WO2008050682A1

WO2008050682A1 - Resin composition for cleaning molds and recovering the release properties of molds and method for cleaning molds and recovering the release properties of molds

Info

Publication number: WO2008050682A1
Application number: PCT/JP2007/070436
Authority: WO
Inventors: Kiyohito Hiromitsu; Hiroaki Nomura; Kenichi Hamaura
Original assignee: Nippon Carbide Kogyo Kabushiki Kaisha
Priority date: 2006-10-27
Filing date: 2007-10-19
Publication date: 2008-05-02
Also published as: JP4948541B2; TWI410316B; KR101395818B1; CN101466515A; MY155928A; CN101466515B; HK1131099A1; JPWO2008050682A1; TW200843927A; KR20090084669A

Abstract

A resin composition for cleaning molds and recovering the release properties of molds which can remove not only stains of a cavity, a runner and a gate but also stains of an air vent and a parting area of a mold and can impart release properties to the surface of a mold. The composition comprises a melamine resin, at least one metal soap type mold-releasing agent, and preferably mannitol and/or a mold-releasing agent other than metal soaps. The composition is a compression-type one which has both the ability to clean a mold and the ability to recover the release properties of a mold and thus dispenses with the release properties recovering step which was to be conducted after the completion of the mold cleaning step in the prior art.

Description

Specification

Resin composition for mold cleaning and release recovery, and mold cleaning and mold release recovery method

Technical field

[0001] The present invention relates to a compression type mold having both cleaning properties and mold release properties, which removes dirt on the mold surface and imparts mold release properties to the mold surface when molding a curable resin molding material. The present invention relates to a mold cleaning and release recovery resin composition, and a mold cleaning and mold release recovery method using the resin composition.

Background art

Conventionally, when molding a molded product such as an integrated circuit using a thermosetting resin such as an epoxy resin, if the molding is continued for a long time, the inner surface of the mold becomes soiled. In many cases, the surface of the molded product becomes dirty or the sealed molded product adheres to the mold and the molding operation cannot be continued. Therefore, it is necessary to periodically clean the mold, and a method of cleaning the mold by molding a mold cleaning resin at a rate of several shots every time hundreds of molding materials are molded has been proposed.

For example, Japanese Examined Patent Publication No. 52-788 discloses that a mold surface is molded with a material mainly composed of an amino resin at the time of molding a curable resin molding material (excluding an amino resin molding material). Thus, a cleaning method "has been proposed, and a mold cleaning resin composition comprising an amino resin, an organic base material and / or an inorganic base material, and a release agent is disclosed.

[0003] In recent years, as integrated circuits and the like (abbreviated as IC'LSI) have been highly integrated, thinned, and surface-mounted, the shape and structure of molded products have been diversified. High fluidity of materials is planned.

For this reason, in the high fluidization type epoxy sealing material, resin clogging occurs in the air vent part, and if these clogging occur immediately, the air does not escape and the resin does not flow. Since it occurs and becomes defective, continuous molding becomes difficult. Therefore, the force transfer that needs to be performed to avoid these situations. For the transfer material, the resin does not flow normally for the above reasons. It was difficult to remove the resin clogged with the resin.

[0004] On the other hand, after cleaning with a mold cleaning resin composition, the surface of the mold becomes clean. On the other hand, the mold release agent is also removed, so the mold was molded immediately after cleaning. However, there was a problem that the releasability deteriorated extremely. Therefore, after using the resin composition for mold cleaning

Therefore, it was necessary to mold the mold release recovery resin composition and transfer the release agent in the mold release recovery resin composition to the mold surface to recover the mold release property.

This mold release recovery resin composition transfers a release agent to the mold surface and quickly recovers the release characteristics. Conventionally, as a mold release recovery resin composition, for example, a composition comprising components such as epoxy resin, phenol resin, curing accelerator, carnauba wax, and silica has been used.

[0005] In these mold release recovery resin compositions as well, the resin cannot flow into the entire air vent due to resin clogging in the air vent portion, as described above. Mold recovery was difficult.

