TWI551417B - Resin composition for mold cleaning - Google Patents
Resin composition for mold cleaning Download PDFInfo
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- TWI551417B TWI551417B TW102102381A TW102102381A TWI551417B TW I551417 B TWI551417 B TW I551417B TW 102102381 A TW102102381 A TW 102102381A TW 102102381 A TW102102381 A TW 102102381A TW I551417 B TWI551417 B TW I551417B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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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
- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/1753—Cleaning or purging, e.g. of the injection unit
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
- C08G14/10—Melamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本發明關於模具清理用樹脂組成物。更詳而言之,本發明為關於去除來自熱硬化性樹脂組成物之成形模具內部表面的污垢,且屬轉移類型的模具清理用樹脂組成物。 The present invention relates to a resin composition for mold cleaning. More specifically, the present invention relates to a resin composition for mold cleaning which is a transfer type for removing dirt from the inner surface of a molding die of a thermosetting resin composition.
在使用含有熱硬化性樹脂組成物之密封成形材料進行密封成形之情況中,在長時間持續進行積體電路或LED元件等的密封成形作業時,容易產生來自密封成形材料的污垢。由於這樣污垢的產生,而有成形模具內弄髒了的不良情況。這樣的污垢被放置在模具內時,會發生污垢附著在積體電路或LED元件等的密封成形物的表面的不良情況。因此,進行密封成形的情況要求能去除成形模具內的污垢。具體而言,在進行密封成形的情況,最好是每進行數百次射出的密封成形以數次射出的比例,成形模具清理用樹脂組成物以取代密封成形材料。藉由成形模具清理用樹脂組成物,可去除成形模具內部表面的污垢。 In the case of performing sealing molding using a sealing molding material containing a thermosetting resin composition, it is easy to cause dirt from the sealing molding material when the sealing forming operation of the integrated circuit or the LED element or the like is continued for a long period of time. Due to the generation of such dirt, there is a problem that the mold is dirty. When such a stain is placed in a mold, there is a problem that dirt adheres to the surface of the sealed product such as an integrated circuit or an LED element. Therefore, it is required to perform the sealing forming to remove the dirt in the forming mold. Specifically, in the case of performing the sealing molding, it is preferable to form the resin composition for mold cleaning in place of the sealing molding material in a ratio of the number of times of sealing formation for several hundred shots. The dirt on the inner surface of the forming mold can be removed by forming the resin composition for mold cleaning.
以往以來已提案有這樣的模具清理用樹脂組成物。例如,專利文獻1記載的模具清理用樹脂組成物係相對於胺基系樹脂的全量而言含有10~70質量%的環氧變性三聚氰胺樹脂,其能提高模具清理時成形所得之成形品的熱時韌性,且提高模具清理的作業性。 Such a resin composition for mold cleaning has been proposed in the past. For example, the resin composition for mold cleaning described in Patent Document 1 contains 10 to 70% by mass of an epoxy-denatured melamine resin based on the total amount of the amine-based resin, which can improve the heat of the molded article obtained by molding the mold. Time toughness and improve the workability of mold cleaning.
近年來,為對應於所使用機器的高性能化,積體電路或LED元件等的密封成形形狀及構造正為多樣化、精密化。因此,用於密封成形步驟之成形模具的形狀及構造逐漸走向多樣化、精密化。這樣的成形模具的清理係要求能去除包括污垢容易殘留的角隅部、至模具空腔的各角落的污垢。 In recent years, in order to improve the performance of the equipment to be used, the shape and structure of the seal forming of an integrated circuit or an LED element are diversified and refined. Therefore, the shape and structure of the molding die used for the sealing forming step are gradually diversified and refined. The cleaning of such a forming mold is required to remove dirt including corners which are easily left by dirt and corners of the cavity of the mold.
專利文獻1係記載一種模具清理用樹脂組成物,其係相對於礦物質類粉體全量而言,最大粒徑為180μm以下、且粒徑100μm以上之礦物質類粉體為1質量%而成者。專利文獻1所記載的模具清理用樹脂組成物係揭露:模具清理用樹脂組成物遍佈空隙內部的各角落,有改善在狹小的澆口部分堵塞所得之清理作業性的效果。然而,其效果不夠充分,還有改善的餘地。此外,專利文獻1所記載的模具清理用樹脂組成物在模具內的污垢除去性能方面也還有改善的餘地。 Patent Document 1 discloses a resin composition for cleaning a mold, wherein the maximum particle diameter is 180 μm or less and the mineral powder having a particle diameter of 100 μm or more is 1% by mass based on the total amount of the mineral powder. By. The resin composition for mold cleaning disclosed in Patent Document 1 discloses that the resin composition for mold cleaning is distributed in various corners of the inside of the gap, and has an effect of improving the cleaning workability obtained by clogging the narrow gate portion. However, the effect is not sufficient and there is room for improvement. Further, the resin composition for mold cleaning described in Patent Document 1 also has room for improvement in the dirt removal performance in the mold.
清理模具時,若使用將填充材小粒化之模具清理用樹脂組成物,則可抑制細緻化之模具空腔內狹小澆口部分的堵塞。可是,若將填充材小粒化,則填充材的物理研磨效果降低,特別是會有角隅部污垢除去性能降低的不良情況。又,將填充材小粒化之模具清理用樹脂組成物在清理時,模具清理用樹脂組成物的流動會變得過度。因此,模具清理用樹脂組成物沒有適當地停留在模具內,所以會有無法充分地去除污垢的不良情況。 When the mold is cleaned, if the resin composition for mold cleaning for granulating the filler is used, clogging of the narrow gate portion in the finished mold cavity can be suppressed. However, when the filler is granulated, the physical polishing effect of the filler is lowered, and in particular, the corner dirt removal performance is deteriorated. In addition, when the resin composition for mold cleaning for granulating the filler is cleaned, the flow of the resin composition for mold cleaning becomes excessive. Therefore, the resin composition for mold cleaning does not properly stay in the mold, so that there is a problem that the scale cannot be sufficiently removed.
【專利文獻1】日本特開2003-62835號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-62835
本發明係有鑑於上述狀況而完成者。也就是說,基於上述狀況,須有例如能得到直至細緻化之模具空腔的角隅部等的良好清理效果,且去除污垢的性能受到改善之模具清理用樹脂組成物。 The present invention has been made in view of the above circumstances. In other words, based on the above-mentioned situation, there is a resin composition for mold cleaning which is capable of obtaining a good cleaning effect such as a corner portion of the mold cavity until the fineness is obtained, and which has improved dirt removal performance.
本發明的模具清理用樹脂組成物為包含三聚氰胺系樹脂、無機填充材、硬化觸媒、飽和脂肪酸與金屬的鹽,其中前述無機填充材為球形,前述無機填充材的最大粒徑為1μm~70μm的範圍,前述硬化觸媒為由肉荳蔻酸及硬脂酸中所選出之至少一者,且前述飽和脂肪酸與金屬的鹽為肉荳蔻酸鋅。 The resin composition for mold cleaning according to the present invention is a salt containing a melamine resin, an inorganic filler, a curing catalyst, a saturated fatty acid, and a metal, wherein the inorganic filler is spherical, and the inorganic filler has a maximum particle diameter of 1 μm to 70 μm. The hardening catalyst is at least one selected from the group consisting of myristic acid and stearic acid, and the salt of the saturated fatty acid and the metal is zinc myristate.
又,在本發明的模具清理用樹脂組成物中,以前述無機填充材之平均粒徑為4μm~10μm、粒徑的標準偏差為7μm以下,且粒徑的平均縱橫比為1~1.2、縱橫比的標準偏差為0.3以下之態樣為佳。 Further, in the resin composition for cleaning a mold according to the present invention, the inorganic filler has an average particle diameter of 4 μm to 10 μm, a standard deviation of particle diameters of 7 μm or less, and an average aspect ratio of the particle diameter of 1 to 1.2, and a cross direction. It is preferable that the standard deviation of the ratio is 0.3 or less.
