TWI410316B - Mold cleaning and mold release resin for mold cleaning, mold cleaning and mold release recovery method - Google Patents
Mold cleaning and mold release resin for mold cleaning, mold cleaning and mold release recovery method Download PDFInfo
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- TWI410316B TWI410316B TW096140490A TW96140490A TWI410316B TW I410316 B TWI410316 B TW I410316B TW 096140490 A TW096140490 A TW 096140490A TW 96140490 A TW96140490 A TW 96140490A TW I410316 B TWI410316 B TW I410316B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/58—Applying the releasing agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/70—Maintenance
- B29C33/72—Cleaning
- B29C33/722—Compositions for cleaning moulds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2061/00—Use of condensation polymers of aldehydes or ketones or derivatives thereof, as moulding material
- B29K2061/20—Aminoplasts
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Abstract
Description
本發明係關於一種於硬化性樹脂成形材料之成形時，能夠去除模具表面之污物且使模具表面具有脫模性而兼具清潔性及脫模性之壓縮型模具清潔用及脫模回復用樹脂組合物、以及使用該樹脂組合物之模具清潔及模具脫模回復方法。The present invention relates to a compression type mold cleaning and mold release recovery capable of removing dirt on a surface of a mold and providing mold release property on the surface of the mold, and having both cleanability and mold release property. A resin composition, and a mold cleaning and mold release recovery method using the resin composition.
先前，於利用環氧樹脂等熱硬化性樹脂而形成積體電路等密封成形物時，若成形時間持續較長，則模具內部表面將有污物附著，若照舊接連繼續成形，則常常會導致密封成形物表面有污物附著，或密封成形物附著於模具上而使得成形操作無法繼續。因此，必須定期對模具進行清潔，故而提出有如下方法：每次進行成形材料數百次射出成形(shot molding)時，以數次之射出比例使模具清潔用樹脂成形，進行模具清潔。When a sealing molded product such as an integrated circuit is formed by using a thermosetting resin such as an epoxy resin, if the molding time continues to be long, dirt may adhere to the inner surface of the mold, and if it continues to be formed in succession, it often results in The surface of the seal molded article has dirt adhering thereto, or the seal molded article adheres to the mold so that the forming operation cannot be continued. Therefore, since it is necessary to clean the mold regularly, it is proposed that the mold cleaning resin is molded at a plurality of injection ratios each time the molding material is subjected to shot molding for several times, and the mold is cleaned.
例如，於日本專利特公昭52-788號公報中，提出有「硬化性樹脂成形材料(胺系樹脂成形材料除外)成形時藉由以胺系樹脂為主體之材料成形來清潔模具表面污物之方法」，其中揭示有由胺系樹脂、有機質基材及/或無機質基材、脫模劑構成之模具清潔用樹脂組合物。For example, in the case of forming a curable resin molding material (excluding an amine resin molding material), it is proposed to mold the surface of the mold by forming a material mainly composed of an amine resin. In the method, a resin composition for mold cleaning comprising an amine resin, an organic substrate, an inorganic substrate, and a release agent is disclosed.
近年來，隨著積體電路等(縮寫為IC(Integrated circuit，積體電路)、LSI(Large Scale Integration，大規模積體電路))之高積體化、薄型化、表面安裝化，成形品之形狀、 構造之多樣化得到發展，因此，期望半導體密封材料實現高流動化。In recent years, with the integration, thinning, and surface mounting of integrated circuits (abbreviated as IC (Integrated Circuit), LSI (Large Scale Integration)), molded products Shape, The diversification of the structure has been developed, and therefore, it is desired to achieve high fluidization of the semiconductor sealing material.
因此，若利用高流動化型之環氧密封材料，則於通氣孔部分易產生樹脂堵塞，當產生該等堵塞時，放氣(air-bleeding)會變得困難，導致樹脂無法流動，從而產生模穴部產生未填充而形成不良，故而難以連續成形。因此，為了避免產生該等狀況，必須進行清潔，但使用轉移型清潔材料時由於上述理由，樹脂無法正常流動，因此，難以去除堵塞於通氣孔之樹脂。Therefore, when a highly fluidized epoxy sealing material is used, resin clogging tends to occur in the vent portion, and when such clogging occurs, air-bleeding becomes difficult, and the resin cannot flow, resulting in generation of resin. The cavity portion is unfilled and poorly formed, so that it is difficult to continuously form. Therefore, in order to avoid such a situation, it is necessary to perform cleaning. However, when the transfer type cleaning material is used, the resin does not flow normally due to the above reasons, and therefore it is difficult to remove the resin that is clogged in the vent hole.
另一方面，使用模具清潔用樹脂組合物進行清潔後，模具表面可變得乾淨，但反之，亦存在如下問題：由於模具表面之脫模劑亦被去除，因此清潔後立即進行成形之模具的脫模性會變得極差。因此，使用模具清潔用樹脂組合物之後，必須使模具脫模回復樹脂組合物成形，以將模具脫模回復樹脂組合物中之脫模劑轉移至模具表面，使脫模性回復。On the other hand, after cleaning with the resin composition for mold cleaning, the surface of the mold can be cleaned, but conversely, there is also a problem that since the release agent on the surface of the mold is also removed, the mold is formed immediately after cleaning. The release property will become extremely poor. Therefore, after the resin composition for mold cleaning is used, it is necessary to mold the mold release-recovery resin composition to transfer the release agent in the mold release-recovery resin composition to the surface of the mold to restore the mold release property.
