TWI373521B - Mold cleaning composition - Google Patents
Mold cleaning composition Download PDFInfo
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- TWI373521B TWI373521B TW096118800A TW96118800A TWI373521B TW I373521 B TWI373521 B TW I373521B TW 096118800 A TW096118800 A TW 096118800A TW 96118800 A TW96118800 A TW 96118800A TW I373521 B TWI373521 B TW I373521B
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/263—Ethers
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3218—Alkanolamines or alkanolimines
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Description
丄373521 九、發明說明: 【發明所屬之技術領域】 本發明係關於-種模具清潔組成物,其為—種用於模具 清潔、更新及其類似工作的模具清潔材料,該等模豆諸: 用於熱塑性樹脂組成物成形材料,已被重複模製工作污染 之模具,特定言之,該模具清潔材料係用於供轉注成形之 模具的模具清潔、更新及其類似工作,該等模具係用於藉 由使用環氧樹脂成形材料進行轉注成形來模製半導體元件 的模製工作》 【先前技術】 對於習知的模具清潔方法,已知藉由將模具自模製裝置 拆卸下來進行模具清潔工作的方法,諸如喷砂法、喷乾冰 法、喷水法及強鹼清潔法。然而,在藉由將模具自模製裝 置拆卸下來進行模具清潔工作的情況下,該工作需要長工 作時間且需要大量勞動。因此,愈來愈多地使用在模具安 裝於模製裝置上的情況下進行清潔工作的方法,且使用三 聚氰胺樹脂的清潔方法、使用紫外線照射的清潔方法、使 用片狀清潔組成物的清潔方法及類似方法已作為該清潔方 法進行。其中’已進行藉由使置放於模具中之片狀清潔組 成物熱固化及移除固化之片狀清潔組成物以將污染物轉移 至該固化之片狀清潔組成物上來自模具中移除污染物的模 具清潔方法,由於該方法具有優良的工作效率。 對於該片狀清潔組成物,可提及例如使用未硫化橡膠之 模具清潔組成物(參見專利文獻丨)。又’可提及片狀基本材 121307.doc 1373521 料經可經成形用於清潔的化合物塗覆之模具清潔材料(參 見專利文獻2)。 少 專利文獻 1 : JP-A-9-262843 專利文獻2: JP-T-63-502497 【發明内容】 然而,使用片狀清潔組成物且將污染物轉移至該片狀清 潔組成物上以移除污染物的模具清潔方法存在一個問題: • 視模具之腔的形狀及尺寸而定,在模製過程中空氣包含在 腔中’且空氣在腔的角落處積累導致片狀清潔組成物無法 填充在角落_的狀況,從而導致不能充分移除污染物。舉 例而言,就jp-A-9-262843中所揭示之模具清潔組成物而 3 ,必需在夾緊過程中藉由略微打開上下模具以留出約工 mm至1.5 mm的間隙,以防止橡膠片在模具中熱硫化之後 在移除橡膠片的過程中將橡膠片切斷,且防止橡膠片殘留 在模具中。然而’在具有小尺寸及大深度之模具腔的腔 • 中,空氣陷於腔角落,導致形成未填充部分。因此,產生 未填充部分處之污染物未充分移除的問題。同樣,就jp_T_ 502497中所揭示之模具清潔材料而言由於腔的整個 、 表面均被覆蓋,陷入空氣無法自腔中溢出從而形成未填充 部分,導致未填充部分處之污染物未充分移除的問題。 因此由於不適合在面臨上述問題的模具中使用片狀清 潔組成物’故對於該等模具採用不同於使用片狀清潔組成 物的清潔方法。然而,如上所述,其他清潔方法需要較長 時間’且大量勞動實際上難以負擔。 121307.doc 1373521 鑒於上述情況而實現本發明,且本發明之目的在於提供 -種具有優良模具填充性能且在模具中實現優良污染物清 . 潔效果的模具清潔組成物。 【實施方式】 • 為實現上述目的,本發明之模具清潔組成物為—種用於 • #反覆熱成形用以模製成形材料之模具的清潔組成物,其 含有作為基本成份之未硫化橡膠、清潔劑及硫化劑,根據 由凝膠滲透層析法(GPC)的量測,該清潔組成物整體且 有設在2〇〇,0〇〇至460,000之範圍内的重量平均分子量 (Mw) 〇 本發明之發明者已進行了深人研究以獲得—種在使用模 具清潔組成物進行模具清潔工作過程中能夠藉由防止形成 另外由產生空氣陷入所致的未填充部分而令人滿意地填充 於模具腔之每-部分中,以及能夠有效移除模具腔中之污 染物的清潔!且成物。發明者注重對模具腔的填充性能且主 _ 要對在將清潔組成物填充於模具腔中的過程中能夠將空氣 陷入降至最低之清潔組成物的流動性進行了一系列研究。 更具體言之,為增強對模具腔的填充性能,必需獲得在填 -. 《清潔組成物的過程中能夠將空氣陷入降至最低的流動狀 , 態,以及必需減小模製過程中的模具間隙以提高模具腔的 内壓。詳S之’就對模具腔之配合性能的角度而言,清潔 組成物可較佳具有低黏度,但黏度過低時,模製過程中模 具腔之内壓降低而無法播出陷入空氣,從而導致形成未填 充口P刀另一方面,當清潔組成物黏度過高時,對模具腔 121307.doc 1373521 的配合性能變差,從而導致容易形成未填充部分。基於上 述發現,發明者進行了進一步研究以獲得具有適當黏度之 清潔組成物,且發現根據藉由凝膠滲透層析法(GPC)的量 測,重量平均分子量(Mw)在上述指定範圍内的清潔組成物 能夠具有適當黏度及良好的填充性能,藉此實現本發明。 亦即’本發明係關於以下各項。丄 373521 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a mold cleaning composition, which is a mold cleaning material for mold cleaning, renewal, and the like, and the mold beans are: A mold for a thermoplastic resin composition forming material which has been repeatedly contaminated by a molding work, in particular, the mold cleaning material is used for mold cleaning, updating, and the like of a mold for transfer molding, and the mold is used for the mold. Molding work for molding a semiconductor element by transfer molding using an epoxy resin molding material [Prior Art] For a conventional mold cleaning method, it is known to perform mold cleaning work by detaching a mold from a molding apparatus. Methods such as sand blasting, spray drying, water spray and strong alkali cleaning. However, in the case where