又,本發明的模具清理用樹脂組成物係以用於轉移型成形機之轉移類型的模具清理用樹脂組成物之態樣為佳。也就是說,本發明的模具清理用樹脂組成物可適當地用於轉移成形。 Moreover, it is preferable that the resin composition for mold cleaning of the present invention is a resin composition for mold cleaning for a transfer type of a transfer molding machine. That is, the resin composition for mold cleaning of the present invention can be suitably used for transfer molding.
依據本發明,藉由特別規定無機填充材的形狀、粒徑的範圍,且使用特定的硬化觸媒及特定的飽和脂肪酸與金屬的鹽,可提供能得到直至細緻化之模具空腔的角隅部的良好清理效果,且污垢的除去性能得到改善之模具清理用樹脂組成物。 According to the present invention, by specifying the shape of the inorganic filler, the range of the particle diameter, and the use of a specific hardening catalyst and a salt of a specific saturated fatty acid and a metal, it is possible to provide a corner of the mold cavity which can be obtained until the detail is obtained. A resin composition for mold cleaning which has a good cleaning effect and is improved in dirt removal performance.
以下,就本發明的模具清理用樹脂組成物的實施形態加以說明。 Hereinafter, an embodiment of the resin composition for mold cleaning of the present invention will be described.
本發明的模具清理用樹脂組成物係至少使用三聚氰胺系樹脂、最大粒徑為1μm~70μm之球形無機填充材、由肉荳蔻酸及硬脂酸所選出之硬化觸媒、及係飽和脂肪酸與金屬的鹽之肉荳蔻酸鋅而構成。本發明的模具清理用樹脂組成物亦可按照需要進一步使用其他成分而構成。 The resin composition for mold cleaning of the present invention is at least a melamine resin, a spherical inorganic filler having a maximum particle diameter of 1 μm to 70 μm, a hardening catalyst selected from myristic acid and stearic acid, and a saturated fatty acid and a metal. The salt of the meat consists of zinc myristic acid. The resin composition for mold cleaning of the present invention may be further composed of other components as needed.
本發明的模具清理用樹脂組成物含有至少一種的三聚氰胺系樹脂。 The resin composition for mold cleaning of the present invention contains at least one type of melamine-based resin.
所謂的三聚氰胺系樹脂係表示三聚氰胺樹脂、三聚氰胺-苯酚共縮合物、或三聚氰胺-尿素共縮合物。 The melamine resin is a melamine resin, a melamine-phenol cocondensate, or a melamine-urea cocondensate.
前述三聚氰胺樹脂為三嗪類與醛類的縮合物。三嗪類可舉出例如三聚氰胺、苯并胍胺及乙胍嗪等。醛類可舉出例如甲醛、多聚甲醛、及乙醛。 The melamine resin is a condensate of a triazine and an aldehyde. Examples of the triazines include melamine, benzoguanamine, and oxazine. Examples of the aldehydes include formaldehyde, paraformaldehyde, and acetaldehyde.
前述三聚氰胺-苯酚共縮合物為三嗪類、酚類、與醛類的共縮合物。酚類可舉出例如苯酚、甲酚、二甲苯酚、乙基苯酚、及丁基苯酚。 The melamine-phenol cocondensate is a cocondensate of a triazine, a phenol, and an aldehyde. Examples of the phenols include phenol, cresol, xylenol, ethylphenol, and butylphenol.
前述三聚氰胺-尿素共縮合物為三嗪類、尿素類、與醛類的共縮合物。 The melamine-urea cocondensate is a cocondensate of a triazine, a urea, and an aldehyde.
本發明的模具清理用樹脂組成物除了三聚氰胺系樹脂以外,亦可在無損於本發明效果之範圍內含有其他的樹脂組成物、例如醇酸樹脂、聚酯樹脂、丙烯酸系樹脂、環氧樹脂、及橡膠類。 In addition to the melamine-based resin, the resin composition for mold cleaning of the present invention may contain other resin compositions such as an alkyd resin, a polyester resin, an acrylic resin, an epoxy resin, or the like insofar as the effects of the present invention are not impaired. And rubber.
本發明的模具清理用樹脂組成物由於含有三聚氰胺系樹脂,所以對於成形模具內部表面的污垢發揮優異的清理性。關於其理由雖然尚未能清楚明白,但一般認為是由於三聚氰胺系樹脂具有之羥甲基的極性高,能對在成形時發生且附著於成形模具內部表面之由密封成形材料而來的污垢(亦即來自於含有熱硬化性樹脂組成物之密封成形材料的污垢)、與本發明的模具清理用樹脂組成物起作用,所以含有三聚氰胺系樹脂之模具清理用樹脂組成物能顯示出優異的性能。 又,一般認為由於三聚氰胺系樹脂對於熱為穩定的,所以即使在清理模具時的溫度即160~190℃附近亦能穩定且發揮優異的清理性。 Since the resin composition for mold cleaning of the present invention contains a melamine-based resin, it exhibits excellent cleaning properties against dirt on the inner surface of the molding die. Although the reason for this is not clearly understood, it is considered that the melamine-based resin has a high polarity of a methylol group, and can be used for sealing the molding material which is generated during molding and adheres to the inner surface of the molding die ( In other words, the resin composition for the mold for cleaning the mold of the present invention acts on the resin composition for cleaning the mold of the present invention. Therefore, the resin composition for mold cleaning containing the melamine resin can exhibit excellent performance. . Further, since the melamine-based resin is generally stable to heat, it is considered to be stable even in the vicinity of 160 to 190 ° C at the time of cleaning the mold, and to exhibit excellent cleanability.
本發明的模具清理用樹脂組成物包含至少一種最大粒徑為1μm~70μm之球形無機填充材。 The resin composition for mold cleaning of the present invention contains at least one spherical inorganic filler having a maximum particle diameter of from 1 μm to 70 μm.
本發明所使用的無機填充材具有球形。所謂的球形較佳為後述之無機填充材的粒徑平均縱橫比為1~1.5者,除了完全的球形外,亦可包含斷面的直徑不一樣的斷面橢圓等、接近被視為球形程度的球形狀之略球形。 The inorganic filler used in the present invention has a spherical shape. The spherical shape is preferably one in which the average aspect ratio of the inorganic filler to be described later is from 1 to 1.5, and in addition to the complete spherical shape, the cross-sectional ellipse having a different diameter of the cross-section may be included. The shape of the ball is slightly spherical.
無機填充材的粒徑的平均縱橫比較佳為1~1.2。因而,本發明的模具清理用樹脂組成物可在清理時保持模具清理用樹脂組成物的流動性。此外,本發明的模具清理用樹脂組成物能期待有直至細緻化之模具空腔的角隅部的良好清理效果,進而能抑制成形模具內部表面及澆口部分的磨損、傷痕。 The average aspect ratio of the particle diameter of the inorganic filler is preferably from 1 to 1.2. Therefore, the resin composition for mold cleaning of the present invention can maintain the fluidity of the resin composition for mold cleaning during cleaning. Further, the resin composition for mold cleaning of the present invention can be expected to have a good cleaning effect of the corner portion of the mold cavity until the fineness, and further, it is possible to suppress abrasion and scratches on the inner surface of the mold and the gate portion.
若模具清理用樹脂組成物的無機填充材的粒徑的平均縱橫比為1.5以下,則在清理時能良好地保持模具清理用樹脂組成物的流動性、能確保直至細緻化之模具空腔的角隅部的良好清理性。又,也能抑制成形模具內部表面及澆口部分的磨損、傷痕的發生。 When the average aspect ratio of the particle diameter of the inorganic filler of the resin composition for mold cleaning is 1.5 or less, the fluidity of the resin composition for mold cleaning can be favorably maintained during cleaning, and the cavity of the mold can be secured until the mold cavity is refined. Good cleanliness of the corners. Further, it is possible to suppress the occurrence of abrasion and scratches on the inner surface of the molding die and the gate portion.