[0006] Patent Document 1: Japanese Patent Publication No. 52-788

Disclosure of the invention

Problems to be solved by the invention

[0007] The present invention relates to the resin clogging of the air vent part accompanying the high fluidization of the semiconductor sealing material as described above, the difficulty of cleaning by the mold cleaning resin composition, and the mold release recovery resin. The present invention intends to solve the difficulty of mold release recovery by the composition. Further, the present invention can easily clean the air vent part and recover the mold release, and after cleaning the mold surface dirt, to replenish the mold release component removed together with the dirt. When using mold recovery resin composition! /, Mold cleaning and mold release recovery power that can be performed at the stage of mold cleaning and mold release recovery power, which is not possible with the conventional two-step process. It aims to provide a compression-type resin composition for mold cleaning and mold release recovery that has both properties.

Means for solving the problem

[0008] The present invention has been made to solve the above-described problems, and removes dirt on the mold surface and imparts releasability to the mold surface when forming a curable resin molding material. so A mold cleaning and mold release recovery resin composition characterized by comprising a melamine resin and containing at least one metal stalagmite mold release agent. In

[0009] The resin composition for mold cleaning and mold release recovery of the present invention preferably further contains a release agent other than mannitol and / or metal sarcophagus.

The invention's effect

[0010] The resin composition for mold cleaning and mold release recovery of the present invention has both the mold cleaning effect and the mold release recovery effect, and is not limited to cubity, runner, and gate contamination. This is a compression-type resin composition that removes dirt from the air vent part and mold parting area, and in particular can easily clean and release the air vent part. Mold cleaning work with mold and mold release recovery resin Mold cleaning and mold release recovery are performed in one stage without the need for complicated two-stage work consisting of mold release recovery work with composition can do.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the resin composition for mold cleaning and mold release recovery of the present invention will be described in detail.

The melamine resin used in the present invention can be produced by a known method. For example, monoole ratio of honore guanole de hydride and melamine crystalol is 1:;! ~ 4: 1, YI is reacted in aqueous solution at 1 · 5: 1 ~ 3: 1 in aqueous solution. To manufacture. Melamine crystallinole concentration 20-60%, reaction temperature 70-; reaction at 100 ° C, slightly alkaline, and the reaction is completed in 10-100 minutes. A part of the formaldehyde can be replaced with paraformaldehyde or an aldehyde component other than formaldehyde, for example, an aliphatic aldehyde such as acetaldehyde.

[0012] The resin composition for mold cleaning and mold release recovery of the present invention contains a metal sarcophagus release agent in addition to the melamine resin.

Examples of the metal stalagmite release agent include calcium stearate, zinc stearate, zinc myristate and the like. The amount of addition is preferably 0.2 to 1.0 parts by weight, more preferably 0.4 to 0. 8 parts by weight. If the addition amount of the metal stalagmite-based release agent is insufficient, the releasability and cleanability are deteriorated.

[0013] The resin composition for mold cleaning and mold release recovery of the present invention preferably further contains mannitol in addition to the melamine resin and the metal stalagmite release agent. By containing mannitol, it is possible to reduce discoloration by heating while maintaining mold releasability.

As mannitol, D-mannitol is preferable.

When mannitol is included, it is preferable that the metal stalagmite-based mold release agent and mannitol contain 90: 10-30: 70, especially 80: 20-40: 60 by weight. . When the ratio of mannitol is excessive, the cleaning property is deteriorated.

The addition amount of mannitol is preferably 0.2 to 1.0 part by weight, more preferably 0.3 to 0.8 part by weight with respect to 100 parts by weight of the melamine resin. If the amount of mannitol added is insufficient, if the addition effect is too small, the mold release property is good, but the cleaning property decreases.

[0014] In addition, the resin composition for mold cleaning and mold release recovery of the present invention includes a release agent other than the metal sarcophagus, in addition to the melamine resin and the metal sarcophagus release agent. It is also preferable to contain it. By including a release agent other than the metal sarcophagus, it becomes possible to exhibit mold releasability without being affected by the release component in the epoxy sealing material.