該模具脫模回復樹脂組合物，係使脫模劑轉移至模具表面而使脫模性迅速回復者。先前，作為模具脫模回復樹脂組合物，例如係使用含有環氧樹脂、苯酚樹脂、硬化加速劑、巴西棕櫚蠟及矽石(silica)等成分者。The mold is released from the resin composition, and the release agent is transferred to the surface of the mold to promptly recover the release property. Conventionally, as the mold release-recovery resin composition, for example, a component containing an epoxy resin, a phenol resin, a hardening accelerator, carnauba wax, and silica is used.
該等模具脫模回復樹脂組合物亦與上述相同，由於在通氣孔部分產生樹脂堵塞，無法使樹脂流入至整個通氣孔，故而難以使通氣孔部分之脫模回復。Similarly to the above, the mold release-recovery resin composition has a resin clogging in the vent hole portion, and the resin cannot flow into the entire vent hole, so that it is difficult to restore the vent hole portion.
專利文獻1：日本專利特公昭52-788號公報Patent Document 1: Japanese Patent Publication No. Sho 52-788
如上所述，本發明係用以解決如下問題：隨著半導體密封材料之高流動化而於通氣孔部分產生樹脂堵塞、因樹脂堵塞而難以利用模具清潔用樹脂組合物進行清潔、以及難以利用模具脫模回復樹脂組合物來使脫模回復。又，本發明提供一種兼具清潔性及脫模回復性之壓縮型模具清潔用及脫模回復用樹脂組合物，其可容易地進行通氣孔部分之清潔或脫模回復，且可於一個步驟內完成模具之清潔及脫模回復，而並非必須於清潔模具表面污物後再使用模具脫模回復樹脂組合物來補給與污物一併去除之脫模成分該等煩雜的兩個步驟操作之先前之技術方法。As described above, the present invention solves the problem that resin clogging occurs in the vent hole portion due to high fluidization of the semiconductor sealing material, it is difficult to clean with the resin composition for mold cleaning due to clogging of the resin, and it is difficult to use the mold. The release resin composition is released to restore the mold release. Moreover, the present invention provides a resin composition for cleaning and mold release of a compression mold which has both cleanability and mold release recovery, which can easily perform cleaning or demolding recovery of a vent portion, and can be carried out in one step. The cleaning of the mold and the release of the mold are completed, and it is not necessary to clean the surface of the mold and then use the mold to release the resin composition to replenish the mold release component which is removed together with the dirt. Previous technical methods.
本發明係為解決上述問題而開發者，提供一種模具清潔用及模具脫模回復用樹脂組合物，其特徵在於，其係於硬化性樹脂成形材料之成形時去除模具表面之污物且使模具表面具有脫模性之樹脂組合物，且含有三聚氰胺樹脂，且含有至少一種金屬皂系脫模劑。In order to solve the above problems, the present invention provides a resin composition for mold cleaning and mold release recovery, which is characterized in that it removes dirt on a mold surface and forms a mold when forming a curable resin molding material. The surface has a releasable resin composition and contains a melamine resin and contains at least one metal soap-based release agent.
本發明之模具清潔用及模具脫模回復用樹脂組合物，較好的是進一步含有甘露糖醇或/及金屬皂以外之脫模劑。The resin composition for mold cleaning and mold release recovery of the present invention preferably further contains a release agent other than mannitol or/metal soap.
本發明之模具清潔用及模具脫模回復用樹脂組合物，係兼具模具清潔效果與模具脫模回復效果之雙重效果，不僅可去除模穴、流道及澆口之污物，且亦可去除通氣孔部分 及模具之分模區(parting area)之污物，尤其可容易地進行通氣孔部分之清潔與脫模回復之壓縮型樹脂組合物，其無須進行先前之包括利用模具清潔用樹脂組合物實施之模具清潔操作與利用模具脫模回復用樹脂組合物實施之模具脫模回復操作該等煩雜的兩個步驟操作，而可於一個步驟內完成模具之清潔與脫模回復。The resin composition for mold cleaning and mold release recovery of the invention has the dual effects of the mold cleaning effect and the mold release recovery effect, and can not only remove the dirt of the cavity, the runner and the gate, but also Remove the vent portion And a contaminant material of a parting area of the mold, in particular, a compression type resin composition which can easily perform cleaning and release of the vent portion, which does not need to be carried out previously including the resin composition for cleaning with a mold The mold cleaning operation and the mold release recovery operation by the mold release recovery resin composition are performed in such a troublesome two-step operation, and the mold cleaning and mold release recovery can be completed in one step.
以下，對本發明之模具清潔用及模具脫模回復用樹脂組合物進行詳細說明。Hereinafter, the resin composition for mold cleaning and mold release recovery of the present invention will be described in detail.
本發明中所使用之三聚氰胺樹脂可採用眾所周知之方法而製備。The melamine resin used in the present invention can be produced by a known method.
例如，使甲醛與三聚氰胺結晶以莫耳比1:1~4:1，較好的是1.5:1~3:1於水溶液中發生反應，來製備初始縮合物水溶液。可使其等在三聚氰胺結晶濃度20~60%、反應溫度70~100℃以及弱鹼性之條件下進行反應，經10~100分鐘反應結束。上述甲醛之一部分，可由三聚甲醛、甲醛以外之醛類成分例如乙醛類等脂肪族醛類來取代。For example, an initial aqueous solution of the condensate is prepared by reacting formaldehyde with melamine in a molar ratio of 1:1 to 4:1, preferably 1.5:1 to 3:1, in an aqueous solution. The reaction can be carried out under the conditions of melamine crystal concentration of 20-60%, reaction temperature of 70-100 ° C and weak alkalinity, and the reaction is completed after 10 to 100 minutes. One part of the above formaldehyde may be substituted by an aliphatic aldehyde such as acetal or an aldehyde component other than formaldehyde.