在本發明中,無機填充材的粒徑的縱橫比係如下述般而獲得。 In the present invention, the aspect ratio of the particle diameter of the inorganic filler is obtained as follows.
也就是說,無機填充材的粒徑的縱橫比與後述之求得粒徑的方法同樣使用電子顯微鏡而獲得。在本說明書中,分別測量一個無機填充材的長徑(X)、及與長徑(X)正交的短徑(Y)5次。並從所得之測量值,依下述式子而求得1個無機填充材的粒徑的縱橫比。但,長徑(X)≧短徑(Y)。 In other words, the aspect ratio of the particle diameter of the inorganic filler is obtained by an electron microscope in the same manner as the method of determining the particle diameter described later. In the present specification, the major axis (X) of one inorganic filler and the minor axis (Y) orthogonal to the major axis (X) are measured five times. From the obtained measured values, the aspect ratio of the particle diameter of one inorganic filler was determined by the following formula. However, the long diameter (X) ≧ short diameter (Y).
粒徑的縱橫比=(X之5次測量值的平均值)/(Y之5次測量值的平均值) Aspect ratio of particle size = (average of 5 measurements of X) / (average of 5 measurements of Y)
而且,分別對150個的無機填充材測量上述的縱橫比,並求得所得之測量值的平均,作為無機填充材粒子的縱橫比。 Further, the above aspect ratio was measured for 150 inorganic fillers, and the average of the obtained measured values was determined as the aspect ratio of the inorganic filler particles.
依據本發明的定義,在長徑(X)與短徑(Y)相等的情況,粒徑的縱橫比為1。在本發明的定義中,粒徑的縱橫比不採用未滿1的值。無機填充材的形狀為球形,越近似球形則粒徑的縱橫比越接近1。假設無機填充材在電子顯微鏡的影像為正方形形狀之情況粒徑的縱橫比為1,本發明所使用的無機填充材的形狀為任一球形(包含略球形),且本發明中粒徑的縱橫比接近1則表示越近似球形。 According to the definition of the present invention, in the case where the major axis (X) and the minor axis (Y) are equal, the aspect ratio of the particle diameter is 1. In the definition of the present invention, the aspect ratio of the particle size does not take a value less than one. The shape of the inorganic filler is spherical, and the closer to the spherical shape, the closer the aspect ratio of the particle diameter is to 1. It is assumed that the inorganic filler has an aspect ratio of the particle diameter when the image of the electron microscope is square, and the shape of the inorganic filler used in the present invention is any spherical shape (including a slightly spherical shape), and the aspect ratio of the particle diameter in the present invention. A ratio closer to 1 indicates a more spherical shape.
在本發明中,無機填充材的粒徑的平均縱橫比為以上述方法所測定之150個的無機填充材之縱橫比的平均值。又,後述之無機填充材之縱橫比的標準偏差為以上述方法所測定之150個的無機填充材粒徑之縱橫比的標準偏差。 In the present invention, the average aspect ratio of the particle diameter of the inorganic filler is an average value of the aspect ratio of the 150 inorganic fillers measured by the above method. Moreover, the standard deviation of the aspect ratio of the inorganic filler mentioned later is the standard deviation of the aspect ratio of the 150 inorganic filler particle diameter measured by the above-mentioned method.
無機填充材為例如由碳化矽、氧化矽(silica)、碳化鈦、氧化鈦、碳化硼、氧化硼、氧化鋁、氧化鎂、及氧化鈣構成群組中所選出之1種以上。此等無機填充材可單獨使用、又亦可組合複數個而使用。 The inorganic filler is, for example, one or more selected from the group consisting of cerium carbide, cerium oxide, titanium carbide, titanium oxide, boron carbide, boron oxide, aluminum oxide, magnesium oxide, and calcium oxide. These inorganic fillers may be used singly or in combination of plural kinds.
本發明的無機填充材較佳為氧化矽(silica)、氧化鈦,特佳為氧化矽。雖然視模具的材質、狀態而定,但作為本發明所使用的無機填充材,從硬度適當、能抑制成形模具內部表面及澆口部分的磨損、傷痕之點而言,氧化矽(silica)或氧化鈦為佳。本發明的發明人認為清理細緻化之模具空腔時,無機填充材能藉由物理性研磨而除去模具表面的污垢。又,氧化矽(silica)或氧化鈦由於即使在清理模具時之160~190℃附近也能熱穩定而為較佳。 The inorganic filler of the present invention is preferably silica or titania, and particularly preferably cerium oxide. Depending on the material and the state of the mold, the inorganic filler used in the present invention is silica or silica from the viewpoint of appropriate hardness and suppression of abrasion and scratches on the inner surface of the mold and the gate portion. Titanium oxide is preferred. The inventors of the present invention believe that the inorganic filler can remove dirt from the surface of the mold by physical grinding when cleaning the refined mold cavity. Further, it is preferable that silica or titanium oxide is thermally stable even in the vicinity of 160 to 190 ° C when the mold is cleaned.
本發明的模具清理用樹脂組成物最好是前述無機填充材的縱橫比之標準偏差為0.3以下。若本發明模具清理用樹脂組成物的前述無機填充材粒徑的縱橫比之標準偏差為0.3以下,則由於能在清理時輕易保持模具清理用樹脂組成物的流動性,所以可輕易得到直至模具空腔之角隅部的清理性,更能抑制成形模具內部表面及澆口部分的磨損、傷痕。 In the resin composition for mold cleaning of the present invention, it is preferable that the standard deviation of the aspect ratio of the inorganic filler is 0.3 or less. When the standard deviation of the aspect ratio of the particle size of the inorganic filler of the resin composition for mold cleaning of the present invention is 0.3 or less, since the fluidity of the resin composition for mold cleaning can be easily maintained during cleaning, it can be easily obtained until the mold The cleaning property of the corner portion of the cavity can suppress the wear and scratches on the inner surface of the forming mold and the gate portion.
其中,作為無機填充材之縱橫比的標準偏差尤以0.15~0.3為更佳。 Among them, the standard deviation of the aspect ratio of the inorganic filler is preferably 0.15 to 0.3.
上述中所謂的「細緻化之模具空腔」係指經由使空腔小型化,而使空腔對 成形模具表面全體的排列被緻密地最適當配置。細緻化之模具空腔因空腔的小型化而使得澆口部分也變得比以往者更為狹窄,其最狹窄處為100μm。 The term "refinement of the mold cavity" as used herein refers to the cavity pair by miniaturizing the cavity. The arrangement of the entire surface of the forming mold is optimally arranged in a dense manner. The meticulous mold cavity is made smaller by the miniaturization of the cavity, and the gate portion is also narrower than the past, and the narrowest portion is 100 μm.
本發明所使用的無機填充材的最大粒徑為1μm~70μm。在本發明的模具清理用樹脂組成物由於所含有之無機填充材的最大粒徑在1μm~70μm的範圍,所以能得到直至細緻化之模具空腔的角隅部的良好清理效果。在本說明書中,最大粒徑為1μm以上係意味著具備無機填充材會對模具表面的污垢起物理性作用程度的形狀。又,若最大粒徑超過70μm,則無機填充劑的粒子彼此變得容易堵塞於空腔部,而流動性下降,結果使得清理效果降低。 The inorganic filler used in the present invention has a maximum particle diameter of from 1 μm to 70 μm. In the resin composition for mold cleaning of the present invention, since the maximum particle diameter of the inorganic filler to be contained is in the range of 1 μm to 70 μm, it is possible to obtain a good cleaning effect of the corner portion of the mold cavity which is refined. In the present specification, the maximum particle diameter of 1 μm or more means that the inorganic filler has a physical effect on the dirt on the surface of the mold. In addition, when the maximum particle diameter exceeds 70 μm, the particles of the inorganic filler are likely to be clogged with each other in the cavity portion, and the fluidity is lowered, and as a result, the cleaning effect is lowered.