Examples of the release agent other than the metal stalagmite include ester release agents such as montanic acid partially hatched ester and polymer composite ester, and synthetic waxes such as modified hydrocarbon wax and mineral oil synthetic wax. Specifically, Lycowax OP (partially saponified ester of montanic acid manufactured by Clariant Japan Co., Ltd.), Roxyol G78 (polymer compound ester manufactured by Cognis Japan Co., Ltd.), Ricorub H-4 (modified hydrocarbon produced by Clariant Japan Co., Ltd.) ) And Roxyol VPN881 (a mineral oil-based synthetic wax manufactured by Cognis Japan Co., Ltd.) can be suitably used. As mold release agents other than metal stalagmites, ester-type mold release agents and synthetic waxes listed here are preferred. When mold release agents other than those listed here are used, cleaning properties may deteriorate. is there.

When a release agent other than these metal sarcophagus is included, the content ratio of the metal sarcophagus release agent and the release agent other than the metal sarcophagus is 90: 10-30: 70, especially 80: 20-40: 60 It is preferable to make it contain. When the ratio of the release agent other than the metal stalagmite is excessive, the cleaning property is deteriorated.

The addition amount of the mold release agent other than the metal sarcophagus is preferably 0.02-0. 7 parts by weight, more preferably 0. is there. If the addition amount of the release agent other than the metal stalagmite is insufficient, the release effect is good if the addition effect is too small, but the cleaning property is lowered.

[0015] The resin composition for mold cleaning and mold release recovery of the present invention preferably contains pulp for improving the cleaning effect. As the pulp, straw pulp, bamboo pulp, wood pulp (conifer pulp, hardwood pulp) and the like are used, and any of chemical pulp and mechanical pulp may be used.

The pulp is in a form (resin impregnated pulp) in which the pulp is impregnated with the melamine resin, which is an essential component of the resin composition for mold cleaning and mold release recovery of the present invention, for mold cleaning of the present invention. And it is preferable to make it contain in the mold release recovery resin composition. The resin impregnated pulp can be prepared by impregnating pulp with an aqueous solution of melamine formaldehyde resin and drying it. In addition, fluidity can be further improved by replacing part or all of the pulp with powdered pulp.

The size of the pulp is not particularly limited, but is generally 5 to 1000 m, preferably about 10 to 200 ^ 111. The content of the pulp is generally 5 to 70 parts by weight, preferably 20 to 60 parts by weight with respect to 100 parts by weight of the melamine resin. If the pulp content is less than 5 parts by weight, the effect of addition is insufficient. If the content exceeds 70 parts by weight, the fluidity becomes poor and the mold contaminants remain without being filled in every corner of the mold, which is preferable.

[0016] Further, the resin composition for mold cleaning and mold release recovery of the present invention preferably contains a curing catalyst. Curing catalysts include organic acids such as phthalic anhydride, oxalic acid, sulfamic acid and paratoluenesulfonic acid, inorganic acids such as hydrochloric acid and sulfuric acid, these acids and triethylamine, triethanolamine, β-dimethylaminoethanol, Examples thereof include salts with 2-methyl-2-amino-1-propanol. The amount of curing catalyst added is generally 1.5 parts by weight or less, preferably 0.05 parts by weight or more, and preferably 1 part by weight or less with respect to 100 parts by weight of the melamine resin. Good. The resin composition for mold cleaning and mold release recovery according to the present invention preferably contains one or more selected from the above pulp and curing catalyst.

In addition, to the resin composition for mold cleaning and mold release recovery of the present invention, a coloring material such as a pigment, a fibrous filler other than pulp, a filler having a low hardness and a small particle diameter, and the like are appropriately added. can do.

[0017] In preparing the resin composition for mold cleaning and mold release recovery of the present invention, melamine resin, metal stalagmite release agent, mannitol, mold release agent other than metal sarcophagus, and pal Any means capable of uniformly mixing other additives such as a slag can be employed.

For example, a kneader, a ribbon blender, a Henschenore mixer, a Bonore minole, a ronore kneading machine, a lazy machine, a tumbler, etc. can be exemplified.