本發明之模具清潔用及模具脫模回復用樹脂組合物，除三聚氰胺樹脂以外，亦含有金屬皂系脫模劑。The resin composition for mold cleaning and mold release recovery of the present invention contains a metal soap-based release agent in addition to the melamine resin.
作為金屬皂系脫模劑之例，例如可列舉硬脂酸鈣、硬脂酸鋅、肉豆蔻酸鋅等。作為金屬皂系脫模劑之添加量，較好的是，相對於100重量份之三聚氰胺樹脂，添加0.2~1.0重量份，更好的是添加0.4~0.8重量份。若金屬皂系脫模劑之添加量不足，則脫模性與清潔性會降低，而若金屬皂系 脫模劑之添加量過多，則脫模性較好，但清潔性降低。Examples of the metal soap-based release agent include calcium stearate, zinc stearate, and zinc myristate. The amount of the metal soap-based release agent added is preferably 0.2 to 1.0 part by weight, more preferably 0.4 to 0.8 part by weight, per 100 parts by weight of the melamine resin. If the amount of the metal soap-based release agent is insufficient, the mold release property and cleanability are lowered, and if the metal soap system is When the amount of the release agent added is too large, the mold release property is good, but the cleanability is lowered.
本發明之模具清潔用及模具脫模回復用樹脂組合物，較好的是，其中除含有三聚氰胺樹脂及金屬皂系脫模劑以外，進一步含有甘露糖醇。藉由含有甘露糖醇，可於維持模具脫模性之同時降低加熱褪色。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 soap release agent. By containing mannitol, it is possible to maintain the mold release property while reducing the heating fading.
作為甘露糖醇，較好的是D-甘露糖醇。As the mannitol, D-mannitol is preferred.
當含有甘露糖醇時，較好的是使金屬皂系脫模劑與甘露糖醇之含有比例以重量比計為90:10~30:70，尤其好的是80:20~40:60。若甘露糖醇之比例過大，則清潔性會變差。When mannitol is contained, it is preferred that the ratio of the metal soap-based release agent to the mannitol is from 90:10 to 30:70 by weight, particularly preferably from 80:20 to 40:60. If the proportion of mannitol is too large, the cleanability will be poor.
作為甘露糖醇之添加量，較好的是，相對於100重量份之三聚氰胺樹脂，添加0.2~1.0重量份，更好的是添加0.3~0.8重量份。若甘露糖醇之添加量不足，則無添加效果，而若甘露糖醇之添加量過多，則脫模性較好，但清潔性降低。The amount of mannitol added is preferably 0.2 to 1.0 part by weight, more preferably 0.3 to 0.8 part by weight, per 100 parts by weight of the melamine resin. When the amount of mannitol added is insufficient, there is no additive effect, and if the amount of mannitol added is too large, the mold release property is good, but the cleanability is lowered.
又，本發明之模具清潔用及模具脫模回復用樹脂組合物，較好的亦有，其中除含有三聚氰胺樹脂及金屬皂系脫模劑以外，進一步含有金屬皂以外之脫模劑。藉由含有金屬皂以外之脫模劑，可不受環氧密封材料中之脫模成分之影響而發揮模具脫模性。Further, the resin composition for mold cleaning and mold release of the present invention is preferably a mold release agent other than the metal soap, in addition to the melamine resin and the metal soap release agent. By containing a mold release agent other than the metal soap, mold release property can be exhibited without being affected by the mold release component in the epoxy sealing material.
作為金屬皂以外之脫模劑，可列舉褐煤酸部分皂化酯或高分子複合酯等酯系脫模劑、改性烴系蠟或礦物油系合成蠟等合成蠟。具體而言，可適當使用Licowax OP(日本科萊恩(Clariant Japan)股份有限公司製褐煤酸部分皂化 酯)、Loxiol G78(日本科寧(Cognis Japan)股份有限公司製高分子複合酯)、Licolub H-4(日本科萊恩股份有限公司製改性烴)及Loxiol VPN881(日本科寧股份有限公司製礦物油系合成蠟)等市售品。作為金屬皂以外之脫模劑，較好的是此處列舉之酯系脫模劑及合成蠟，若使用此處列舉以外之脫模劑，則清潔性有時會變差。Examples of the release agent other than the metal soap include an ester-based release agent such as a montanic acid partially saponified ester or a polymer complex ester, and a synthetic wax such as a modified hydrocarbon wax or a mineral oil-based synthetic wax. Specifically, Licowax OP (partial saponification of montanic acid produced by Clariant Japan Co., Ltd.) can be suitably used. Ester), Loxiol G78 (polymer complex ester made by Cognis Japan Co., Ltd.), Licolub H-4 (modified hydrocarbon manufactured by Clariant Co., Ltd., Japan), and Loxiol VPN881 (manufactured by Nippon Corning Co., Ltd.) Commercial products such as mineral oil synthetic wax). The release agent other than the metal soap is preferably an ester-based release agent and a synthetic wax as exemplified above. When a release agent other than those listed herein is used, the cleanability may be deteriorated.
當含有該等金屬皂以外之脫模劑時，較好的是使金屬皂系脫模劑與金屬皂以外之脫模劑之含有比例以重量比計為90:10~30:70，尤其好的是80:20~40:60。若金屬皂以外之脫模劑之比例過大，則清潔性會變差。When a mold release agent other than the metal soap is contained, it is preferred that the ratio of the metal soap release agent to the mold release agent other than the metal soap is 90:10 to 30:70 by weight, particularly preferably It is 80:20~40:60. If the proportion of the release agent other than the metal soap is too large, the cleanability may be deteriorated.