其中,作為無機填充材的最大粒徑尤以10μm~50μm為更佳,特佳為20μm~45μm,最佳為45μm。 Among them, the maximum particle diameter of the inorganic filler is preferably from 10 μm to 50 μm, more preferably from 20 μm to 45 μm, and most preferably 45 μm.
本發明所使用的無機填充材的平均粒徑最好是4μm~10μm。本發明的發明人認為平均粒徑顯著小的無機填充材由於質量或表面積小,所以難以發揮模具空腔的清理性能。在本發明的模具清理用樹脂組成物中,若前述無機填充材的平均粒徑為4μm以上,則更能得到成形模具全體的清理性。又,若前述無機填充材的平均粒徑為10μm以下,則更能得到直至細緻化之模具空腔的角隅部的清理性。此外,在本發明中無機填充材的平均粒徑若為10μm以下,則更能抑制成形模具內部表面及澆口部分的磨損、傷痕。 The inorganic filler used in the present invention preferably has an average particle diameter of 4 μm to 10 μm. The inventors of the present invention considered that the inorganic filler having a significantly small average particle diameter has a small mass or surface area, so that it is difficult to exhibit the cleaning performance of the mold cavity. In the resin composition for mold cleaning of the present invention, when the average particle diameter of the inorganic filler is 4 μm or more, the cleanability of the entire mold can be obtained. In addition, when the average particle diameter of the inorganic filler is 10 μm or less, the cleaning property of the corner portion of the mold cavity to be refined can be obtained more. Further, in the present invention, when the average particle diameter of the inorganic filler is 10 μm or less, abrasion and scratches on the inner surface of the molding die and the gate portion can be more suppressed.
其中,作為無機填充材的平均粒徑尤以5μm~8μm為更佳。 Among them, the average particle diameter of the inorganic filler is preferably from 5 μm to 8 μm.
本發明所使用的無機填充材的粒徑的標準偏差最好是7μm以下。在本發明的模具清理用樹脂組成物中,若無機填充材的粒徑的標準偏差為7μm以下,由於在清理時能保持模具清理用樹脂組成物的流動性,所以更能得到直至模具空腔的角隅部的清理性。 The standard deviation of the particle diameter of the inorganic filler used in the present invention is preferably 7 μm or less. In the resin composition for mold cleaning of the present invention, if the standard deviation of the particle diameter of the inorganic filler is 7 μm or less, since the fluidity of the resin composition for mold cleaning can be maintained during cleaning, it is possible to obtain a cavity up to the mold. The cleanliness of the corners.
其中,作為無機填充材的粒徑的標準偏差尤以1μm~7μm為更佳。 Among them, the standard deviation of the particle diameter of the inorganic filler is preferably from 1 μm to 7 μm.
在本發明中,前述無機填充材的粒徑係如下述般而求得。 In the present invention, the particle diameter of the inorganic filler is determined as follows.
也就是說,使用電子顯微鏡(製品名;JSM-5510、日本電子股份有限公司製), 以在1個視野中大概含有30個無機填充材的方式,以1500倍來攝影無機填充材,並分別測定5個不同視野各自的無機填充材的粒徑。繼續測量無機填充材的長徑(X)、及與長徑(X)正交的短徑(Y),且求得各5次的測量值的平均值。針對合計150個的無機填充材來測量X及Y,利用下述式子求得1個無機填充材的粒徑,並將150個的無機填充材的粒徑(計算值)進行平均,以求得無機填充材的粒徑。 In other words, an electron microscope (product name; JSM-5510, manufactured by JEOL Ltd.) is used. The inorganic filler was photographed at 1500 times so that approximately 30 inorganic fillers were contained in one field of view, and the particle diameters of the inorganic fillers in each of five different fields of view were measured. The long diameter (X) of the inorganic filler and the short diameter (Y) orthogonal to the long diameter (X) were continuously measured, and the average value of the measured values of each of the five times was obtained. X and Y were measured for a total of 150 inorganic fillers, and the particle diameter of one inorganic filler was determined by the following formula, and the particle diameters (calculated values) of 150 inorganic fillers were averaged. The particle size of the inorganic filler material is obtained.
粒徑=((X之5次測量值的平均值)+(Y之5次測量值的平均值))/2 Particle size = ((the average of 5 measurements of X) + (the average of 5 measurements of Y)) / 2
在本發明中,平均粒徑為以上述方法所測定之150個的無機填充材粒徑的平均值。又,粒徑的標準偏差為以上述方法所測定之150個的無機填充材粒徑的標準偏差。 In the present invention, the average particle diameter is an average value of the particle diameters of 150 inorganic fillers measured by the above method. Further, the standard deviation of the particle diameter is the standard deviation of the particle diameter of 150 inorganic fillers measured by the above method.
適合使用於本發明的無機填充材為例如非晶質的球形氧化矽,具體而言,可舉出新日鐵住金材料股份有限公司MICRON公司(新日鐵材料股份有限公司MICRON公司)製的製品名「S440-4」、「HS-202」、「HS-204」、「UF-320」等。 The inorganic filler to be used in the present invention is, for example, an amorphous spherical cerium oxide, and specifically, a product manufactured by Nippon Steel & Metal Materials Co., Ltd. MICRON (Nippon Steel Materials Co., Ltd.) Names "S440-4", "HS-202", "HS-204", "UF-320", etc.
本發明的模具清理用樹脂組成物含有由肉荳蔻酸及硬脂酸所選出之至少一者作為硬化觸媒。 The resin composition for mold cleaning of the present invention contains at least one selected from myristic acid and stearic acid as a curing catalyst.
模具清理用樹脂組成物若為球形(包含略球形)、且將最大粒徑為1μm~70μm的前述無機填充材用於模具清理用樹脂組成物,則清理細緻化之模具空腔時,會有由於模具清理用樹脂組成物的流動會變得過度,模具清理用樹脂組成物不會適當地停留於模具內,而無法充分地除去污垢的情況。本發明的發明人利用使用肉荳蔻酸及/或硬脂酸作為硬化觸媒,發現在清理細緻化之模具空腔時,能防止模具清理用樹脂組成物的流動變得過度。 When the resin composition for mold cleaning is spherical (including a spherical shape) and the inorganic filler having a maximum particle diameter of 1 μm to 70 μm is used for the resin composition for mold cleaning, when the fine mold cavity is cleaned, there will be Since the flow of the resin composition for mold cleaning becomes excessive, the resin composition for mold cleaning does not properly stay in the mold, and the dirt cannot be sufficiently removed. The inventors of the present invention have found that the use of myristic acid and/or stearic acid as a hardening catalyst can prevent the flow of the resin composition for mold cleaning from becoming excessive when the fined mold cavity is cleaned.
因而,本發明的模具清理用樹脂組成物藉由使模具清理用樹脂組成物適當地停留在模具內,而能清理細緻化之模具空腔的角隅部,並且也能改善污垢的除去性能。 Therefore, the resin composition for mold cleaning of the present invention can clean the corner portion of the fined mold cavity by appropriately holding the resin composition for mold cleaning in the mold, and can also improve the dirt removal performance.
本發明所使用的肉荳蔻酸及硬脂酸於組成物中的含量,相對於前述三聚氰胺系樹脂100質量份而言,以0.1質量份~3.0質量份為佳,0.5質量份~2.0質量份為更佳,特佳為1.0質量份~2.0質量份。前述肉荳蔻酸的含量若為0.1質量份以上,則本發明的模具清理用樹脂組成物於清理時容易硬化,能使細緻化之模具空腔的污垢被更良好地除去。又,若前述肉荳蔻酸為3.0質量份以下,則本發明的模具清理用樹脂組成物的儲藏穩定性更為優異。 The content of myristic acid and stearic acid in the composition of the present invention is preferably 0.1 parts by mass to 3.0 parts by mass, and 0.5 parts by mass to 2.0 parts by mass, based on 100 parts by mass of the melamine-based resin. More preferably, it is preferably 1.0 part by mass to 2.0 parts by mass. When the content of the myristic acid is 0.1 part by mass or more, the resin composition for mold cleaning of the present invention is easily cured at the time of cleaning, and the fineness of the fine mold cavity can be more effectively removed. In addition, when the amount of myristic acid is 3.0 parts by mass or less, the resin composition for mold cleaning of the present invention is more excellent in storage stability.
