KR101436809B1 - Resin composition for recovering mold releasability and method for recovering mold releasability - Google Patents

Abstract

The resin composition for restoring mold release of the present invention is a resin composition for imparting releasability to the surface of a mold after removing dirt on the surface of the mold at the time of molding of the curable resin molding material. The resin composition contains a melamine resin, A soap-based releasing agent, an organic fatty acid ester-based releasing agent and / or a synthetic wax. The resin composition for recovering mold release of the present invention has excellent mold releasability and mold releasability is retained for a long time, so that continuous molding of the encapsulated molded article for a long time is possible.

Curable resin, molding, mold, mold release recovery, releasing agent, resin composition

Description

TECHNICAL FIELD [0001] The present invention relates to a resin composition for recovering mold release and a method for recovering mold release,

The present invention relates to a resin composition for mold release recovery which imparts releasability to the surface of a mold after removing dirt on the surface of the mold during molding of the curable resin molding material and a mold release recovery method using the resin composition for recovering mold release . According to the resin composition for mold release recovery of the present invention, the releasability of the surface of the mold is excellent, and subsequent sealing of the molding material can be performed continuously for a long time.

An epoxy resin molding material, etc., the mold releasing agent contained in the thermosetting resin molding material seeps into the interface between the molded article and the mold to form a cull portion, a cavity And the runner portion. If such molding is continued for a plurality of times, there arises a phenomenon such that the releasability of the molded article remarkably deteriorates, or the surface of the molded article becomes rough, thereby causing a problem in appearance of the molded article or a defect in the printing step after molding Occurs.

This is presumably because the release agent contained in the molding material is sequentially laminated on the surface of the mold by repetition of molding at a high temperature and gradually oxidized to form an oxidized deteriorated layer of a hard release agent.

Therefore, although the mold is cleaned in order to avoid such situations, after the cleaning is completed, the surface of the mold is cleaned, while the mold releasing system of the mold surface is removed. Therefore, if the molding is performed immediately after the end of cleaning, There was a problem. Therefore, after use of the cleaning material, it is necessary to mold the resin composition for recovering the mold release mold and to transfer the mold release agent in the resin composition for mold release recovery to the surface of the mold to restore the mold releasability.

Patent Document 1 discloses a process for producing a molded article comprising a molding material containing at least one kind of a releasing agent selected from the group consisting of at least 10 parts by weight of a metal soap, at least 5 parts by weight of waxes and at least 0.5 part by weight of an oligomer, Thereby releasing the releasing agent to the surface of the mold and quickly restoring the mold releasing property. As a result, it is said that troublesome work of spraying the release agent onto the surface of the mold is solved. However, in this method, the number of times of continuous molding of the molded article after releasability recovery was very small.

On the other hand, in recent years, as the integration, thinning, and surface mounting of integrated circuits (IC and LSI) have become more and more complicated, the shapes and structures of molded products have been diversified. While these sealing resins are being fluidized, there is a new problem that the productivity is poor because the mold is liable to be dirty due to poor mold release. Therefore, the mold cleaning work is performed frequently, and furthermore, the mold release restoration work is frequently performed. Therefore, the mold release property after the mold release recovery is maintained for a long time and the mold release recovery A resin composition is required.

Patent Document 1: JP-A-48-79849

As described above, the present invention provides a resin composition for mold release recovery that corresponds to the frequent cleaning work and release recovery work accompanying the high-temperature molding of a semiconductor encapsulating material, that is, the mold release after mold release is maintained for a long time, And to provide a resin composition for mold release recovery that enables continuous molding of a molded article to be molded for a long period of time after recovery from mold release.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-described problems, and it is an object of the present invention to provide a resin composition for imparting releasability to a surface of a mold after removal of dirt on the surface of the mold at the time of molding the curable resin molding material, which comprises a melamine resin, Which is characterized by containing a soap-based releasing agent, an organic fatty acid ester-based releasing agent and / or a synthetic wax. As a result, it is possible to obtain a mold release recovery resin composition capable of continuous molding of a molded article after release recovery for a long time.

The resin composition for recovering mold releasability of the present invention is a resin composition for recovering mold releasability of a curable resin molding material in which the dirt on the surface of the mold and the parting area of the mold are removed, ). This makes it possible to obtain a mold release recovery resin composition capable of releasing the air vent portion and continuously molding the molded article after recovery of the mold release for a long period of time It is.