作為金屬皂以外之脫模劑之添加量，較好的是，相對於100重量份之三聚氰胺樹脂，添加0.02~0.7重量份，更好的是添加0.1~0.5重量份。若金屬皂以外之脫模劑之添加量不足，則無添加效果，而若金屬皂以外之脫模劑之添加量過多，則脫模性較好，但清潔性降低。The amount of the release agent other than the metal soap is preferably 0.02 to 0.7 parts by weight, more preferably 0.1 to 0.5 part by weight, per 100 parts by weight of the melamine resin. When the amount of the release agent other than the metal soap is insufficient, there is no additive effect, and if the amount of the release agent other than the metal soap is too large, the mold release property is good, but the cleanability is lowered.
本發明之模具清潔用及模具脫模回復用樹脂組合物，為了提高清潔效果，較好的是其中含有紙漿。作為該紙漿，可使用草紙漿、竹紙漿、木材紙漿(針葉樹紙漿、闊葉樹紙漿)等，亦可使用化學紙漿、機械紙漿中之任一者。In the resin composition for mold cleaning and mold release recovery of the present invention, in order to improve the cleaning effect, it is preferred to contain pulp. As the pulp, grass pulp, bamboo pulp, wood pulp (conifer pulp, hardwood pulp), or the like, or any of chemical pulp and mechanical pulp can be used.
較好的是，於使作為本發明之模具清潔用及模具脫模回復用樹脂組合物之必要成分的三聚氰胺樹脂浸漬於該紙漿中之形態(樹脂浸漬紙漿)下，該紙漿存在於本發明之模具清潔用及模具脫模回復用樹脂組合物中。該樹脂含浸紙漿可藉由將紙漿浸漬於三聚氰胺-甲醛樹脂水溶液中後加以 乾燥而製備。又，亦可將上述紙漿之一部分或全部替換成粉末紙漿，藉此，可進一步提高流動性。Preferably, the melamine resin which is an essential component of the resin composition for mold cleaning and mold release recovery of the present invention is immersed in the form of the pulp (resin impregnated pulp), and the pulp is present in the present invention. The resin composition for mold cleaning and mold release recovery. The resin impregnated pulp can be obtained by immersing the pulp in a melamine-formaldehyde resin aqueous solution. Prepared by drying. Further, part or all of the above pulp may be replaced with powdered pulp, whereby the fluidity can be further improved.
對上述紙漿之大小並無特別限定，通常為5~1000μm，較好的是10~200μm左右。又，相對於100重量份之三聚氰胺樹脂，上述紙漿之含量通常為5~70重量份，較好的是20~60重量份。若紙漿之含量未滿5重量份，則無添加效果；若超過70重量份，則流動性變差，而無法填充至模具之各個角落，使模具上殘留有汚物，故而不好。The size of the above pulp is not particularly limited, but is usually from 5 to 1,000 μm, preferably from about 10 to 200 μm. Further, the content of the above pulp is usually 5 to 70 parts by weight, preferably 20 to 60 parts by weight, per 100 parts by weight of the melamine resin. If the content of the pulp is less than 5 parts by weight, there is no additive effect; if it exceeds 70 parts by weight, the fluidity is deteriorated, and it is not possible to fill the respective corners of the mold, so that dirt remains on the mold, which is not preferable.
較好的是，本發明之模具清潔用及模具脫模回復用樹脂組合物中進一步含有硬化觸媒。作為硬化觸媒，可列舉鄰苯二甲酸酐、草酸、磺胺酸、對甲苯磺酸等有機酸、鹽酸、硫酸等無機酸，該等酸類與三乙胺、三乙醇胺、β-二甲胺乙醇、2-甲基-2-胺基-1-丙醇等之鹽類。作為硬化觸媒之添加量，相對於100重量份之三聚氰胺樹脂，通常添加1.5重量份以下0.05重量份以上，較好的是1重量份以下0.1重量份以上。It is preferable that the resin composition for mold cleaning and mold release recovery of the present invention further contains a curing catalyst. Examples of the curing catalyst include organic acids such as phthalic anhydride, oxalic acid, sulfamic acid, and p-toluenesulfonic acid, and inorganic acids such as hydrochloric acid and sulfuric acid, such as triethylamine, triethanolamine, and β-dimethylamine ethanol. a salt such as 2-methyl-2-amino-1-propanol. The amount of the curing catalyst to be added is usually 1.5 parts by weight or less and 0.05 part by weight or more, preferably 1 part by weight or less and 0.1 part by weight or more based on 100 parts by weight of the melamine resin.
較好的是，本發明之模具清潔用及模具脫模回復用樹脂組合物中含有選自上述紙漿及硬化觸媒中之一種以上。It is preferable that the resin composition for mold cleaning and mold release of the present invention contains at least one selected from the group consisting of the above-mentioned pulp and a curing catalyst.
此外，本發明之模具清潔用及模具脫模回復用樹脂組合物中，可適當添加顏料等著色劑、紙漿以外之纖維狀填充料、低硬度小粒徑之填充材料等。Further, in the resin composition for mold cleaning and mold release recovery of the present invention, a coloring agent such as a pigment, a fibrous filler other than pulp, a filler having a low hardness and a small particle diameter, and the like can be appropriately added.