本發明的模具清理用樹脂組成物含有肉荳蔻酸鋅作為飽和脂肪酸與金屬的鹽。本發明的發明人認為在清理細緻化之模具空腔時,飽和脂肪酸與金屬的鹽對污垢起作用,例如經由使污垢膨潤而能輕易地從成形模具表面剝離下來。也就是說,本發明的發明人發現經由選擇性地使用飽和脂肪酸與金屬的鹽、特別是肉荳蔻酸鋅,能在清理細緻化之模具空腔時防止本發明的模具清理用樹脂組成物的流動變得過度。 The resin composition for mold cleaning of the present invention contains zinc myristate as a salt of a saturated fatty acid and a metal. The inventors of the present invention believe that the salt of saturated fatty acid and metal acts on the soil during the cleaning of the refined mold cavity, and can be easily peeled off from the surface of the forming mold, for example, by swelling the dirt. That is, the inventors of the present invention have found that by selectively using a salt of a saturated fatty acid and a metal, particularly zinc myristate, it is possible to prevent the resin composition for mold cleaning of the present invention from being cleaned when the mold cavity is cleaned. The flow has become excessive.
肉荳蔻酸鋅的熔點為123℃~130℃。又,清理使用含熱硬化性樹脂組成物之密封成形材料的模具空腔時的溫度通常為160℃~190℃。 The melting point of zinc myristate is 123 ° C ~ 130 ° C. Further, the temperature at which the mold cavity using the seal molding material containing the thermosetting resin composition is cleaned is usually 160 ° C to 190 ° C.
本發明的發明人認為由於本發明的模具清理用樹脂組成物中所含有的肉荳蔻酸鋅在清理作業環境溫度之160℃~190℃的範圍中顯示出適當的流動性,所以本發明的模具清理用樹脂組成物的流動係在適合清理之範圍。 The inventors of the present invention have considered that the zinc crotonate contained in the resin composition for mold cleaning of the present invention exhibits appropriate fluidity in the range of 160 ° C to 190 ° C in the cleaning working environment temperature, so the mold of the present invention The flow of the cleaning resin composition is suitable for cleaning.
因而,本發明的模具清理用樹脂組成物經由使模具清理用樹脂組成物適當地停留在模具內,而能清理細緻化之模具空腔的角隅部,且能改善污垢的除去性能。 Therefore, the resin composition for mold cleaning of the present invention can clean the corner portion of the fined mold cavity by appropriately holding the resin composition for mold cleaning in the mold, and can improve the removal performance of the dirt.
作為飽和脂肪酸與金屬的鹽使用的肉荳蔻酸鋅的含量,相對於前述三聚氰胺系樹脂100質量份而言,以0.1質量份~3.0質量份為佳、0.5質量份~2.0質量份為更佳,特佳為1.0質量份~2.0質量份。肉荳蔻酸鋅的含量若為0.1質量份以上,則本發明的模具清理用樹脂組成物在清理時容易變得硬化,能使細緻化之模具空腔的污垢被良好地除去。又,若肉荳蔻酸鋅的含量為3.0質量份以下,則 本發明的模具清理用樹脂組成物的流動不會變得過度,故為較佳。 The content of the zinc myristate used as the salt of the saturated fatty acid and the metal is preferably 0.1 parts by mass to 3.0 parts by mass, more preferably 0.5 parts by mass to 2.0 parts by mass, per 100 parts by mass of the melamine-based resin. It is particularly preferably 1.0 part by mass to 2.0 parts by mass. When the content of the zinc myristate is 0.1 parts by mass or more, the resin composition for mold cleaning of the present invention is easily hardened during cleaning, and the fineness of the fine mold cavity can be favorably removed. Moreover, if the content of zinc myristate is 3.0 parts by mass or less, then The flow of the resin composition for mold cleaning of the present invention does not become excessive, which is preferable.
本發明的模具清理用樹脂組成物亦可含有其他的添加劑。作為其他的添加劑,可舉出例如著色劑、抗氧化劑、滑劑等。 The resin composition for mold cleaning of the present invention may contain other additives. As another additive, a coloring agent, an antioxidant, a slip agent, etc. are mentioned, for example.
作為滑劑,可舉出例如脂肪醯胺系滑劑,詳而言之,可舉出如月桂醯胺、肉荳蔻醯胺、芥醯胺、油醯胺、硬脂醯胺般的飽和或不飽和單醯胺型滑劑,如亞甲基雙硬脂醯胺、伸乙基雙硬脂醯胺、伸乙基雙油醯胺般的飽和或不飽和雙醯胺型滑劑等。 The slip agent may, for example, be a fatty amide-based slip agent, and more specifically, it may be saturated or not like lauric acid, myristylamine, mesamine, ceramide or stearylamine. A saturated monoamine-type slip agent, such as methylenebisstearylamine, ethyl bis-stearylamine, ethyl bis-indoleamine-like saturated or unsaturated biguanide-type slipper, and the like.
本發明的模具清理用樹脂組成物適合於從成形模具內部的表面去除:自包含以環氧樹脂、聚矽氧樹脂、酚醛樹脂、及聚醯亞胺樹脂為代表的熱硬化性樹脂組成物之密封成形材料由來的污垢。 The resin composition for mold cleaning of the present invention is suitable for removal from the surface inside the mold: from a thermosetting resin composition typified by an epoxy resin, a polyoxymethylene resin, a phenol resin, and a polyimide resin. Seals the dirt from the forming material.
本發明的模具清理用樹脂組成物可經由將三聚氰胺系樹脂、無機填充材、硬化觸媒、飽和脂肪酸與金屬的鹽、及可按照需要的其他添加劑大略均勻混合而調製。作為用以大略均勻混合之方法,可舉出例如使用捏和機、螺條混合機、亨舍爾混合機、球磨機、輥軋機、擂潰機、及滾筒等的方法。 The resin composition for mold cleaning of the present invention can be prepared by uniformly mixing a melamine resin, an inorganic filler, a curing catalyst, a salt of a saturated fatty acid and a metal, and other additives as needed. As a method for roughly uniformly mixing, for example, a method using a kneader, a ribbon blender, a Henschel mixer, a ball mill, a roll mill, a kneader, and a drum can be mentioned.
本發明的模具清理用樹脂組成物適合於轉移型成形機所使用之轉移類型的模具清理用樹脂組成物。 The resin composition for mold cleaning of the present invention is suitable for a resin composition for mold cleaning of a transfer type used in a transfer type molding machine.
本發明的模具清理用樹脂組成物係加工為一般錠狀,使用於通常成形模具內的清理作業。詳而言之,將引線框架配置於模具上後,使錠狀的模具清理用樹脂組成物朝槽部插入,在鎖緊之後以活塞沖壓推動。此時,使樹脂由槽部經由流道部,從澆口部分流入模具空腔內部。清理作業係在經過規定的成形時間後,打開模具,去除包含與引線框架成為一體之模具清理用樹脂組成物及污垢的成形物而進行。 The resin composition for mold cleaning of the present invention is processed into a general ingot shape and used for cleaning work in a usual molding die. Specifically, after the lead frame is placed on the mold, the ingot-shaped mold cleaning resin composition is inserted into the groove portion, and after being locked, the piston is pushed by the piston. At this time, the resin flows from the groove portion through the flow path portion into the inside of the mold cavity from the gate portion. The cleaning operation is performed after the predetermined molding time has elapsed, the mold is opened, and the molded product including the resin composition for mold cleaning and the dirt integrated with the lead frame is removed.