the mold is cleaned by detaching the mold from the molding apparatus, the work requires a long working time and requires a lot of labor. Therefore, more and more methods for performing cleaning work in the case where the mold is mounted on the molding apparatus, a cleaning method using melamine resin, a cleaning method using ultraviolet irradiation, a cleaning method using a sheet-like cleaning composition, and the like are increasingly used. A similar method has been carried out as the cleaning method. Where 'has been performed by thermally curing the sheet-like cleaning composition placed in the mold and removing the cured sheet-like cleaning composition to transfer contaminants to the cured sheet-like cleaning composition from the mold. The mold cleaning method for contaminants has excellent working efficiency due to the method. For the sheet-like cleaning composition, for example, a mold cleaning composition using an unvulcanized rubber can be mentioned (see Patent Document 丨). Further, a sheet-like base material can be mentioned. 121307.doc 1373521 A mold-cleaning material coated with a compound which can be shaped for cleaning (see Patent Document 2). Patent Document 1: JP-A-9-262843 Patent Document 2: JP-T-63-502497 SUMMARY OF THE INVENTION However, a sheet-like cleaning composition is used and contaminants are transferred to the sheet-like cleaning composition to be moved. There is a problem with mold cleaning methods other than contaminants: • Depending on the shape and size of the cavity of the mold, air is contained in the cavity during the molding process and air accumulates at the corners of the cavity, causing the sheet-like cleaning composition to fail to fill. In the corner _ condition, resulting in insufficient removal of contaminants. For example, with respect to the mold cleaning composition disclosed in jp-A-9-262843, it is necessary to leave the upper and lower molds slightly during the clamping process to leave a gap of about mm to 1.5 mm to prevent rubber. After the sheet is thermally vulcanized in the mold, the rubber sheet is cut during the process of removing the rubber sheet, and the rubber sheet is prevented from remaining in the mold. However, in a cavity having a mold cavity of a small size and a large depth, air is trapped in the corner of the cavity, resulting in the formation of an unfilled portion. Therefore, there is a problem that the contaminants at the unfilled portion are not sufficiently removed. Similarly, in the case of the mold cleaning material disclosed in jp_T_502497, since the entire surface of the cavity is covered, the trapped air cannot overflow from the cavity to form an unfilled portion, resulting in insufficient removal of contaminants at the unfilled portion. problem. Therefore, since it is not suitable to use the sheet-like cleaning composition in the mold facing the above problems, a cleaning method different from the use of the sheet-like cleaning composition is employed for the molds. However, as described above, other cleaning methods take a long time' and a large amount of labor is actually unaffordable. 