製備本發明之模具清潔用及模具脫模回復用樹脂組合物時，可採用將三聚氰胺樹脂、金屬皂系脫模劑、與甘露糖醇、金屬皂以外之脫模劑及紙漿等其他添加劑類均勻混合 而製得之任意方法。When preparing the resin composition for mold cleaning and mold release recovery of the present invention, it is possible to use a melamine resin, a metal soap release agent, a release agent other than mannitol or metal soap, and other additives such as pulp. mixing And any method of making it.
例如可列舉混煉機、帶型攪拌機、亨舍爾混合機、球磨機、滾筒攪拌機、石磨機、滾打機等。For example, a kneader, a belt type mixer, a Henschel mixer, a ball mill, a drum mixer, a stone mill, a roller machine, etc. are mentioned.
作為可使用本發明之模具清潔用及模具脫模回復用樹脂組合物來進行模具之清潔及脫模回復的硬化性樹脂成形材料，例如可列舉環氧樹脂成形材料、苯酚樹脂成形材料等，較好的是環氧樹脂成形材料，尤其好的是半導體封裝用環氧樹脂成形材料。又，本發明之模具清潔用及模具脫模回復用樹脂組合物可用於欲使該硬化性樹脂成形材料自動成形時所使用之任意模具中，但通常用於由鐵、鉻等構成之模具時效果較佳。The curable resin molding material which can be used for cleaning and releasing the mold for the mold cleaning and the mold release-recovering resin composition of the present invention is, for example, an epoxy resin molding material or a phenol resin molding material. Preferably, it is an epoxy resin molding material, and particularly preferably an epoxy resin molding material for semiconductor packaging. Further, the resin composition for mold cleaning and mold release of the present invention can be used in any mold used for automatic molding of the curable resin molding material, but it is usually used for a mold composed of iron, chromium or the like. The effect is better.
利用模具來使本發明之模具清潔用及模具脫模回復用樹脂組合物成形，藉此，可去除該模具表面之污物且可使模具表面具有脫模性。本發明之模具清潔用及模具脫模回復用樹脂組合物之成形條件較好的是模具溫度160~190℃，成形壓力10~20MPa，硬化時間2~3分鐘。The mold for cleaning the mold and the mold release for mold release of the present invention are molded by a mold, whereby the dirt on the surface of the mold can be removed and the surface of the mold can be released. 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.
以下，舉出實施例等，進一步對本發明進行詳細說明，但本發明並不被該等實施例等所限定。Hereinafter, the present invention will be described in detail by way of examples and the like, but the invention is not limited by the examples and the like.
利用眾所周知之方法，使480重量份之三聚氰胺與520重量份之福馬林(37%水溶液)以及350重量份之水進行加熱反應，製作三聚氰胺-甲醛樹脂，於所獲得之三聚氰胺樹脂水溶液中添加257重量份之紙漿並加以混煉，其後，經減 壓乾燥，獲得樹脂含量約為72%之混合有紙漿之三聚氰胺-甲醛樹脂粉末(三聚氰胺樹脂浸漬紙漿)。Using a well-known method, 480 parts by weight of melamine and 520 parts by weight of formalin (37% aqueous solution) and 350 parts by weight of water are subjected to a heat reaction to prepare a melamine-formaldehyde resin, and 257 weights are added to the obtained aqueous melamine resin solution. The pulp is mixed and then reduced The mixture was dried by pressure to obtain a melamine-formaldehyde resin powder (melamine resin impregnated pulp) mixed with pulp having a resin content of about 72%.
利用噴霧乾燥機，於約200℃之溫度對製造例1中所獲得之三聚氰胺樹脂水溶液(固體含量約為60重量%)進行乾燥處理，藉此獲得粉末狀三聚氰胺樹脂。The aqueous melamine resin solution (solid content: about 60% by weight) obtained in Production Example 1 was dried by a spray dryer at a temperature of about 200 ° C, whereby a powdery melamine resin was obtained.
利用球磨機，將1000重量份之製造例1中所獲得之樹脂含量約72%之混合有紙漿之三聚氰胺-甲醛樹脂粉末、0.5重量份之鄰苯二甲酸酐與6.0重量份之硬脂酸鋅加以混合，藉此獲得模具清潔用及模具脫模回復用樹脂組合物A。利用下述測試方法，評估所獲得之樹脂組合物A之模具清潔性及模具脫模性。其結果示於表1中。如表1所示，樹脂組合物A發揮出優良之模具清潔性。又，於利用樹脂組合物A進行模具清潔後未使用模具脫模回復用樹脂組合物之情況下使環氧密封材料成形時，此時呈現出之模具脫模性並不遜於先前之使用有模具脫模回復用樹脂組合物時之模具脫模性。Using a ball mill, 1000 parts by weight of a melamine-formaldehyde resin powder mixed with pulp having a resin content of about 72%, 0.5 parts by weight of phthalic anhydride, and 6.0 parts by weight of zinc stearate were used. By mixing, the resin composition A for mold cleaning and mold release recovery was obtained. The mold cleanability and mold release property of the obtained resin composition A were evaluated by the following test methods. The results are shown in Table 1. As shown in Table 1, the resin composition A exhibited excellent mold cleanability. Further, when the epoxy resin sealing material is formed without using the resin composition for mold release recovery after the mold cleaning by the resin composition A, the mold release property exhibited at this time is not inferior to that of the previous mold. The mold release property when the resin composition for mold release is released.