本發明的模具清理用樹脂組成物係適合使用於除去在積體電路等密封成形作業中的成形模具內的污垢。前述成形模具的材質可舉出例如鐵或鉻等。成形模具內一般係經電鍍處理。經由重複密封成形作業、及成形模具內部的表面清理作業,會在成形模具內產生有微米尺寸的傷痕,而使得模具磨損。由於這樣的傷痕或摩損的產生,而會在成形模具內發生電鍍處理面的脫落或表面狀態的龜裂。成形模具由於內部傷痕的發生、及成形模具內部表面的電鍍處理面的脫落或表面狀態的龜裂,而會產生密封成形作業時的成形性及脫模性的降低、或表面外觀不良。因此,進而發生成形模具內的清理作業性損失之不良情況。本發明的模具清理用樹脂組成物經由適當地選擇球形(包含略球形)的無機填充材的最大粒徑,可抑制清理時的成形模具內的傷痕。 The resin composition for mold cleaning of the present invention is suitably used for removing dirt in a molding die in a sealing molding operation such as an integrated circuit. The material of the molding die may, for example, be iron or chromium. The forming mold is generally subjected to electroplating treatment. Through the repeated sealing forming operation and the surface cleaning operation inside the forming mold, micron-sized scratches are generated in the forming mold, and the mold is worn. Due to such occurrence of scratches or abrasions, peeling of the plated surface or cracking of the surface state occurs in the molding die. In the molding die, the occurrence of internal flaws and the peeling of the plated surface of the inner surface of the molding die or the cracking of the surface state cause a decrease in moldability and mold release property at the time of the sealing molding operation or a poor surface appearance. Therefore, the problem of the cleaning workability loss in the forming mold is further caused. The resin composition for mold cleaning of the present invention can suppress the flaw in the molding die at the time of cleaning by appropriately selecting the maximum particle diameter of the spherical filler (including a substantially spherical shape).
以下,列舉實施例及比較例來對本發明進一步地詳細說明。此外,本發明並不受限於此等實施例。 Hereinafter, the present invention will be further described in detail by way of examples and comparative examples. Further, the invention is not limited to the embodiments.
將作為三聚氰胺系樹脂之以眾所週知的方法加熱反應後經減壓乾燥者粉末化所製作之三聚氰胺-苯酚共縮合物21.3質量份及三聚氰胺樹脂50質量份、作為無機填充材之非晶質的球形氧化矽(製品名:S440-4、新日鐵住金材料股份有限公司MICRON公司(新日鐵材料股份有限公司MICRON公司)製的無機填充材)20質量份、作為有機填充材之闊葉樹紙漿7.8質量份、作為飽和脂肪酸與金屬的鹽之肉荳蔻酸鋅0.5質量份、作為硬化觸媒之肉荳蔻酸0.05質量份,加入球磨機後予以粉碎。然後,於圓錐形混合機(Nauta Mixer)加入0.35質量份作為滑劑之硬脂醯胺。如此,以製作模具清理用樹脂組成物。 21.3 parts by mass of a melamine-phenol cocondensate and 50 parts by mass of a melamine resin produced by pulverizing a melamine resin by a well-known method and then pulverized by a vacuum drying, amorphous spherical oxidation as an inorganic filler制品 (product name: S440-4, inorganic filler material manufactured by MICRON Co., Ltd. (Nippon Steel Co., Ltd. MICRON)), 20 parts by mass, 7.8 parts by mass of broadleaf pulp as organic filler 0.5 parts by mass of zinc myristate as a salt of a saturated fatty acid and a metal, and 0.05 parts by mass of myristic acid as a curing catalyst were added to a ball mill and then pulverized. Then, 0.35 parts by mass of stearic acid amine as a slip agent was added to a conical mixer (Nauta Mixer). In this way, a resin composition for mold cleaning is produced.
以電子顯微鏡觀察無機填充材,S440-4粒徑的平均縱橫比為1.16(球形)。又,用於實施例的後述任意其他無機填充材的粒徑的平均縱橫比亦均為1~1.5範圍的球形。 The inorganic filler was observed under an electron microscope, and the average aspect ratio of the S440-4 particle diameter was 1.16 (spherical). Moreover, the average aspect ratio of the particle diameter of any other inorganic filler used later in the examples is also a spherical shape in the range of 1 to 1.5.
下述表1中,彙整顯示於實施例1所製作之模具清理用樹脂組成物的組成及量(質量份)、無機填充材的平均粒徑、最大粒徑、及平均縱橫比。 In the following Table 1, the composition and amount (parts by mass) of the resin composition for mold cleaning produced in Example 1, the average particle diameter of the inorganic filler, the maximum particle diameter, and the average aspect ratio are shown.
此外,無機填充材的粒徑的標準偏差為7μm,無機填充材之縱橫比的標準偏差為0.23。 Further, the standard deviation of the particle diameter of the inorganic filler was 7 μm, and the standard deviation of the aspect ratio of the inorganic filler was 0.23.
又,對於所製作之模具清理用樹脂組成物,利用以下所示之試驗方法評價其清理性。此外,所製作之模具清理用樹脂組成物為轉移類型。 Moreover, the cleanability of the resin composition for mold cleaning produced was evaluated by the following test method. Further, the resin composition for mold cleaning produced was of a transfer type.
準備使用QFP(Quad Flat Package,四面扁平封裝)模具的自動成形機,使用係市售環氧樹脂成形材料之EME-G700L(住友電木股份有限公司製),於模具溫度175℃進行400次射出的成形,使在成形模具內部的表面出現污垢。使用該模具,經由將上述所製作之模具清理用樹脂組成物重複成形直至其內部表面的污垢能被除去,以進行清理作業。模具清理用樹脂組成物的重複成形係將模具溫度設成與環氧樹脂成形材料成形時同樣的175℃而進行。 An automatic molding machine using a QFP (Quad Flat Package) mold was used, and EME-G700L (manufactured by Sumitomo Bakelite Co., Ltd.), which is a commercially available epoxy resin molding material, was used to perform 400 shots at a mold temperature of 175 ° C. Forming causes dirt to appear on the surface inside the forming mold. Using the mold, the resin composition for mold cleaning prepared above is repeatedly molded until the dirt on the inner surface thereof can be removed to perform the cleaning operation. The repetitive molding of the resin composition for mold cleaning was carried out at a temperature of 175 ° C which was the same as that at the time of molding the epoxy resin molding material.
此外,於評價所使用之模具空腔的澆口部分其寬度為800μm,高度為300μm。此外,該模具空腔的澆口部分其最狹窄的部位為100μm。 Further, the gate portion of the mold cavity used for evaluation was 800 μm in width and 300 μm in height. Further, the gate portion of the mold cavity has a narrowest portion of 100 μm.
清理性的評價係特別注重是否能清理至模具空腔的澆口部分或角隅部,藉由判定模具空腔的角隅部污垢的除去性、與清理模具空腔的澆口部分及角隅部之必要射出數而進行。清理性係射出數越小越優異。表1係彙整各實施例及比較例的評價結果。 The clean evaluation is particularly focused on whether it can be cleaned to the gate portion or the corner portion of the mold cavity, by determining the removal of the dirt at the corner of the mold cavity, and the gate portion and corner of the cavity of the cleaning mold. It is necessary to shoot the number of parts. The smaller the cleaning system, the better the number of shots. Table 1 summarizes the evaluation results of the respective examples and comparative examples.
角隅部污垢的除去性係利用目視來確認在模具空腔的角隅部中有無污垢並加以評價。評價係將模具清理用樹脂組成物能良好地通過模具空腔的澆口部分、沒有污垢或污垢少而良好者判定為「A」,有污垢殘存、於成形時引起不良情況者判定為「B」。 The removal of the corners of the corners was visually confirmed by the presence or absence of dirt in the corners of the cavity of the mold. In the evaluation, the resin composition for mold cleaning can be satisfactorily passed through the gate portion of the mold cavity, and there is no dirt or dirt, and it is judged as "A". If the dirt remains and the defect occurs during molding, it is judged as "B". "."