EFFECTS OF THE INVENTION [

INDUSTRIAL APPLICABILITY The resin composition for mold release recovery of the present invention exhibits a mold release recovery effect by containing a metal soap-based releasing agent, an organic fatty acid ester-based releasing agent and / or a synthetic wax in a melamine resin, It becomes possible to perform continuous molding of the molded article after the sealing for a long time. In addition, in the case of the compression mold, the release effect of the air vent portion and the continuous molding of the molded article after the release molding can be performed for a long time.

Hereinafter, the resin composition for 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, formaldehyde and melamine crystals are reacted in an aqueous solution at a molar ratio of 1: 1 to 4: 1, advantageously from 1.5: 1 to 3: 1 to prepare an aqueous solution of the initial condensate. The reaction can be carried out under conditions of a melamine crystal concentration of 20 to 60%, a reaction temperature of 70 to 100 ° C and a weakly alkaline condition, and the reaction is completed within 10 to 100 minutes. The formaldehyde may be partially substituted with aldehyde components other than paraformaldehyde and formaldehyde, for example, aliphatic aldehydes such as acetaldehyde.

The resin composition for mold release recovery of the present invention contains, in addition to the melamine resin, a metal soap-based releasing agent, an organic fatty acid ester-based releasing agent and / or a synthetic wax as a releasing agent.

Examples of the metal soap-based releasing agent include calcium stearate, zinc stearate, zinc myristate and the like.

Examples of the organic fatty acid ester-based releasing agent include a montanic acid partial saponification ester and a polymer complex ester. Examples of the synthetic wax include a modified hydrocarbon wax and a mineral oil synthetic wax. Specific examples thereof include Licowax OP (montanic acid partial saponified ester manufactured by Client Japan K.K.), Loxiol G78 (polymer complex ester manufactured by Cognis Japan K.K.), Licolub, H-4 (modified hydrocarbon wax manufactured by Client Japan Kogyo Co., Ltd.) and Roxiol VPN881 (manufactured by Cognis Japan KK, mineral waxy synthetic wax).

The content ratio of the metal soap-based releasing agent and the other releasing agent (organic fatty acid ester releasing agent and synthetic wax) is preferably from 90:10 to 30:70, particularly preferably from 80:20 to 40:60 by weight in terms of the former. If the proportion of the other release agent is excessive, the continuous formability is deteriorated, which is not preferable.

The total amount of the metal soap type releasing agent and the other releasing agent is preferably from 0.2 to 5.0 parts by weight, more preferably from 0.5 to 3.0 parts by weight, based on 100 parts by weight of the melamine resin. If the total content of these releasing agents is insufficient, mold releasability is deteriorated. If the amount is too large, mold releasability is good. However, the flowability of the resin composition for recovering mold releasability is lowered remarkably and the moldability is deteriorated. In addition, It is not preferable because the number of times of shot increases.

In addition to the melamine resin and the release agent described above, it is preferable that the resin composition for recovering the mold releasability of the present invention contains pulp in order to improve the handling property when the molding is removed from the mold. As the pulp, straw pulp, bamboo pulp, wood pulp (softwood pulp, hardwood pulp) and the like may be used, and any of chemical pulp and mechanical pulp may be used.

In addition, the pulp may be used as a form impregnated with the melamine resin (resin impregnated pulp) which is an essential component of the resin composition for mold release recovery of the present invention. The resin-impregnated pulp can be prepared, for example, by impregnating a pulp with a melamine-formaldehyde resin aqueous solution and drying it. In addition, part or all of the pulp may be replaced with powdered pulp, so that the fluidity can be adjusted as necessary.

The pulp size is not particularly limited, but it is generally about 5 to 1000 mu m, preferably about 10 to 200 mu m. The content of the pulp is generally 5 to 70 parts by weight, preferably 20 to 60 parts by weight, based on 100 parts by weight of the melamine resin. If the content of the pulp is less than 5 parts by weight, there is no addition effect. When the amount of the pulp is more than 70 parts by weight, the fluidity at the time of use deteriorates and the resin composition for recovering mold releasability is not filled up to every corner of the mold. It can not be imparted.

It is preferable that the resin composition for recovering mold release of the present invention contains a curing catalyst. Examples of the curing catalyst include organic acids such as phthalic anhydride, oxalic acid, sulfamic acid and paratoluenesulfonic acid, inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as triethylamine, triethanolamine,? -Dimethylaminoethanol, -Amino-1-propanol, and the like. The amount of the curing catalyst to be added is generally at least 1.5 parts by weight, preferably at least 0.1 part by weight per 100 parts by weight of the melamine resin.