利用球磨機，將1000重量份之製造例1中所獲得之樹脂含量約為72%之混合有紙漿之三聚氰胺-甲醛樹脂粉末、30重量份之製造例2中所獲得之粉末狀三聚氰胺樹脂、30重量份之粉末紙漿、0.5重量份之鄰苯二甲酸酐、2.5重量份之硬脂酸鋅及3.5重量份之硬脂酸鈣加以混合，藉此獲得 模具清潔用及模具脫模回復用樹脂組合物B。利用與實施例1同樣之方式，評估所獲得之樹脂組合物B的模具清潔性及模具脫模性。其結果揭示於表1中。如表1所示，樹脂組合物B發揮出優良之模具清潔性。又，於利用樹脂組合物B進行模具清潔後未使用模具脫模回復用樹脂組合物之情況下使環氧密封材料成形時，此時呈現出之模具脫模性並不遜於先前之使用有模具脫模回復用樹脂組合物時之模具脫模性。Using a ball mill, 1000 parts by weight of a melamine-formaldehyde resin powder mixed with pulp having a resin content of about 72% obtained in Production Example 1, 30 parts by weight of a powdery melamine resin obtained in Production Example 2, and 30 parts by weight a portion of the powdered pulp, 0.5 parts by weight of phthalic anhydride, 2.5 parts by weight of zinc stearate, and 3.5 parts by weight of calcium stearate, Resin composition B for mold cleaning and mold release. The mold cleanability and mold release property of the obtained resin composition B were evaluated in the same manner as in Example 1. The results are shown in Table 1. As shown in Table 1, the resin composition B exerted excellent mold cleanability. Further, when the epoxy resin sealing material is formed without using the resin composition for mold release recovery after the mold cleaning by the resin composition B, the mold release property exhibited at this time is not inferior to that of the previous mold. The mold release property when the resin composition for mold release is released.
清潔性測試 使用市售之聯苯系環氧樹脂成形材料(住友電木(Sumitomo Bakelite)股份有限公司製EME-7351T)，利用TQFP(Thin Quad Flat Pack，薄四方扁平封裝)之模具，藉由500次射出成形，而形成模具之污物。藉由下述方式進行評估：使用該已有污物附著之模具，反覆使模具清潔用及模具脫模回復用樹脂組合物成形，直至將模具表面清潔乾淨為止。 For the cleanability test, a commercially available biphenyl-based epoxy resin molding material (EME-7351T manufactured by Sumitomo Bakelite Co., Ltd.) was used, and a mold of TQFP (Thin Quad Flat Pack) was used. 500 shots were formed to form a dirt of the mold. The evaluation was carried out by using the mold to which the existing dirt adhered, and repeatedly molding the resin composition for mold cleaning and mold release, until the surface of the mold was cleaned.
脫模回復測試 清潔性測試結束後，使用市售之聯苯系環氧樹脂成形材料(住友電木股份有限公司製EME-7351T)進行連續成形測試，藉此，確認模具脫模性。再者，對模具清潔性較差而未完成洗淨之模具清潔用及模具脫模回復用樹脂組合物，未進行脫模回復測試。 Reply release end of the test after the cleaning test, the commercially available biphenyl-based epoxy resin molding material (manufactured by Sumitomo Bakelite Co., EME-7351T) continuous molding test, whereby the mold releasability confirmed. Further, the mold composition for mold cleaning and mold release recovery which was inferior in mold cleanability and which was not cleaned was not subjected to the mold release recovery test.
利用球磨機，將1000重量份之製造例1中所獲得之樹脂含量約為72%之混合有紙漿之三聚氰胺-甲醛樹脂粉末、0.5重量份之鄰苯二甲酸酐、3.0重量份之硬脂酸鋅以及2.0重量份之D-甘露糖醇加以混合，藉此獲得模具清潔用及模具脫模回復用樹脂組合物C。利用與實施例1同樣之方式，評估所獲得之樹脂組合物C的模具清潔性及模具脫模性。 其結果揭示於表2中。如表2所示，樹脂組合物C發揮出優良之模具清潔性。又，於利用樹脂組合物C進行模具清潔後未使用模具脫模回復用樹脂組合物之情況下使環氧密封材料成形時，此時呈現出之模具脫模性並不遜於先前之使用有模具脫模回復用樹脂組合物時之模具脫模性。Using a ball mill, 1000 parts by weight of the melamine-formaldehyde resin powder mixed with pulp having a resin content of about 72%, 0.5 parts by weight of phthalic anhydride, and 3.0 parts by weight of zinc stearate obtained in Production Example 1 were used. And 2.0 parts by weight of D-mannitol were mixed, whereby a resin composition C for mold cleaning and mold release recovery was obtained. The mold cleanability and mold release property of the obtained resin composition C were evaluated in the same manner as in Example 1. The results are disclosed in Table 2. As shown in Table 2, the resin composition C exhibited excellent mold cleanability. Further, when the epoxy resin sealing material is molded without using the resin composition for mold release recovery after the mold cleaning by the resin composition C, the mold release property exhibited at this time is not inferior to that of the previous mold. The mold release property when the resin composition for mold release is released.
