, a curing accelerator, an inorganic filler, and an organopolysiloxane represented by the general formula (1) as essential components. By recovering the mold release property, the mold release property can be recovered with a small number of moldings, and in the semiconductor sealing molding immediately after the mold release property recovery, oil floating and dirt may be generated on the surface of the semiconductor device. In addition, a remarkable effect can be obtained that a further good releasability can be maintained for a long time.
Hereinafter, the present invention will be described in detail.

  Although it does not specifically limit as an epoxy resin used by this invention, For example, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a biphenyl type epoxy resin, a bisphenol type epoxy resin, a stilbene type epoxy resin, a triphenolmethane Type epoxy resin, phenol aralkyl type epoxy resin, naphthalene type epoxy resin, alkyl-modified triphenol methane type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene-modified phenol type epoxy resin, etc. It may be used.

The phenolic resin used in the present invention is not particularly limited. Examples thereof include phenol aralkyl resins having a phenylene and / or diphenylene skeleton, and these may be used alone or in combination.
The blending ratio of the epoxy resin and the phenol resin is not particularly limited, but the ratio of epoxy group / phenolic hydroxyl group is preferably 0.7 to 1.5, more preferably 0.9 to 1.2, More preferably, 0.95 to 1.15 is desirable. If it deviates significantly from this range, the mold release recovery resin composition will not be sufficiently cured, and workability such as deterioration of mold release may be deteriorated.

  The curing accelerator used in the present invention is one that can be a catalyst for the crosslinking reaction between the epoxy resin and the phenol resin, and examples thereof include tributylamine, 1,8-diazabicyclo (5,4,0) undecene-7, and the like. Amine compounds, organic phosphorus compounds such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate salts, and imidazole compounds such as 2-methylimidazole, but are not limited thereto. These curing accelerators may be used alone or in combination.

（式中、Ｒ_１は水素、又は炭素数３０以下のフルオロアルキル基、フェニル基若しくはメチル基から選ばれる有機基であり、互いに同一であっても異なっていてもよいが、少なくとも１方は炭素数３０以下のフルオロアルキル基である。Ｒ_２は水素、又はフェニル基、若しくはメチル基から選ばれる有機基であり、互いに同一であっても異なっていてもよい。ｍは平均値で０〜５０の正数であり、ｎは平均値で１〜５０の正数である。） Since the organopolysiloxane represented by the general formula (1) used in the present invention has a function of improving the releasability, the mold release recovery resin composition using the organopolysiloxane is used after the cleaning material is used. Excellent mold release recovery. R ₁ in the organopolysiloxane represented by the general formula (1) is hydrogen or an organic group selected from a fluoroalkyl group having 30 or less carbon atoms, a phenyl group or a methyl group, and they are the same or different from each other. At least one is a fluoroalkyl group having 30 or less carbon atoms. R ₂ is hydrogen, or an organic group selected from a phenyl group or a methyl group, and may be the same or different from each other. Moreover, m in General formula (1) is a positive number of 0-50 with an average value, and n is a positive number of 1-50 with an average value. If the value of m exceeds the upper limit value, the dispersibility in the resin is deteriorated, and there is a disadvantage that oil floating and dirt are generated in the semiconductor device molded immediately after the release of the mold is recovered. If the value of n exceeds the upper limit value, it will be difficult to ooze out from the resin, and there will be no release recovery, and if n is 0 and there is no fluoroalkyl group, the dispersibility in the resin will deteriorate. However, it is not preferable because there is a drawback that oil floating or dirt occurs in the semiconductor device molded immediately after the release of the mold release.

(In the formula, R ₁ is hydrogen or an organic group selected from a fluoroalkyl group having 30 or less carbon atoms, a phenyl group or a methyl group, which may be the same or different, but at least one of them is carbon. It is a fluoroalkyl group having a number of 30 or less, R ₂ is an organic group selected from hydrogen, a phenyl group, or a methyl group, and may be the same or different, and m is an average value of 0 to 50. And n is an average value of 1 to 50 positive numbers.)

  The organopolysiloxane represented by the general formula (1) used in the present invention can be obtained by adding a fluoroalkyl group to a Si-H group-containing polysiloxane with a platinum catalyst.

  The compounding amount of the organopolysiloxane represented by the general formula (1) is 0.1 to 10% by weight in the total epoxy resin composition. If the value is below the lower limit, the mold release agent does not sufficiently migrate to the mold surface, and there is a possibility that the expected mold release recoverability may not be obtained. If the upper limit is exceeded, the mold may exude excessively, and oil floating may occur in the semiconductor device formed immediately after the release of the mold.

In addition to the components (A) to (E), the mold release recovery resin composition for semiconductor encapsulation of the present invention includes a mold release agent such as carnauba wax, stearic acid, and montanic acid wax as needed. Additives such as colorants such as ring agents, antioxidants, and carbon black may be used.
The mold release recovery resin composition for semiconductor encapsulation of the present invention is obtained by mixing the raw materials sufficiently uniformly using a mixer or the like, then melt-kneading with a hot roll or kneader, etc., cooling and pulverizing. .

Examples of the present invention are shown below, but the present invention is not limited thereto. The blending ratio is parts by weight.
The organopolysiloxanes 1 to 8 used in Examples and Comparative Examples are collectively shown in Table 1 for R1, R2, and m, n in the general formula (1).