又,清理直至模具空腔的澆口部分或角隅部的必要射出數的評價,結束射出數為10次以下之情況係記錄射出數,清理10次也無法除去污垢之情況則判定為「NG」。 In addition, the number of shots required to be cleaned up to the gate portion or the corner portion of the mold cavity is evaluated, and when the number of shots is 10 or less, the number of shots is counted, and if the number of shots is not removed 10 times, the stain is judged as "NG". "."
除了將實施例1中作為硬化觸媒所使用的肉荳蔻酸取代為硬脂酸以外,與實施例1同樣地製作模具清理用樹脂組成物,並評價清理性。評價結果表示於表1。 A resin composition for mold cleaning was prepared in the same manner as in Example 1 except that the myristic acid used as the curing catalyst in Example 1 was replaced with stearic acid, and the cleanability was evaluated. The evaluation results are shown in Table 1.
除了將實施例1中的無機填充材變更為下述表1所示者以外,與實施例1同樣地製作模具清理用樹脂組成物,並評價清理性。評價結果表示於表1。 A resin composition for mold cleaning was prepared in the same manner as in Example 1 except that the inorganic filler in the first embodiment was changed to the one shown in the following Table 1, and the cleanability was evaluated. The evaluation results are shown in Table 1.
除了使用苯甲酸作為實施例1中的硬化觸媒以外,與實施例1同樣地製作模具清理用樹脂組成物,並評價清理性。評價結果表示於表1。 A resin composition for mold cleaning was prepared in the same manner as in Example 1 except that benzoic acid was used as the curing catalyst in Example 1, and the cleanability was evaluated. The evaluation results are shown in Table 1.
除了使用硬脂酸鋅作為實施例1中的飽和脂肪酸與金屬的鹽以外,與實施例1同樣地製作模具清理用樹脂組成物,並評價清理性。評價結果表示於表1。 A resin composition for mold cleaning was prepared in the same manner as in Example 1 except that zinc stearate was used as the salt of the saturated fatty acid and the metal in Example 1, and the cleanability was evaluated. The evaluation results are shown in Table 1.
除了使用山森土木礦業所股份有限公司製的結晶質氧化矽(製品名:R-1)作為實施例1中的無機填充材以外,與實施例1同樣地製作模具清理用樹脂組成物,並評價清理性。評價結果表示於表1。 A resin composition for mold cleaning was prepared and evaluated in the same manner as in Example 1 except that the crystalline cerium oxide (product name: R-1) manufactured by Yamamoto Engineering Co., Ltd. was used as the inorganic filler in Example 1. Clean up. The evaluation results are shown in Table 1.
此外,比較例3所使用的無機填充材具有表1所示之粒徑及縱橫比,又該無機填充材的形狀經使用電子顯微鏡確認後為不定形。 Further, the inorganic filler used in Comparative Example 3 had the particle diameter and the aspect ratio shown in Table 1, and the shape of the inorganic filler was confirmed to be amorphous after confirmation using an electron microscope.
除了使用瀨戸窯業原料股份有限公司製的結晶質氧化矽(製品名:純矽石粉)作為實施例1中的無機填充材以外,與實施例1同樣地製作模具清理用樹脂組成物,並評價清理性。評價結果表示於表1。 A resin composition for mold cleaning was prepared and evaluated in the same manner as in Example 1 except that the crystalline cerium oxide (product name: pure vermiculite powder) manufactured by Kawasaki Materials Co., Ltd. was used as the inorganic filler in Example 1. Clean up. The evaluation results are shown in Table 1.
此外,於比較例4所使用之無機填充材具有表1所示之粒徑及縱橫比。 Further, the inorganic filler used in Comparative Example 4 had the particle diameter and the aspect ratio shown in Table 1.
除了將實施例1中的無機填充材變更為下述表1所者以外,與實施例1同樣地製作模具清理用樹脂組成物,並評價清理性。評價結果表示於表1。 A resin composition for mold cleaning was prepared in the same manner as in Example 1 except that the inorganic filler in the first embodiment was changed to the following Table 1, and the cleanability was evaluated. The evaluation results are shown in Table 1.
表1中的無機填充材的詳細內容係如下所述。 The details of the inorganic filler in Table 1 are as follows.
.S440-4:新日鐵住金材料股份有限公司MICRON公司(新日鐵材料股份有限公司MICRON公司)製的非晶質球形氧化矽 . S440-4: Amorphous spherical cerium oxide produced by MICRON Corporation (Nippon Steel Materials Co., Ltd. MICRON) of Nippon Steel & Sumitomo Metal Materials Co., Ltd.
.HS-202:新日鐵住金材料股份有限公司MICRON公司(新日鐵材料股份有限公司MICRON公司)製的非晶質球形氧化矽 . HS-202: Amorphous spherical cerium oxide produced by MICRON Corporation (Nippon Steel Materials Co., Ltd. MICRON Corporation) of Nippon Steel & Sumitomo Metal Materials Co., Ltd.
.R-1:山森土木礦業所股份有限公司製的結晶質氧化矽 . R-1: Crystalline bismuth oxide produced by Shansen Civil Engineering Co., Ltd.
.HS-302:新日鐵住金材料股份有限公司MICRON公司(新日鐵材料股份有限公司MICRON公司)製的非晶質球形氧化矽 . HS-302: Amorphous spherical cerium oxide produced by MICRON Corporation (Nippon Steel Materials Co., Ltd. MICRON) of Nippon Steel & Sumitomo Metal Materials Co., Ltd.
.UF-320:股份有限公司Tokuyama製的非晶質球形氧化矽 . UF-320: Amorphous spherical cerium oxide produced by Tokuyama Co., Ltd.
.HS-204:新日鐵住金材料股份有限公司MICRON公司(新日鐵材料股份有限公司MICRON公司)製的非晶質球形氧化矽 . HS-204: Amorphous spherical cerium oxide manufactured by New Japan Railway Materials Co., Ltd. MICRON (Nippon Steel Materials Co., Ltd. MICRON)
.純矽石粉:瀨戸窯業原料股份有限公司製的結晶質氧化矽 . Pure vermiculite powder: crystalline cerium oxide produced by Hao Kiln Raw Materials Co., Ltd.
如前述表1所示,本發明的模具清理用樹脂組成物能良好地清理直至細緻化之模具空腔的角隅部,且能改善污垢的除去性能。 As shown in the above Table 1, the resin composition for mold cleaning of the present invention can be cleaned well until the corner portion of the finished mold cavity, and the dirt removal performance can be improved.
又,如表1所示,實施例1~5的模具清理用樹脂組成物由於分別包含三聚氰胺系樹脂、球形且最大粒徑為1μm~70μm的無機填充材、作為硬化觸媒之肉荳蔻酸或硬脂酸、及作為飽和脂肪酸與金屬的鹽之肉荳蔻酸鋅,所以對於在澆口部分最狹窄的部位為100μm的模具,能良好地清理直至角隅部,且顯示清理結束射出數以4次即能完成之優異的污垢除去性能。此外,觀察清理後的模具表面,實施例1~5的模具清理用樹脂組成物並不會弄傷模具表面。 In addition, as shown in Table 1, the resin composition for mold cleaning of Examples 1 to 5 each contains a melamine-based resin, an inorganic filler having a spherical shape and a maximum particle diameter of 1 μm to 70 μm, or myristic acid as a hardening catalyst. Stearic acid, and zinc myristic acid, which is a salt of a saturated fatty acid and a metal, can be cleaned up to the corners of the mold at a position where the narrowest part of the gate is 100 μm, and the number of shots is 4 Excellent dirt removal performance that can be completed in a second time. Further, the surface of the mold after cleaning was observed, and the resin composition for mold cleaning of Examples 1 to 5 did not damage the surface of the mold.
另一方面,比較例1的模具清理用樹脂組成物由於含有作為硬化觸媒之苯甲酸,故模具清理用樹脂組成物的流動過度,且清理結束射出數變多。因而,污垢的除去性能比實施例1差。 On the other hand, since the resin composition for mold cleaning of Comparative Example 1 contains benzoic acid as a curing catalyst, the flow of the resin composition for mold cleaning is excessive, and the number of shots at the end of cleaning is increased. Thus, the dirt removal performance was inferior to that of Example 1.