利用球磨機，將1000重量份之製造例1中所獲得之樹脂含量約為72%之混合有紙漿之三聚氰胺-甲醛樹脂粉末、0.5重量份之鄰苯二甲酸酐、1.5重量份之硬脂酸鋅及3.0重量份之D-甘露糖醇加以混合，藉此獲得模具清潔用及模具脫模回復用樹脂組合物D。利用與實施例1同樣之方式，評估所獲得之樹脂組合物D的模具清潔性及模具脫模性。其 結果揭示於表2中。如表2所示，樹脂組合物D發揮出優良之模具清潔性。又，於利用樹脂組合物D進行模具清潔後未使用模具脫模回復用樹脂組合物之情況下使環氧密封材料成形時，此時呈現出之模具脫模性並不遜於先前之使用有模具脫模回復用樹脂組合物時之模具脫模性。Using a ball mill, 1000 parts by weight of a melamine-formaldehyde resin powder mixed with pulp having a resin content of about 72%, 0.5 part by weight of phthalic anhydride, and 1.5 parts by weight of zinc stearate obtained in Production Example 1 were used. And 3.0 parts by weight of D-mannitol were mixed, whereby a resin composition D for mold cleaning and mold release recovery was obtained. The mold cleanability and mold release property of the obtained resin composition D were evaluated in the same manner as in Example 1. its The results are disclosed in Table 2. As shown in Table 2, the resin composition D exhibited excellent mold cleanability. Further, when the epoxy resin sealing material is molded without using the resin composition for mold release recovery after the mold cleaning by the resin composition D, the mold release property exhibited at this time is not inferior to that of the previous mold. The mold release property when the resin composition for mold release is released.
利用球磨機，將1000重量份之製造例1中所獲得之樹脂含量約為72%之混合有紙漿之三聚氰胺-甲醛樹脂粉末、0.5重量份之鄰苯二甲酸酐、2.5重量份之硬脂酸鋅及3.5重量份之Licowax OP(日本科萊恩股份有限公司製褐煤酸部分皂化酯)加以混合，藉此獲得模具清潔用及模具脫模回復用樹脂組合物E。利用與實施例1同樣之方式，評估所獲得之樹脂組合物E之模具清潔性及模具脫模性。其結果揭示於表3中。如表3所示，樹脂組合物E發揮出優良之模具清潔性。又，於利用樹脂組合物E進行模具清潔後未使用模具脫模回復用樹脂組合物之情況下使環氧密封材料成形時，此時呈現出之模具脫模性並不遜於先前之使用有模具脫模回復用樹脂組合物時之模具脫模性。Using a ball mill, 1000 parts by weight of a melamine-formaldehyde resin powder mixed with pulp having a resin content of about 72%, 0.5 parts by weight of phthalic anhydride, and 2.5 parts by weight of zinc stearate obtained in Production Example 1 were used. And 3.5 parts by weight of Licowax OP (a partially saponified ester of montanic acid manufactured by Clariant Co., Ltd., Japan) was mixed, whereby a resin composition E for mold cleaning and mold release recovery was obtained. The mold cleanability and mold release property of the obtained resin composition E were evaluated in the same manner as in Example 1. The results are disclosed in Table 3. As shown in Table 3, the resin composition E exhibited excellent mold cleanability. Further, when the epoxy resin sealing material is molded without using the resin composition for mold release recovery after the mold cleaning by the resin composition E, the mold release property exhibited at this time is not inferior to that of the previous mold. The mold release property when the resin composition for mold release is released.
利用球磨機，將1000重量份之製造例1中所獲得之樹脂含量約為72%之混合有紙漿之三聚氰胺-甲醛樹脂粉末、0.5重量份之鄰苯二甲酸酐、2.5重量份之硬脂酸鋅及1.0重量份之Loxiol G78(日本科寧股份有限公司製高分子複合酯)加以混合，藉此獲得模具清潔用及模具脫模回復用樹脂組合物F。利用與實施例1同樣之方式，評估所獲得之樹脂組合物F的模具清潔性及模具脫模性。其結果揭示於表3中。如表3所示，樹脂組合物F發揮出優良之模具清潔性。 又，於利用樹脂組合物F進行模具清潔後未使用模具脫模回復用樹脂組合物之情況下使環氧密封材料成形時，此時呈現出之模具脫模性並不遜於先前之使用有模具脫模回復用樹脂組合物時之模具脫模性。Using a ball mill, 1000 parts by weight of a melamine-formaldehyde resin powder mixed with pulp having a resin content of about 72%, 0.5 parts by weight of phthalic anhydride, and 2.5 parts by weight of zinc stearate obtained in Production Example 1 were used. The resin composition F for mold cleaning and mold release recovery was obtained by mixing 1.0 parts by weight of Loxiol G78 (polymer complex ester manufactured by Nippon Corning Co., Ltd.). The mold cleanability and mold release property of the obtained resin composition F were evaluated in the same manner as in Example 1. The results are disclosed in Table 3. As shown in Table 3, the resin composition F exhibited excellent mold cleanability. Further, when the epoxy resin sealing material is formed without using the resin composition for mold release recovery after the mold cleaning by the resin composition F, the mold release property exhibited at this time is not inferior to that of the previous mold. The mold release property when the resin composition for mold release is released.