It is preferable that the resin composition for recovering a mold release of the present invention contains at least one selected from the pulp and the curing catalyst.

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

Examples of the coloring material include inorganic pigments such as titanium oxide, carbon black, zinc oxide and ferric oxide, organic pigments such as phthalocyanine type, azo type and diazo type, benzooxazole type, naphthotriazole type, coumarin Examples of the fibrous filler include natural fibers such as wood flour, cotton, hemp and cotton linters, aramid fibers, cotton fibers, cotton fibers, And inorganic fibers such as glass fibers, glass fibers, silicate powder, untreated calcium carbonate, talc, aluminum hydroxide, barium sulfate, zinc sulfide, calcium sulfate and the like can be used as the inorganic filler. .

The resin composition for recovering a mold release of the present invention may be a resin composition for recovering a mold of a compression type and a resin composition for recovering a mold release of a transfer type.

In the case of compression molding, pulp, a curing catalyst, an antioxidant and the like are preferably blended in addition to the essential components melamine resin, metal soap-based release agent, organic fatty acid ester-based release agent and / or synthetic wax. For example, a preferable composition of the resin composition for recovering a mold releasing mold of compression type is as follows.

[Prescription example of compression type]

Melamine resin 100 parts by weight

0.3 to 1.0 part by weight of a metal soap-based releasing agent

Organic fatty acid ester releasing agent 0.5 to 1.5 parts by weight

Or / and synthetic wax

Pulp 20 to 40 parts by weight

0.02 to 0.50 parts by weight of a curing catalyst

In the case of compression molding, the combination of the metal soap-based releasing agent and the organic fatty acid ester releasing agent and / or synthetic wax may be a combination of zinc stearate and montanic acid partial saponification ester, a combination of calcium stearate and modified hydrocarbon wax , A combination of calcium stearate and a polymer complex ester, and the like.

In addition, in the case of the transfer type, inorganic fillers such as fibrous fillers such as pulp, curing catalyst, and silica powder, coloring agents such as melamine resin, metal soap type releasing agent, organic fatty acid ester releasing agent and / , An antioxidant, and the like. For example, a preferable combination composition of the resin composition for transfer mold recovery is as follows.

[Prescription Example of Transfer Type]

Melamine resin 100 parts by weight

0.3 to 1.0 part by weight of a metal soap-based releasing agent

Organic fatty acid ester releasing agent 0.5 to 1.5 parts by weight

Or / and synthetic wax

Pulp 5 to 20 parts by weight

0.02 to 0.1 part by weight of a curing catalyst

10 to 40 parts by weight of silica

In the case of the transfer type, the combination of the metal soap type releasing agent and the organic fatty acid ester releasing agent and / or the synthetic wax may be a combination of zinc stearate and montanic acid partial saponification ester, a combination of zinc stearate and modified hydrocarbon wax , A combination of calcium stearate and a mineral oil synthetic wax, and the like.

In the preparation of the resin composition for mold release recovery of the present invention, any means capable of uniformly mixing a melamine resin, a metal soap releasing agent, an organic fatty acid ester releasing agent and / or a synthetic wax, and other additives such as pulp, Can be adopted.

For example, a kneader, a ribbon blender, a Henschel mixer, a ball mill, a roll mill, a stone mill, and a tumbler can be exemplified.

Examples of the curable resin molding material that can be released and recovered by using the resin composition for restoring mold release of the present invention include an epoxy resin molding material and a phenol resin molding material, In particular, an epoxy resin molding material for semiconductor encapsulation. The resin composition for mold release recovery of the present invention can be used in any mold as long as it is used for the automatic molding of the curable resin molding material, but it is generally applicable to a mold made of iron, chromium or the like .

Molding can be imparted to the surface of the mold by molding the resin composition for recovering mold release of the present invention in a mold. The molding conditions of the mold release recovery resin composition of the present invention are preferably a mold temperature of 160 to 190 DEG C, a molding pressure of 10 to 20 MPa, and a curing time of 2 to 3 minutes.

<Examples>

Hereinafter, the present invention will be described in more detail by way of examples and the like, but the present invention is not limited at all by these examples and the like.

(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 were heated to prepare a melamine-formaldehyde resin by a known method. 257 parts by weight of pulp was added to the resulting melamine resin aqueous solution, Dried to obtain a pulp-mixed melamine-formaldehyde resin powder (melamine resin impregnated pulp) having a resin content of about 73%.