121307.doc 1373521 The present invention has been achieved in view of the above circumstances, and an object of the present invention is to provide a mold cleaning composition which has excellent mold filling properties and achieves an excellent contaminant cleaning effect in a mold. [Embodiment] In order to achieve the above object, the mold cleaning composition of the present invention is a cleaning composition for a mold which is used for molding a molding material, which contains an unvulcanized rubber as a basic component, and is cleaned. And a vulcanizing agent according to the measurement by gel permeation chromatography (GPC), the cleaning composition as a whole and having a weight average molecular weight (Mw) 设 in the range of 2 〇〇, 0 〇〇 to 460,000 The inventors of the present invention have conducted intensive studies to obtain a satisfactory filling of the mold in the mold cleaning operation using the mold cleaning composition by preventing the formation of an unfilled portion which is additionally caused by air trapping. Each part of the cavity, as well as the cleaning that effectively removes contaminants in the mold cavity! The inventors focused on the filling performance of the mold cavity and conducted a series of studies on the fluidity of the cleaning composition capable of minimizing air trapping during the process of filling the cleaning composition into the mold cavity. More specifically, in order to enhance the filling performance of the mold cavity, it is necessary to obtain a flow in which the air can be minimized during the process of cleaning the composition, and it is necessary to reduce the mold during the molding process. The gap is to increase the internal pressure of the mold cavity. In view of the matching performance of the mold cavity, the cleaning composition may preferably have a low viscosity, but when the viscosity is too low, the internal pressure of the mold cavity is lowered during the molding process, and the air may not be trapped. This results in the formation of an unfilled port P. On the other hand, when the viscosity of the cleaning composition is too high, the fitting property to the mold cavity 121307.doc 1373521 is deteriorated, resulting in easy formation of an unfilled portion. Based on the above findings, the inventors conducted further studies to obtain a cleaning composition having an appropriate viscosity, and found that the weight average molecular weight (Mw) was within the above specified range according to the measurement by gel permeation chromatography (GPC). The cleaning composition can have an appropriate viscosity and good filling properties, thereby realizing the present invention. That is, the present invention relates to the following items.
(1) 一種模具清潔組成物,其包含未硫化橡膠、清潔劑 及硫化劑,其中根據藉由凝膠滲透層析法(Gpc)的量測, 該清潔組成物整體具有在200,000至460,000之範圍内的重 量平均分子量(Mw)。 (2) 如(1)之模具清潔組成物,其中根據藉由凝膠滲透層 析法(GPC)的量測,清潔組成物整體具有在22〇 〇〇〇至 43 0,000之範圍内的重量平均分子量(mw) β (3) 如(1)或(2)之模具清潔組成物,其形狀為片狀或帶 狀。(1) A mold cleaning composition comprising an unvulcanized rubber, a detergent, and a vulcanizing agent, wherein the cleaning composition as a whole has a range of 200,000 to 460,000 according to a measurement by gel permeation chromatography (Gpc) Weight average molecular weight (Mw). (2) The mold cleaning composition according to (1), wherein the cleaning composition as a whole has a weight average in the range of 22 〇〇〇〇 to 43 0,000 according to the measurement by gel permeation chromatography (GPC). Molecular weight (mw) β (3) The mold cleaning composition of (1) or (2), which is in the form of a sheet or a belt.