利用球磨機，將1000重量份之製造例1中所獲得之樹脂含量約為72%之混合有紙漿之三聚氰胺-甲醛樹脂粉末、30重量份之製造例2中所獲得之粉末狀三聚氰胺樹脂、30重量份之粉末紙漿、0.5重量份之鄰苯二甲酸酐、2.5重量份之硬脂酸鋅及3.5重量份之Licolub H-4(日本科萊恩股份有限公司製改性烴)加以混合，藉此獲得模具清潔用及模具脫模回復用樹脂組合物G。利用與實施例1同樣之方式，評估所獲得之樹脂組合物G的模具清潔性及模具脫模性。其結果揭示於表3中。如表3所示，樹脂組合物G發揮出優良之模具清潔性。又，於利用樹脂組合物G進行模具清潔後未使用模具脫模回復用樹脂組合物之情況下使環氧密封材 料成形時，此時呈現出之模具脫模性並不遜於先前之使用有模具脫模回復用樹脂組合物時之模具脫模性。Using a ball mill, 1000 parts by weight of a melamine-formaldehyde resin powder mixed with pulp having a resin content of about 72% obtained in Production Example 1, 30 parts by weight of a powdery melamine resin obtained in Production Example 2, and 30 parts by weight a portion of the powdered pulp, 0.5 parts by weight of phthalic anhydride, 2.5 parts by weight of zinc stearate, and 3.5 parts by weight of Licolub H-4 (modified hydrocarbon manufactured by Clariant Co., Ltd., Japan) are mixed. Resin composition G for mold cleaning and mold release. The mold cleanability and mold release property of the obtained resin composition G were evaluated in the same manner as in Example 1. The results are disclosed in Table 3. As shown in Table 3, the resin composition G exhibited excellent mold cleanability. Moreover, after the mold cleaning by the resin composition G, the epoxy resin sealing material is used without using the mold release-recovering resin composition. When the material is formed, the mold release property exhibited at this time is not inferior to that of the previous mold release resin composition for mold release recovery.
利用球磨機，將1000重量份之製造例1中所獲得之樹脂含量約為72%之混合有紙漿之三聚氰胺-甲醛樹脂粉末、30重量份之製造例2中所獲得之粉末狀三聚氰胺樹脂、30重量份之粉末紙漿、0.5重量份之鄰苯二甲酸酐、2.5重量份之硬脂酸鋅及3.0重量份之Loxiol VPN881(日本科寧股份有限公司製礦物油系合成蠟)加以混合，藉此獲得模具清潔用及模具脫模回復用樹脂組合物H。利用與實施例1同樣之方式，評估所獲得之樹脂組合物H的模具清潔性及模具脫模性。其結果揭示於表3中。如表3所示，樹脂組合物H發揮出優良之模具清潔性。又，於利用樹脂組合物H進行模具清潔後未使用模具脫模回復用樹脂組合物之情況下使環氧密封材料成形時，此時呈現出之模具脫模性並不遜於先前之使用有模具脫模回復用樹脂組合物時之模具脫模性。Using a ball mill, 1000 parts by weight of a melamine-formaldehyde resin powder mixed with pulp having a resin content of about 72% obtained in Production Example 1, 30 parts by weight of a powdery melamine resin obtained in Production Example 2, and 30 parts by weight a portion of the powdered pulp, 0.5 parts by weight of phthalic anhydride, 2.5 parts by weight of zinc stearate, and 3.0 parts by weight of Loxol VPN 881 (mineral oil-based synthetic wax made by Nippon Corning Co., Ltd.) are mixed. Resin composition H for mold cleaning and mold release. The mold cleanability and mold release property of the obtained resin composition H were evaluated in the same manner as in Example 1. The results are disclosed in Table 3. As shown in Table 3, the resin composition H exhibited excellent mold cleanability. Moreover, when the epoxy sealing material is formed without using the resin composition for mold release recovery after the mold cleaning by the resin composition H, the mold release property exhibited at this time is not inferior to that of the previous mold. The mold release property when the resin composition for mold release is released.
藉由使用本發明之模具清潔用及模具脫模回復用樹脂組 合物，可去除因近年來環氧密封樹脂之高功能化及半導體素子之高功能化所造成之模穴部、通氣孔部等處之明顯污物，又，無須如先前般於模具清潔操作結束後必須實施模具脫模回復操作，即可使模具具有脫模性。因此，可減少非常煩雜之一系列模具清潔操作及模具脫模回復操作，從而可縮短操作時間。並且，無須使用轉移成形時所必需之引線框架或虛設框架(dummy frame)等構件，因此亦可減少一系列模具清潔操作及模具脫模回復操作之相關成本。Resin group for mold cleaning and mold release recovery by using the present invention The compound can remove the obvious dirt at the cavity portion, the vent hole portion and the like due to the high functionalization of the epoxy sealing resin and the high functionalization of the semiconductor element in recent years, and it is not necessary to clean the mold as before. After the end, the mold release operation must be carried out to make the mold release. Therefore, it is possible to reduce the troublesome operation of one of the series of mold cleaning operations and the mold release recovery operation, thereby shortening the operation time. Moreover, it is not necessary to use a member such as a lead frame or a dummy frame necessary for transfer molding, and thus it is also possible to reduce the costs associated with a series of mold cleaning operations and mold release recovery operations.
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| JP6803165B2 (en) * | 2015-08-07 | 2020-12-23 | 日本カーバイド工業株式会社 | Resin composition for mold cleaning |
| JP2022190598A (en) * | 2021-06-14 | 2022-12-26 | Ｔｏｗａ株式会社 | Mold maintenance member, resin molding apparatus, and method for manufacturing resin molded product |
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| JPH0957762A (en) * | 1995-08-23 | 1997-03-04 | Nippon Carbide Ind Co Inc | Resin composition for cleaning mold |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0957762A (en) * | 1995-08-23 | 1997-03-04 | Nippon Carbide Ind Co Inc | Resin composition for cleaning mold |
| JP2001247755A (en) * | 2000-03-08 | 2001-09-11 | Teijin Ltd | Resin pellet mixture for connector |
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| CN101466515A (en) | 2009-06-24 |
| WO2008050682A1 (en) | 2008-05-02 |
| MY155928A (en) | 2015-12-31 |
| KR101395818B1 (en) | 2014-05-16 |
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| HK1131099A1 (en) | 2010-01-15 |
| JP4948541B2 (en) | 2012-06-06 |
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| JPWO2008050682A1 (en) | 2010-02-25 |
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