[0018] Examples of the curable resin molding material capable of cleaning and releasing the mold using the resin composition for cleaning the mold and recovering the mold release of the present invention include, for example, an epoxy resin molding material and a phenol resin. Examples thereof include an epoxy resin molding material, and particularly an epoxy resin molding material for semiconductor encapsulation. In addition, the resin composition for mold cleaning and mold release recovery of the present invention is a force that can be used for any mold as long as it is a mold used when automatically molding the curable resin molding material. It can be suitably applied to a mold made of chromium or the like.

By molding the resin composition for mold cleaning and mold release recovery of the present invention with a mold, dirt on the mold surface can be removed and mold release can be imparted to the mold surface. . The molding conditions of the resin composition for mold cleaning and mold release recovery of the present invention are preferably a mold temperature of 160 to 190 ° C, a molding pressure of 10 to 20 MPa, and a curing time of 2 to 3 minutes.

Example

Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited to these examples and the like.

[0020] (Production Example 1)

480 parts by weight of melamine, 520 parts by weight of formalin (37% aqueous solution) and 350 parts by weight of water are heated and reacted to make a melamine formaldehyde resin by a known method, and 257 parts by weight of pulp is added to the resulting aqueous solution of melamine resin. After kneading, the resin content is about 72 % Of pulp-containing melamine formaldehyde resin powder (melamine resin impregnated pulp) was obtained.

(Production Example 2)

The melamine resin aqueous solution (solid content: about 60% by weight) obtained in Production Example 1 was dried at about 200 ° C. with a spray dryer apparatus to obtain a powdery melamine resin.

[Example 1]

By mixing in a ball mill 1000 parts by weight of pulp-containing melamine formaldehyde resin powder obtained in Production Example 1 and 0.5 parts by weight of phthalic anhydride and 6.0 parts by weight of zinc stearate. Resin composition A for mold cleaning and mold release recovery was obtained. With respect to the obtained resin composition A, mold cleaning properties and mold releasability were evaluated by the following test methods. The results are shown in Table 1. As shown in Table 1, resin composition A exhibited excellent mold cleaning properties. In addition, after the mold was cleaned with resin composition A, an epoxy encapsulant was molded without using the mold release recovery resin composition. Compared with the conventional mold release recovery resin composition. As a result, mold releasability comparable to that of the mold was shown.

[Example 2]

1000 parts by weight of pulp-containing melamine formaldehyde resin powder with a resin content of about 72% obtained in Production Example 1 and 30 parts by weight of powdered melamine resin obtained in Production Example 2, 30 parts by weight of powder pulp, phthalic anhydride 0.5 parts by weight, zinc stearate 2.5 parts by weight and calcium stearate 3.5 parts by weight were mixed in a ball mill to obtain a resin composition B for mold cleaning and mold release recovery. . With respect to the obtained resin composition B, the mold cleaning property and the mold release property were evaluated in the same manner as in Example 1. The results are shown in Table 1. As shown in Table 1, resin composition B exhibited excellent mold cleaning properties. In addition, after the mold was cleaned with the resin composition B, the mold release recovery resin composition was not used! /, And when an epoxy sealing material was molded, the conventional mold release recovery resin composition was The mold releasability is comparable to that when used.

[0023] [Test method]

Study

Commercially available biphenyl epoxy resin molding material (Sumitomo Bakelite Co., Ltd. EME -Using 7351T), the mold was soiled by molding 500 shots with a TQFP mold. Using this dirty mold, evaluation was performed by repeatedly molding the resin composition for mold cleaning and mold release recovery until the mold surface was cleaned cleanly.

Thumbtack

After completion of the cleaning property test, mold releasability was confirmed by a continuous molding test using a commercially available biphenyl epoxy resin molding material (EME-7351T manufactured by Sumitomo Bakelite Co., Ltd.). In addition, the mold release recovery test was not performed for the mold cleaning and mold release recovery resin compositions, which had poor mold cleaning properties and were not completely cleaned.