(4) 如(1)至(3)中任一項之模具清潔組成物,其中該清潔 劑為選自由下列各物組成之群之至少一員:二醇醚、咪 嗤、咪唑淋及胺基醇。 (5) 如(1)至(4)中任一項之模具清潔組成物,其中該清潔 劑之含量相對於100重量份的未硫化橡膠為1〇至6〇重量 份。 (6) 如(1)至(5)中任一項之模具清潔組成物,其進一步包 含1重量%至20重量%量之水。 ⑺如⑴至(6)中任-項之模具清潔組成物,其進一步包 121307.doc 含脫模劑》 W如⑴至(7)t任-項之模具清潔組成物,彡中該模且 物之㈣為其中複數個線性缝隙在-個方 向上以肢間距且彼此平行設置於其片表面上。 J9)如(8)之模具清潔組成物,#中該等縫隙經設置以使 得該片狀模具清潔組成物能夠折疊。 ⑽如(8)之模具清潔組成物,#中該等缝隙經設置以使 得該片狀模具清潔組成物能夠沿該等缝隙切割。 (11)如(1U(1G)中任_項之模具清潔組成物其為用於 供反覆熱成形用以模製成形材料之模具的清潔組成物。 如上所述’本發明之模具清潔組成物含有未硫化橡膠、 清潔劑及硫化劑作為基本成份,且根據藉由凝膠滲透層析 法(^)的量測’作為—整體’其重量平均分子量(Mw)係 在扣疋範圍内。因& ’該清潔組成物具有適當黏度且實現 優良的填充於模具中之性能。以,當藉由使用本發明之 模具清潔組成物來清潔模具表面時,模具腔經模具清潔組 成物均句填充以使得模具表面上之污染物黏附於該模具清 潔組成物上,藉此有效地將污染物與模具清潔組成物自模 具整體式移除◎舉例而言,將用於模製半導體元件之轉注 成形之模具(其已反覆用於使用環氧樹脂組成物進行的模 製中)表面上的污染物組合於待自該模具有效移除之由該 模具清潔組成物製得的模製物品中,藉此可有效進行模具 清潔。因此’#由使用經本發明之模具清潔組成物清潔的 模具形成的半導體器件具有優良外觀。 121307.doc 1373521 在模具清潔組成物呈片狀或帶狀的情況下,可能容易地 定位該模具清潔組成物以清潔模具腔。 . 此外,藉由使用二醇醚、咪唑、咪唑啉或胺基醇作為清 . 潔劑可能獲得優良的模具清潔效果。 當模具清潔組成物含有1重量。/。至2〇重量%量之水時,可 能獲得更優良的清潔性能。 當模具清潔組成物經模製以呈片狀且於其片表面上具有 _ 複數個設置於一個方向上的線性縫隙時,藉由沿該等缝隙 折疊該片可能容易地將其堆疊。在此情況下,由於由平行 缝隙分割開的各別塊狀片段在該等缝隙以下的部分處彼此 連接,因此可將該片整齊地堆疊而在折疊過程中無需移 置,且各別塊狀片段在堆疊時不相交或出現類似現象。因 此,所得堆疊形狀規則。藉由使用整齊堆疊之片狀清潔組 成物來清潔模具,可能消除另外由(例如)未硫化橡膠與模 具表面之間壓力接觸不足所引起的清潔缺陷。此外,由於 _ 不必量測該片之尺寸以將該片切割成相同尺寸的片段,且 不必進行將所切片段對齊的複雜工作用於堆疊,因此可能 簡化清潔工作。 -· 此外’當模具清潔組成物呈片狀,且尤其在其片表面上 • 具有複數個設置於一個方向上的線性縫隙以便沿該等縫隙 切割片狀模具清潔組成物時,可能容易地切割該片以配合 規則的較小模具尺寸。 以下將描述本發明之實施例。 本發明之模具清潔組成物整體具有特定重量平均分子量 121307.doc 1373521 二稀或其混合物。丁二烯橡膠之摩尼黏度(Mooney viSC〇Sity)ML1+4(i〇〇t)可為 20 至 80,更佳為 35 至 60。較佳 使用重量平均分子量(Mw)為200,000至60〇,〇〇〇,更佳為 400,000 至 6〇〇,000 的 丁二烯橡膠。 清潔劑的實例包括二醇醚、咪唑、咪唑啉及胺基醇。該 等清潔劑可單獨使用或其中之二或多者組合使用。 上述二醇醚為下式(丨)所示之化合物:(4) The mold cleaning composition according to any one of (1) to (3), wherein the cleaning agent is at least one member selected from the group consisting of glycol ether, imipenem, imidazole, and amine group. alcohol. (5) The mold cleaning composition according to any one of (1) to (4), wherein the detergent is contained in an amount of from 1 to 6 parts by weight based on 100 parts by weight of the unvulcanized rubber. (6) The mold cleaning composition according to any one of (1) to (5), which further comprises water in an amount of from 1% by weight to 20% by weight. (7) The mold cleaning composition according to any one of (1) to (6), further comprising 121307.doc comprising a mold release agent, such as a mold cleaning composition of (1) to (7) t-, and wherein the mold is The fourth (4) is that a plurality of linear slits are disposed on the surface of the sheet in parallel with each other in the direction of the limbs. J9) The mold cleaning composition of (8), wherein the gaps are set such that the sheet mold cleaning composition can be folded. (10) The mold cleaning composition of (8), wherein the slits are disposed such that the sheet mold cleaning composition can be cut along the slits. (11) A mold cleaning composition according to any of (1U (1G), which is a cleaning composition for a mold for reversing thermoforming to mold a material. As described above, the mold cleaning composition of the present invention Containing unvulcanized rubber, detergent and vulcanizing agent as essential components, and based on the measurement by gel permeation chromatography (^), the weight average molecular weight (Mw) is within the range of the buckle. The cleaning composition has an appropriate viscosity and achieves excellent properties of filling in a mold. When the mold surface is cleaned by using the mold cleaning composition