(Production Example 2)

The melamine resin aqueous solution (solid content: about 60% by weight) obtained in Preparation Example 1 was dried at about 200 캜 by a spray drier to obtain a powdery melamine resin.

[Example 1]

30 parts by weight of pulp-mixed melamine-formaldehyde resin powder having a resin content of about 73% obtained in Preparation Example 1, 50 parts by weight of the powdery melamine resin obtained in Preparation Example 2, 20 parts by weight of silica powder having a grain size of # 200, 0.3 part by weight of zinc stearate, 0.3 part by weight of ethylenebisstearic acid amide, and 0.35 part by weight of Ricohax OP (montanic acid partial saponified ester, manufactured by Client Japan K.K.) were mixed in a ball mill to prepare a mold releasing recovery resin composition A . As shown in Table 1, the obtained resin composition A for mold release recovery exhibited excellent mold releasability. Further, when the epoxy sealant was molded after the mold release recovery using the resin composition A for mold release recovery, excellent continuous moldability was exhibited.

[Example 2]

In Example 1, 0.1 part by weight of Roxiol G78 (polymer complex ester, manufactured by Cognis Japan K.K.) was used in place of 0.35 part by weight of Ricoh Wax OP (montanic acid partial saponification ester manufactured by Client Japan K.K.) , A resin composition B for mold release recovery was obtained in the same manner as in Example 1. As shown in Table 1, the obtained resin composition B for mold release recovery exhibited excellent mold releasability. Further, after the mold releasing recovery was performed using the resin composition B for recovering the mold releasing mold, the epoxy encapsulant was molded to exhibit excellent continuous moldability.

[Example 3]

0.35 parts by weight of Recolube H-4 (modified hydrocarbon manufactured by Client Japan K.K.) was used in place of 0.35 parts by weight of Ricoh wax OP (a montanic acid partial saponification ester manufactured by Client Japan K.K.) , A resin composition C for mold release recovery was obtained in the same manner as in Example 1. [ As shown in Table 1, the resulting resin composition C for recovering mold release showed excellent mold releasability. Further, when the epoxy sealant was molded after the mold releasing recovery using the resin composition C for recovering the mold release, excellent continuous moldability was exhibited.

[Example 4]

Except that 0.30 part by weight of Roxiol VPN881 (manufactured by Cognis Japan K.K., a mineral oil based synthetic wax) was used instead of 0.35 part by weight of Ricoh wax OP (manufactured by Client Japan K.K., montanic acid partial saponification ester) , A resin composition D for mold releasing recovery was obtained in the same manner as in Example 1. As shown in Table 1, the resulting resin composition D for mold release recovery exhibited excellent mold releasability. Further, after molding release recovery using the resin composition D for recovering the mold releasing mold, the epoxy sealing material was molded to exhibit excellent continuous moldability.

[Test Example 1]

Initialization of mold

In order to perform the mold release recovery test on the mold releasing recovery resin compositions A to D, it is necessary to make the surface of the mold surface normal before the test. Therefore, a commercially available melamine resin mold cleaning material (NIKKA CARBIDE KOGYO KABUSHIKI KAISHA, (Nikaret ECR-SW7320, manufactured by Nippon Kogaku Kogyo Kabushiki Kaisha) using a commercially available melamine resin mold cleaning material (Nikark ECR-CL) Two shots were cleaned by molding to perform mold cleaning.

<Molding conditions>

Mold: QFP

Mold temperature: 175 ° C / 175 ° C

Curing time: ECR-CL 300 sec

           SW7320 180 seconds

Dissolution recovery test

After completion of the cleaning for mold initialization, the resin compositions A to D for mold releasability recovery were each subjected to three shot molding at a curing time of 180 seconds by transfer molding. Thereafter, molding was carried out using a commercially available biphenyl-based epoxy resin molding material (EME-7351T, manufactured by Sumitomo Bakelite Co., Ltd.), and mold releasability and continuous moldability were confirmed.

<Molding conditions>

Mold: QFP

Mold temperature: 175 ° C / 175 ° C

Curing time: 100 seconds

[Example 5]

1000 parts by weight of pulp-mixed melamine-formaldehyde resin powder having a resin content of about 73% obtained in Production Example 1, 0.5 part by weight of phthalic anhydride, 2.5 parts by weight of zinc stearate, and Ricoh wax OP (manufactured by Client Japan Kogyo Co., And 3.5 parts by weight of a partially saponified ester) were mixed with a ball mill to obtain a resin composition E for mold release recovery. As shown in Table 2, the obtained resin composition E for mold release recovery exhibited excellent mold releasability. Further, after molding release recovery using the resin composition E for recovering the mold releasing mold, the epoxy encapsulant was molded to exhibit excellent continuous moldability.