[table 1]

[Example 3]

1000 parts by weight of melamine-formaldehyde resin powder with a resin content of about 72% obtained in Production Example 1, 0.5 parts by weight of phthalic anhydride, 3.0 parts by weight of zinc stearate and 2.0 parts by weight of D-mannitol Were mixed with a ball mill to obtain a resin composition C for mold cleaning and mold release recovery. With respect to the obtained resin composition C, in the same manner as in Example 1, the mold cleaning property and the mold release property were evaluated. The results are shown in Table 2. Resin composition C exhibited excellent mold cleaning properties as shown in Table 2. Also, after the mold was cleaned with resin composition C, the mold release recovery resin composition was not used! /, And when an epoxy sealant was molded, the conventional mold release recovery resin composition was The mold releasability is comparable to that when used.

[Example 4]

1000 parts by weight of melamine-formaldehyde resin powder with a resin content of about 72% obtained in Production Example 1, 0.5 parts by weight of phthalic anhydride, 1.5 parts by weight of zinc stearate and 3.0 parts by weight of D-mannitol Is mixed with a ball mill for mold cleaning and Resin composition D for mold release recovery was obtained. With respect to the obtained resin composition D, the mold cleaning property and the mold release property were evaluated in the same manner as in Example 1. The results are shown in Table 2. Resin Composition D exhibited excellent mold cleaning properties as shown in Table 2. In addition, when a mold release recovery resin composition is not used after cleaning the mold with resin composition D! /, The conventional mold release recovery resin composition is obtained. The mold releasability is comparable to that when used.

[Table 2]

[Example 5]

1000 parts by weight of melamine-formaldehyde resin powder with a resin content of about 72% obtained in Production Example 1, 0.5 parts by weight of phthalic anhydride, 2.5 parts by weight of zinc stearate, and Lycowax OP (Clariant Japan Co., Ltd.) (Montannic acid partially saponified ester manufactured by company) 3-5 parts by weight were mixed in a ball mill to obtain a resin composition E for mold cleaning and mold release recovery. With respect to the obtained resin composition E, the mold cleaning property and the mold release property were evaluated in the same manner as in Example 1. The results are shown in Table 3. As shown in Table 3, resin composition E exhibited excellent mold cleaning properties. In addition, after the mold was cleaned with resin composition E, an epoxy encapsulant was molded without using the mold release recovery resin composition, compared with the conventional mold release recovery resin composition. As a result, mold releasability comparable to that of the mold was shown.

[Example 6]

1000 parts by weight of melamine-formaldehyde resin powder with a resin content of about 72% obtained in Production Example 1, 0.5 parts by weight of phthalic anhydride, 2.5 parts by weight of zinc stearate, and Roxyol G78 (Cognis Japan Co., Ltd.) Polymer Composite Ester) 1.0 parts by weight were mixed with a ball mill to obtain a resin composition F for mold cleaning and mold release recovery. For the obtained resin composition F, in the same manner as in Example 1, the mold cleaning property and the mold The mold releasability was evaluated. The results are shown in Table 3. Resin Composition F exhibited excellent mold cleaning properties as shown in Table 3. In addition, after the mold was cleaned with the resin composition F, an epoxy sealing material was molded without using the mold release recovery resin composition, and when the conventional mold release recovery resin composition was used. Compared with that, mold releasability comparable to that of the mold was shown.

[Example 7]

1000 parts by weight of pulp-containing melamine formaldehyde resin powder with a resin content of about 72% obtained in Production Example 1 and 30 parts by weight of powdered melamine resin obtained in Production Example 2, 30 parts by weight of powder pulp, phthalic anhydride 0. 5 parts by weight, zinc stearate 2.5 parts by weight and Recolb H-4 (modified hydrocarbon manufactured by Clariant Japan Co., Ltd.) 3. 5 parts by weight are mixed in a ball mill for mold cleaning and mold release. Resin composition G for mold recovery was obtained. The obtained resin composition G was evaluated in the same manner as in Example 1 for mold cleaning properties and mold release properties. The results are shown in Table 3. As shown in Table 3, resin composition G exhibited excellent mold cleaning properties. In addition, after the mold was cleaned with the resin composition G, an epoxy encapsulant was molded without using the mold release recovery resin composition, and compared with the conventional mold release recovery resin composition. As a result, mold releasability comparable to that of the mold was shown.