of the present invention, the mold cavity is filled with the mold cleaning composition. Allowing contaminants on the surface of the mold to adhere to the mold cleaning composition, thereby effectively removing contaminants and mold cleaning composition from the mold integrally. For example, the molding for molding the semiconductor element is formed. The mold on the surface of the mold (which has been used in the molding using the epoxy resin composition) is combined with the mold prepared by the mold cleaning composition to be effectively removed from the mold. In the article, the mold cleaning can be performed efficiently. Therefore, the semiconductor device formed by using the mold cleaned by the mold cleaning composition of the present invention has an excellent appearance. 121307.doc 1373521 The mold cleaning composition is in the form of a sheet or a belt. In this case, the mold cleaning composition may be easily positioned to clean the mold cavity. Further, it is possible to obtain an excellent mold cleaning effect by using a glycol ether, an imidazole, an imidazoline or an amino alcohol as a cleaning agent. When the cleaning composition contains 1% by weight to 2% by weight of water, it is possible to obtain more excellent cleaning performance. When the mold cleaning composition is molded to be in the form of a sheet and has a plurality of settings on the surface of the sheet In the case of a linear slit in one direction, it may be easily stacked by folding the sheet along the slits. In this case, since the respective block segments separated by the parallel slits are at portions below the slits Connected to each other, so the sheets can be stacked neatly without dislocation during the folding process, and the individual block segments do not intersect or appear similarly when stacked Therefore, the resulting stacked shape is regular. By using a neatly stacked sheet-like cleaning composition to clean the mold, it is possible to eliminate cleaning defects caused by, for example, insufficient pressure contact between the unvulcanized rubber and the mold surface. The size of the sheet is measured to cut the sheet into pieces of the same size, and complicated work of aligning the cut pieces is not necessary for stacking, so that the cleaning work may be simplified. - In addition, when the mold cleaning composition is in the form of a sheet And especially on the surface of the sheet • having a plurality of linear slits disposed in one direction to cut the sheet mold cleaning composition along the slits, the sheet may be easily cut to fit a regular smaller mold size. An embodiment of the present invention will be described. The mold cleaning composition of the present invention as a whole has a specific weight average molecular weight of 121307.doc 1373521 dilute or a mixture thereof. The Mooney viscosity of the butadiene rubber (Mooney viSC〇Sity) ML1+4 (i〇〇t) may be from 20 to 80, more preferably from 35 to 60. It is preferred to use a butadiene rubber having a weight average molecular weight (Mw) of 200,000 to 60 Å, hydrazine, more preferably 400,000 to 6,000 Å. Examples of the detergent include glycol ethers, imidazoles, imidazolines, and amino alcohols. These detergents may be used singly or in combination of two or more of them. The above glycol ether is a compound represented by the following formula (丨):