比較例2的模具清理用樹脂組成物中由於含有作為飽和脂肪酸與金屬 的鹽之硬脂酸鋅,故模具清理用樹脂組成物的流動過度,且清理結束射出數變多。因而,污垢的除去性能比實施例1差。 The resin composition for mold cleaning of Comparative Example 2 contains as a saturated fatty acid and metal The zinc stearate of the salt is excessively flowed by the resin composition for mold cleaning, and the number of shots at the end of the cleaning is increased. Thus, the dirt removal performance was inferior to that of Example 1.
比較例3的模具清理用樹脂組成物由於無機填充材的最大粒徑為352μm且為不定形,所以無法清理模具空腔的角隅部,而且模具的污垢除去性能也較差。 In the resin composition for mold cleaning of Comparative Example 3, since the maximum particle diameter of the inorganic filler was 352 μm and it was amorphous, the corner portion of the mold cavity could not be cleaned, and the mold removal performance of the mold was also inferior.
比較例4的模具清理用樹脂組成物由於無機填充材的最大粒徑為100μm,所以雖然模具清理用樹脂組成物的流動適當,但模具空腔的角隅部的清理困難。又,模具的污垢的除去性能也較差。 In the resin composition for mold cleaning of Comparative Example 4, since the maximum particle diameter of the inorganic filler is 100 μm, the flow of the resin composition for mold cleaning is appropriate, but the cleaning of the corner portion of the mold cavity is difficult. Moreover, the dirt removal performance of the mold is also poor.
比較例5的模具清理用樹脂組成物從無機填充材的最大粒徑為75μm且粒子彼此容易堵塞於空腔部之傾向而觀之,無法確保良好的流動性,且無法良好地清理模具空腔的角隅部。因而,模具的污垢的除去性能也較差。 The resin composition for mold cleaning of Comparative Example 5 was observed from the tendency that the maximum particle diameter of the inorganic filler was 75 μm and the particles were easily clogged with the cavity portion, and good fluidity could not be ensured, and the mold cavity could not be cleaned well. The corner of the horn. Therefore, the dirt removal performance of the mold is also poor.
如以上之實施例及比較例所示,發現:於無機填充材的最大粒徑為1μm~70μm之情況,藉由適當地選擇硬化觸媒及飽和脂肪酸與金屬的鹽,可控制利用模具清理用樹脂組成物清理時的流動,且得到直至細緻化之模具空腔的角隅部的良好清理效果。又,模具清理用樹脂組成物適當地停留於模具內,模具內的污垢除去性能亦能獲得改善。 As shown in the above examples and comparative examples, it has been found that when the maximum particle diameter of the inorganic filler is from 1 μm to 70 μm, it is possible to control the use of the mold cleaning by appropriately selecting the hardening catalyst and the salt of the saturated fatty acid and the metal. The flow of the resin composition at the time of cleaning, and a good cleaning effect of the corner portion of the mold cavity until the fineness is obtained. Further, the resin composition for mold cleaning is appropriately retained in the mold, and the dirt removal performance in the mold can be improved.
本發明的模具清理用樹脂組成物為用於去除自熱硬化性樹脂組成物由來的模具表面污垢的模具清理用樹脂組成物,且能適當地使用於轉移型成形機的轉移成形。 The resin composition for mold cleaning of the present invention is a resin composition for mold cleaning for removing dirt on the surface of a mold from the thermosetting resin composition, and can be suitably used for transfer molding of a transfer molding machine.
參照日本專利申請2012-011544的揭示全體並將其併入本說明書。 The entire disclosure of Japanese Patent Application No. 2012-011544 is incorporated herein by reference.
本說明書中所記載的全部文獻、專利申請、及技術規格,係將各個文獻、專利申請、及技術規格所參照引用者以具體且與各個記述的情況相同的程度,參照而併入本說明書中。 All the documents, patent applications, and technical specifications described in the specification are incorporated herein by reference to the same extent as the same as the description of each of the documents, patent applications, and technical specifications. .
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JP (1) | JP5991997B2 (en) |
KR (1) | KR102019456B1 (en) |
CN (1) | CN104066563B (en) |
MY (1) | MY170065A (en) |
PH (1) | PH12014501669A1 (en) |
SG (1) | SG11201404265PA (en) |
TW (1) | TWI551417B (en) |
WO (1) | WO2013111709A1 (en) |
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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 |
JP2017177623A (en) * | 2016-03-31 | 2017-10-05 | 日本カーバイド工業株式会社 | Resin composition for cleaning die |
JP2020001336A (en) * | 2018-06-29 | 2020-01-09 | Toyo Tire株式会社 | Vent sleeve for tire vulcanization mold and tire vulcanization mold |
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CN1073499C (en) * | 1994-08-24 | 2001-10-24 | 日本电石工业株式会社 | Amino resin composition for mold cleaning |
JP2002160225A (en) * | 2000-11-28 | 2002-06-04 | Sumitomo Bakelite Co Ltd | Mold cleaning material for sealing semiconductor |
TW537956B (en) * | 2000-10-11 | 2003-06-21 | Nippon Carbide Kogyo Kk | Mold cleaning resin composition |
TWI223657B (en) * | 2000-10-18 | 2004-11-11 | Chang Chun Plastics Co Ltd | Amino resin composition for the cleaning of the mold |
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SG30613G (en) | 1989-05-15 | 1995-09-01 | Du Pont | Process for molding target electrode used in the application of electrostatic charge to a fibrous structure |
JP3809781B2 (en) | 2001-08-28 | 2006-08-16 | 松下電工株式会社 | Mold cleaning resin composition and transfer press mold cleaning molding material |
JP4781908B2 (en) * | 2006-05-24 | 2011-09-28 | 日本ユニカー株式会社 | Resin composition for cleaning plastic molding machines |
KR101395818B1 (en) * | 2006-10-27 | 2014-05-16 | 닛뽕 카바이도 고교 가부시키가이샤 | Resin composition for cleaning molds and recovering the release properties of molds and method for cleaning molds and recovering the release properties of molds |
WO2013011876A1 (en) * | 2011-07-15 | 2013-01-24 | 日本カーバイド工業株式会社 | Mold-cleaning resin composition |
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- 2013-01-21 WO PCT/JP2013/051107 patent/WO2013111709A1/en active Application Filing
- 2013-01-21 JP JP2013555249A patent/JP5991997B2/en active Active
- 2013-01-21 KR KR1020147019489A patent/KR102019456B1/en active IP Right Grant
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- 2013-01-21 MY MYPI2014701951A patent/MY170065A/en unknown
- 2013-01-22 TW TW102102381A patent/TWI551417B/en active
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Patent Citations (4)
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CN1073499C (en) * | 1994-08-24 | 2001-10-24 | 日本电石工业株式会社 | Amino resin composition for mold cleaning |
TW537956B (en) * | 2000-10-11 | 2003-06-21 | Nippon Carbide Kogyo Kk | Mold cleaning resin composition |
TWI223657B (en) * | 2000-10-18 | 2004-11-11 | Chang Chun Plastics Co Ltd | Amino resin composition for the cleaning of the mold |
JP2002160225A (en) * | 2000-11-28 | 2002-06-04 | Sumitomo Bakelite Co Ltd | Mold cleaning material for sealing semiconductor |
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JPWO2013111709A1 (en) | 2015-05-11 |
JP5991997B2 (en) | 2016-09-14 |
MY170065A (en) | 2019-07-02 |
CN104066563B (en) | 2016-12-14 |
KR102019456B1 (en) | 2019-09-06 |
WO2013111709A1 (en) | 2013-08-01 |
SG11201404265PA (en) | 2014-10-30 |
TW201341146A (en) | 2013-10-16 |
PH12014501669B1 (en) | 2014-10-20 |
KR20140117405A (en) | 2014-10-07 |
CN104066563A (en) | 2014-09-24 |
PH12014501669A1 (en) | 2014-10-20 |
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