[Example 8]

1000 parts by weight of pulp-containing melamine formaldehyde resin powder with a resin content of about 72% obtained in Production Example 1 and 30 parts by weight of powdered melamine resin obtained in Production Example 2, 30 parts by weight of powder pulp, phthalic anhydride 0. 5 parts by weight, zinc stearate 2.5 parts by weight and mouth oxy VPN881 (mineral oil based synthetic wax, manufactured by Cognis Japan Co., Ltd.) 3. Resin composition H for mold release recovery was obtained. With respect to the obtained resin composition H, the mold cleaning property and the mold release property were evaluated in the same manner as in Example 1. The results are shown in Table 3. As shown in Table 3, Resin Composition H exhibited excellent mold cleaning properties. In addition, after the mold was cleaned with the resin composition H, an epoxy encapsulant was molded without using the mold release recovery resin composition, and compared with the conventional mold release recovery resin composition. As a result, mold releasability comparable to that of the mold was shown.

[0032] [Table 3] Resin composition Mold cleanability Mold releasability

Number of shots completed

h type / lower type

Example 5 E 5 times / 5 times Good

Example 6 F 5 times / 5 times Good

Example 7 G 4 times / 4 times Good

Example 8 H 6 times Z 6 times Good Industrial applicability

By using the resin composition for mold cleaning and mold release recovery according to the present invention, a cavity part, an air vent part, etc. due to the recent enhancement of the functionality of epoxy sealing resin and the enhancement of the function of semiconductor elements. In addition, it is possible to remove mold stains, and it is possible to impart mold releasability to a mold without performing mold release recovery work that was conventionally required after completion of mold cleaning work. . As a result, a series of extremely complicated mold cleaning operations and mold release recovery operations can be reduced, and the operation time can be shortened. In addition, the lead frame, dummy frame, and other parts required for transfer molding are no longer required, so the costs for a series of mold cleaning and mold release recovery operations can be reduced.

Claims

The scope of the claims

[I] A resin composition that removes dirt on the mold surface and imparts releasability to the mold surface during molding of the curable resin molding material, contains a melamine resin, and contains at least one metal stone A resin composition for mold cleaning and mold release recovery, characterized by containing a mold release agent.

[2] The mold cleaning and mold according to claim 1, which contains 0.2 to 1.0 part by weight of the metal sarcophagus release agent with respect to 100 parts by weight of melamine resin. Resin composition for mold release recovery.

[3] The resin composition for mold cleaning and mold release recovery according to claim 1 or 2, further comprising mannitol.

[4] The resin composition for mold cleaning and mold release recovery according to claim 3, wherein the mannitol is D-mannitol.

[5] The content ratio of the above-mentioned metal stalagmite-based mold release agent and the above-mentioned mannitol is 90: 10-3 by weight ratio

5. The resin composition for mold cleaning and mold release recovery according to claim 3 or 4, which is 0:70.

[6] The resin composition for mold cleaning and mold release recovery according to any one of claims 1 to 5, further comprising a release agent other than the metal sarcophagus.

[7] The resin composition for mold cleaning and mold release recovery according to claim 6, wherein the release agent other than the metal sarcophagus is an ester release agent or a synthetic wax.

[8] The resin composition for mold cleaning and mold release recovery according to [7], wherein the ester release agent is a montanic acid partially hatched ester or a polymer composite ester.

[9] The resin composition for mold cleaning and mold release recovery according to claim 7, wherein the synthetic wax is a modified hydrocarbon wax or a mineral oil-based synthetic wax.

[10] The content ratio of the metal stalagmite-based release agent and the mold release agent other than the metal sarcophagus is expressed by weight ratio.

The resin composition for mold cleaning and mold release recovery according to any one of claims 6 to 9, which is 90: 10-30: 70.

[I I] The resin composition for mold cleaning and mold release recovery according to any one of claims 1 to 10, further comprising at least one of a pulp and a curing catalyst.

[12] The resin composition according to any one of claims 1 to 11, wherein the resin composition is a compression type. The resin composition for mold cleaning and mold release recovery as described in 1.

A mold cleaning and mold release recovery method according to any one of claims 1 to 12; and a mold cleaning and mold release recovery method.