Ri 0 CHi 0^· a Rj ··· (1) 0 (在式(1)中,n為正整數,且心與尺2各自為氫或烷基。當Ri 與R2中之一者為氫時,另一者為烷基。當心與心均為烷基 時’ R!與r2可相同或不同。) 式(1)所示之二醇醚之實例包括乙二醇二甲醚、二乙二 醇二甲醚、三乙二酵二甲醚、四乙二醇二曱醚、聚乙二醇 二甲喊、二乙二醇單丙醚、二乙二醇單丁醚、二乙二醇二Ri 0 CHi 0^· a Rj · (1) 0 (In the formula (1), n is a positive integer, and each of the core and the rule 2 is hydrogen or an alkyl group. When one of Ri and R2 is hydrogen The other one is an alkyl group. When both the heart and the heart are alkyl groups, 'R! and r2 may be the same or different.) Examples of the glycol ether represented by the formula (1) include ethylene glycol dimethyl ether, diethyl Diol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dioxime ether, polyethylene glycol dimethyl sulfonate, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol two
乙喊、乙二醇單曱醚、乙二醇單***、乙二醇單丙醚及乙 二醇單丁醚。該等二醇醚可單獨使用或其中之二或多者組 合使用。 在式(1)所示之上述二醇醚中’較佳使用重複數11為1至2 且Ri與Rz中之一者為具有1至4個碳原子的烷基同時另一者 為氣的二醇醚;或重複數n為1至2且當心與心均為烷基 時其為具有1至4個碳原子的院基。本文中,在重複數η 為3或更大的情況下,與橡膠的相容性變差。此外,在烷 基中的碳原子數目為5或更大的情況下,對氧化降解脫模 121307.doc 劑層或其類似層的滲透性變差。二醇醚之沸點可較佳為約 130°C至250°C。更具體言之,因為模具模製通常係在 150°C至185°C下進行,因此當二醇醚之沸點低於13〇<t 時,清潔過程中的蒸發非常快而使清潔工作環境在某些情 況下劣化。當沸點超過25〇t時,蒸發變得困難而使二醇 醚殘留在硫化橡膠中,從而使得清潔後的硫化橡膠強度降 低且在自模具取出清潔組成物後硫化橡膠可出現斷裂或類 似現象。因此,難以令人滿意地將氧化降解脫模劑層或其 類似層自模具表面剝離,從而導致清潔工作效率降低的傾 向。 在使用中’每一種二醇醚可按原狀使用或與水,諸如曱 :、乙醇及正丙醇之醇或諸如甲苯及二甲苯之有機溶劑混 合使用。在將二醇醚與有機溶劑混合的情況下,相對於 1〇0重量份的二醇醚,有機溶劑的量較佳設為50重量份或 更少,更佳為20重量份或更少。 藉由使用下式(2)所示之咪嗤作為上述咪峻可獲得良好 效果:B, ethylene glycol monoterpene ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether. These glycol ethers may be used singly or in combination of two or more of them. In the above glycol ether represented by the formula (1), it is preferred to use a repeating number of 11 to 1 and 2, and one of Ri and Rz is an alkyl group having 1 to 4 carbon atoms while the other is gas. a glycol ether; or a repeating number n of 1 to 2 and which is a group having 1 to 4 carbon atoms when both the center and the heart are alkyl groups. Herein, in the case where the repetition number η is 3 or more, the compatibility with the rubber is deteriorated. Further, in the case where the number of carbon atoms in the alkyl group is 5 or more, the permeability to the oxidative degradation demolding 121307. doc layer or the like is deteriorated. The boiling point of the glycol ether may preferably be from about 130 ° C to 250 ° C. More specifically, since the mold is usually molded at 150 ° C to 185 ° C, when the boiling point of the glycol ether is lower than 13 〇 < t, the evaporation during the cleaning process is very fast and the cleaning work environment is cleaned. Degraded in some cases. When the boiling point exceeds 25 Torr, evaporation becomes difficult to cause the glycol ether to remain in the vulcanized rubber, so that the strength of the vulcanized rubber after cleaning is lowered and the vulcanized rubber may be broken or the like after the cleaning composition is taken out from the mold. Therefore, it is difficult to satisfactorily peel the oxidative degradation release agent layer or the like from the mold surface, resulting in a tendency to reduce the cleaning work efficiency. In use, each glycol ether can be used as it is or in combination with water such as hydrazine: an alcohol of ethanol and n-propanol or an organic solvent such as toluene and xylene. In the case of mixing the glycol ether with an organic solvent, the amount of the organic solvent is preferably 50 parts by weight or less, more preferably 20 parts by weight or less, per 100 parts by weight of the glycol ether. Good results can be obtained by using the rice shown in the following formula (2) as the above-mentioned mic:
R RR R
…⑴ 弋()中每一 R’為H、具有取代基且具有1〇個或1〇個以 原子之直鏈烴基、不具有取代基且具有個或個以 下碳原子之直鏈烴基,或芳基,且R,可相同或不同。) 12 J307.doc μ該味唾之實例包括2-甲基妹嗤、2-乙基·4-甲基味唑、2- 苯基味唾、q -卞&-2-甲基咪唑及2 4·二胺基_6[2,_甲基咪唑 基 '(1)Ί 乙其L ς = πΑ ^ —井。該等咪唑可單獨使用或其中之二或 多者組合使用。 藉由使用下式(3)所示之咪唑啉作為上述咪唑啉可獲得 良好效果:(1) each R' in 弋() is H, has a substituent and has 1 or 1 unit of a linear hydrocarbon group having an atom, a linear hydrocarbon group having no substituent and having one or more carbon atoms, or Aryl groups, and R, may be the same or different. 12 J307.doc μ Examples of such saliva include 2-methyl oxime, 2-ethyl 4-methyl oxazole, 2-phenyl odor saliva, q-卞 & -2-methylimidazole and 2 4 · Diamino _6 [2, _ methyl imidazolyl ' (1) 乙 B its L ς = π Α ^ - well. These imidazoles may be used singly or in combination of two or more thereof. Good results can be obtained by using the imidazoline represented by the following formula (3) as the above imidazoline:
(在式(3)中’每一 R'為Η、具有取代基且具有1〇個或1〇個以 下碳原子之直鏈烴基、不具有取代基且具有1〇個或1〇個以 下碳原子之直鏈烴基,或芳基,且R,可相同或不同。) 咪。坐啉之實例包括2_曱基咪唑啉、2·甲基_4_乙基咪唑 啉、2-苯基咪唑啉、丨_苄基_2_甲基咪唑啉、2_苯基_4_甲基_ 5-羥基甲基咪唑啉、2,4-二胺基_6[2,-甲基咪唑啉基乙 基-s-三畊、2,4-二胺基_6[2,-甲基_4,-咪唑啉基_(1),]乙基·s_ 二p井、1-氰基乙基-2-甲基味吐琳及1-氰基乙基_2_甲基_4-乙 基咪唑啉。該等咪唑啉可單獨使用或其中之二或多者組合 使用。 與二醇醚之情況相同,在使用中,味唾及。米唾琳之每一 者可按原狀使用或與諸如曱醇、乙醇及正丙醇之醇或諸如 甲苯及二甲笨之有機溶劑混合使用。在將咪唑與醇或有機 溶劑混合的情況下’相對於1 〇〇重量份的咪唑及味唑琳中 12l307.doc • 14- 之至少一者,醇或有機溶劑的量較佳設為50重量份或更 少,更佳為20重量份或更少。 對於上述胺基醇,可使用下列胺基醇來獲得良好效果。 胺基醇之代表性實例包括單乙胺醇、二乙胺醇、三乙胺 醇、N-甲基乙胺醇,N,N-二曱基乙胺醇、ν,Ν·二丁基乙胺 醇、Ν,Ν-二乙基乙胺醇、Ν-甲基-Ν,Ν-二乙胺醇、2-胺基-2 -甲基丙醇、3-胺基丙醇及2-胺基丙醇。該等胺基醇可單 獨使用或其令之二或多者組合使用。 與上述其他清潔劑之情況相同,在使用中,胺基醇可按 原狀使用或與諸如甲醇、乙醇及正丙醇之醇或諸如曱苯及 —曱笨之有機溶劑混合使用。在將醇胺與醇及或有機溶劑 混合的情況下’相對於100重量份的胺基醇,醇或有機溶 劑的量可較佳設為50重量份或更少,更佳為20重量份或更 少。 相對於100重量份的未硫化橡膠,清潔劑(二醇醚、咪 唑、咪唑啉或胺基醇)的含量可較佳地設在1〇重量份至 重量份、更佳15重量份至25重量份之範圍内。當清潔劑的 含量小於10重量份時,難以展示出對模具之令人滿意的清 潔效果。當在藉由使用由此獲得的模具清潔組成物來清潔 模具的情況下清潔劑之含量超過6〇重量份時,組成物黏著 於模具上,從而使自模具剝離組成物的工作效率降低。 硫化劑無待別限制,且可使用習知的硫化劑。硫化劑之 實例包括硫及有機過氧化物,諸如正丁基_4,4•雙(第三丁 基過氧基)戊酸酯及U-二(第三丁基過氧基)3,3,5_三曱基 121307.doc 1373521 環己烧。該等硫化劑可單獨使用或其中之二或多者組合使 用°相對於100重量份的未硫化橡膠,硫化劑的含量可較 佳設在1重量份至3重量份之範圍内。 此外’本發明之模具清潔組成物除含有未硫化橡膠、清 潔劑及硫化劑外,可視情況含有脫模劑、增強劑及其類似 物。(In the formula (3), 'each R' is an anthracene, a linear hydrocarbon group having a substituent and having 1 or less carbon atoms, a substituent having no substituent and having 1 or less carbon atoms a linear hydrocarbon group of an atom, or an aryl group, and R, which may be the same or different.) Examples of the porphyrin include 2-mercaptoimidazoline, 2·methyl-4-isoimidazoline, 2-phenylimidazoline, 丨-benzyl-2-methylimidazoline, 2_phenyl_4_ Methyl 5-hydroxymethylimidazoline, 2,4-diamino- 6 [2,-methylimidazolidinylethyl-s-trin, 2,4-diamino] 6 [2,- Methyl-4,-imidazolinyl-(1),]ethyl·s_di-p well, 1-cyanoethyl-2-methyl-tauline and 1-cyanoethyl-2-methyl_ 4-ethylimidazoline. These imidazolines may be used singly or in combination of two or more of them. As in the case of the glycol ether, in use, the taste is saliva. Each of the rice sages may be used as it is or mixed with an alcohol such as decyl alcohol, ethanol and n-propanol or an organic solvent such as toluene and dimethyl stearate. In the case where imidazole is mixed with an alcohol or an organic solvent, the amount of the alcohol or the organic solvent is preferably set to 50 by weight with respect to at least one of 1 part by weight of the imidazole and the oxazoline 12l307.doc • 14-. Parts or