Example 1
Orthocresol novolac type epoxy resin (softening point 65 ° C., epoxy equivalent 209)
20.2 parts by weight Phenol novolac resin (softening point 90 ° C., hydroxyl group equivalent 104) 10.0 parts by weight 1,8-diazabicyclo (5,4,0) undecene-7 (hereinafter referred to as DBU)
0.2 parts by weight Fused spherical silica (average particle size 21 μm) 67.0 parts by weight Organopolysiloxane 1 2.0 parts by weight Carnauba wax 0.3 parts by weight Carbon black 0.3 parts by weight After mixing, the kneaded material sheet obtained by kneading 20 times using biaxial rolls having a surface temperature of 95 ° C. and 25 ° C. was cooled, and the pulverized material of 4 mesh or less was pulverized after cooling. The characteristics of the obtained resin composition were evaluated by the following methods. The evaluation results are shown in Table 2.

Evaluation Method Mold Release Recovery: Using a melamine resin-based cleaning material (EMEC3, manufactured by Sumitomo Bakelite Co., Ltd.) for cleaning the mold surface, the molded product was molded three times with a mold for load release evaluation. After removing the mold release agent component on the surface of the mold, the mold release recovery resin composition was molded three times, and the mold temperature was 175 ° C., the injection pressure was 6.9 MPa, and the curing time was 2 minutes. The material for evaluation was transfer molded, and the release load at the time of product extraction was measured. The unit is MPa. The judgment criteria were 30 MPa or higher as rejected and 30 MPa or lower as acceptable. The mold for load release evaluation consists of an upper mold, a middle mold, and a lower mold. After molding, a round molded product with a diameter of 14 mm and a thickness of 1.5 mm attached to the middle mold is pushed from the upper hole of the middle mold with a push pull gauge. And the load applied when the molded product was protruded was measured. As an evaluation material, Sumitomo Bakelite Co., Ltd., epoxy resin molding material EME-7351 for semiconductor encapsulation was used.

  Mold release sustainability: Using a melamine resin-based cleaning material (EMEC3, manufactured by Sumitomo Bakelite Co., Ltd.) for cleaning the mold surface, the molded product was molded three times with a mold for load release evaluation, After removing the mold release agent component on the mold surface, the mold release recovery resin composition was molded three times, and then the evaluation material was obtained at a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 2 minutes. Transfer molding was performed, and the mold release load at the time of product extraction was measured. The mold release load is molded using a mold for load evaluation at the time of mold release composed of an upper mold, a middle mold, and a lower mold. After molding, a 14.5 mmΦ and 1.5 mm thick circular molded product attached to the middle mold A push bull gauge was applied from the upper hole of the middle mold, and the load applied when the molded product was projected. Subsequently, the evaluation material was molded into 200 shots, and the change in the release load for each shot was measured. At this time, the number of shots when the load was 80 MPa or more was described in the results. 200 <means 200 shots or more, and expresses that the load is 80 MPa or less even after 200 shots. The judgment criteria were less than 150 shots as unacceptable and 150 shots or more as acceptable.

  Molded product stain: Immediately after the use of the mold release recovery resin composition, the oil floating on the molded product surface of the molded evaluation material was visually confirmed. The case where the surface of the product was stained was expressed as x, and the case where the surface was not stained was expressed as ○.

Examples 2-10, Comparative Examples 1-6
Using the organopolysiloxane shown in Table 1, a resin composition was prepared in the same manner as in Example 1 according to the formulations in Tables 2, 3 and 4, and evaluated in the same manner as in Example 1. The results are shown in Table 2, Table 3, and Table 4. The biphenyl type epoxy resin (YX-4000 manufactured by Japan Epoxy Resin Co., Ltd.) used in Example 2 has a melting point of 105 ° C. and an epoxy equivalent of 195. The phenol aralkyl resin (Mitsui Chemicals, XL-225) used in Example 2 has a softening point of 79 ° C. and a hydroxyl group equivalent of 174. In Example 3, montanic acid wax was used as a release agent.

  The mold release recovery resin composition for semiconductor encapsulation of the present invention can recover the mold release property by molding a few times, and oil is applied to the surface of the semiconductor device in the semiconductor seal molding immediately after the mold release recovery. It is industrially useful because it contributes to the improvement of productivity in the manufacture of semiconductor devices, because it can maintain a good release property for a long time without causing floating and dirt.

Claims (2)

(A) An epoxy resin, (B) a phenol resin, (C) a curing accelerator, (D) an inorganic filler, (E) an organopolysiloxane represented by the general formula (1) as an essential component, and a general formula (1 The mold release recovery resin composition for semiconductor encapsulation, characterized in that 0.1 to 10% by weight is contained in the total epoxy resin composition.

(In the formula, R ₁ is hydrogen or an organic group selected from a fluoroalkyl group having 30 or less carbon atoms, a phenyl group or a methyl group, which may be the same or different, but at least one of them is carbon. It is a fluoroalkyl group having a number of 30 or less, R ₂ is an organic group selected from hydrogen, a phenyl group, or a methyl group, and may be the same or different, and m is an average value of 0 to 50. And n is an average value of 1 to 50 positive numbers.) In the manufacturing method of the resin sealing type semiconductor device which shape-seals a semiconductor element using the resin composition for semiconductor sealing, a mold metal using the mold release recovery resin composition for semiconductor sealing according to claim 1 A method for manufacturing a resin-encapsulated semiconductor device, wherein mold release properties are restored.