[Example 6]

In Example 5, 1.0 part by weight of Roxiol G78 (polymer complex ester, manufactured by Cognis Japan K.K.) was used in place of 3.5 parts by weight of Ricoh Wax OP (a montanic acid partial saponification ester manufactured by Client Japan K.K.) , A resin composition F for mold releasing recovery was obtained in the same manner as in Example 5. As shown in Table 2, the obtained resin composition F for recovering mold release showed excellent mold releasability. In addition, when the epoxy sealant was molded after the mold release recovery was performed using the resin composition F for recovering the mold release mold, excellent continuous moldability was exhibited.

[Example 7]

3.5 parts by weight of Recolube H-4 (modified hydrocarbon manufactured by Client Japan K.K.) was used in place of 3.5 parts by weight of Ricoh wax OP (manufactured by Client Japan K.K., montanic acid partial saponification ester) , A resin composition G for mold release recovery was obtained in the same manner as in Example 5. As shown in Table 2, the resin composition G for recovering the mold release moldings exhibited excellent mold releasability. In addition, when the epoxy sealant was molded after the mold releasing recovery using the resin composition G for recovering the mold release, excellent continuous moldability was exhibited.

[Example 8]

In Example 5, 3.0 parts by weight of Roxiol VPN881 (manufactured by Cognis Japan Co., Ltd., mineral oil synthetic wax) was used in place of 3.5 parts by weight of Ricoh Wax OP (manufactured by Client Japan K.K., montanic acid partial saponification ester) Resin composition H for mold release recovery was obtained in the same manner as in Example 5. As shown in Table 2, the obtained resin composition H for recovering mold release showed excellent mold releasability. Furthermore, when the epoxy sealing material was molded after recovering the mold release by using the resin composition H for recovering the mold release, excellent continuous moldability was exhibited.

[Test Example 2]

Initialization of mold

The mold was cleaned in the same manner as in Test Example 1.

Dissolution recovery test

After completion of the cleaning for mold initialization, the resin compositions E to H for recovering the mold release molds were respectively subjected to compression molding to form three shot portions at a curing time of 180 seconds. Thereafter, molding was carried out using a commercially available biphenyl-based epoxy resin molding material (EME-7351T, manufactured by Sumitomo Bakelite Co., Ltd.), and mold releasability and continuous moldability were confirmed.

<Molding conditions>

Mold: QFP

Mold temperature: 175 ° C / 175 ° C

Curing time: 100 seconds

By using the resin composition for recovering a mold release of the present invention, excellent mold releasability can be obtained, and sticking (sealing) caused in the cavity portion, the air vent portion, etc. caused by the recent enhancement of the function of the epoxy- sticking can be prevented. In addition, since the mold releasability is maintained for a long time, excellent continuous moldability is exhibited, leading to improvement in productivity.

Claims (9)

1. A resin composition comprising a melamine resin and at least one metal soap-based releasing agent and an organic fatty acid ester-releasing agent, wherein the releasing agent is a releasing agent, Wherein the ratio of the content of the metal soap-based releasing agent to the total content of the organic fatty acid ester-based releasing agent and the synthetic wax is in a weight ratio of electrons: 90:10 to 30:70 And the resin composition for recovering mold releasability. The method according to claim 1, Wherein the resin composition contains an organic fatty acid ester releasing agent and the organic fatty acid ester releasing agent is a montanic acid partial saponification ester or a polymer composite ester. The method according to claim 1, Wherein the resin composition contains a synthetic wax and the synthetic wax is a modified hydrocarbon wax or a mineral oil synthetic wax. delete 4. The method according to any one of claims 1 to 3, Wherein the total amount of the content of the metal soap releasing agent, the content of the organic fatty acid ester releasing agent and the content of the synthetic wax is 0.2 to 5.0 parts by weight based on 100 parts by weight of the melamine resin. 4. The method according to any one of claims 1 to 3, Wherein the resin composition is a compression type. 4. The method according to any one of claims 1 to 3, Wherein the resin composition is a transfer type. 4. The method according to any one of claims 1 to 3, And further contains at least one of a pulp and a curing catalyst. A method of recovering a mold release using the resin composition for recovering mold release according to any one of claims 1 to 3.