less, more preferably 20 parts by weight or less. For the above amino alcohol, the following amino alcohol can be used to obtain a good effect. Representative examples of the amino alcohol include monoethylamine, diethylamine, triethylamine, N-methylethylamine, N,N-dimercaptoethanol, ν, Ν·dibutyl Amine alcohol, hydrazine, hydrazine-diethylethylamine, hydrazine-methyl-hydrazine, hydrazine-diethylamino alcohol, 2-amino-2-methylpropanol, 3-aminopropanol and 2-amine Propyl alcohol. These amino alcohols may be used singly or in combination of two or more. As in the case of the above other detergents, in use, the amino alcohol may be used as it is or in combination with an alcohol such as methanol, ethanol and n-propanol or an organic solvent such as benzene and hydrazine. In the case where the alcohol amine is mixed with an alcohol and or an organic solvent, the amount of the alcohol or the organic solvent may be preferably 50 parts by weight or less, more preferably 20 parts by weight or less based on 100 parts by weight of the amino alcohol. less. The content of the detergent (glycol ether, imidazole, imidazoline or amino alcohol) may preferably be from 1 part by weight to part by weight, more preferably from 15 parts to 25 parts by weight, per 100 parts by weight of the unvulcanized rubber. Within the scope. When the content of the detergent is less than 10 parts by weight, it is difficult to exhibit a satisfactory cleaning effect on the mold. When the content of the detergent exceeds 6 Å by weight in the case where the mold is cleaned by using the thus obtained mold cleaning composition, the composition adheres to the mold, thereby lowering the work efficiency of peeling the composition from the mold. The vulcanizing agent is not limited, and a conventional vulcanizing agent can be used. Examples of vulcanizing agents include sulfur and organic peroxides such as n-butyl-4,4•bis(t-butylperoxy)valerate and U-di(t-butylperoxy)3,3. , 5_ 三曱基121307.doc 1373521 环己烧. These vulcanizing agents may be used singly or in combination of two or more thereof. The vulcanizing agent may be preferably contained in an amount of from 1 part by weight to 3 parts by weight per 100 parts by weight of the unvulcanized rubber. Further, the mold cleaning composition of the present invention may contain, in addition to the unvulcanized rubber, the cleaning agent and the vulcanizing agent, a release agent, a reinforcing agent and the like.
脫模劑無特別限制’且可使用習知的脫模劑。脫模劑之 實例包括:長鏈脂肪酸’諸如硬脂酸及二十二碳烷酸;長 鍵脂肪酸的金屬鹽’以硬脂酸鋅及硬脂酸鈣為代表;酯基 躐’以巴西棕櫊蠟(carnauba wax)、褐煤蠟及褐煤酸的部 分皂化醋為代表;長鏈脂族醯胺,以硬脂醯基乙二胺為代 表;及石蠟,以聚乙烯蠟為代表。The release agent is not particularly limited' and a conventional release agent can be used. Examples of the release agent include: long-chain fatty acids such as stearic acid and behenic acid; metal salts of long-chain fatty acids are represented by zinc stearate and calcium stearate; Partially saponified vinegar of carnauba wax, montan wax and montanic acid; long-chain aliphatic decylamine, represented by stearyl ethylenediamine; and paraffin wax, represented by polyethylene wax.
相對於模具清潔組成物的總重量,脫模劑的含量可較佳 設在1重量%至1〇重量%之範圍内。當脫模劑的含量小於i 重量°/。時’難以展示出足夠的脫模效果。當其含量超過1〇 重量%時,清潔能力可能降低且藉由使用重複利用之後的 模具製造的模製物品之外觀受到影響。 增強劑之實例包括無機增強劑(填充劑),諸如二氧化 矽、氧化鋁、碳黑、碳酸鈣、矽酸鈣、氫氧化鋁、二氧化 鈦及氧化鈦。相對於100重量份的未硫化橡膠,增強劑的 含量可較佳設在10重量份至50重量份之範圍内。 此外,當清潔組成物含有未硫化橡膠膏團作為基本材料 時,可向未琉化橡膠中添加水。相對於模具清潔組成物的 總重量,水的含量可較佳設在!重量%至2〇重量%之範圍 121307.doc 16 1373521 内0 本發明之模具清潔組成物可(例如)如下所述製造。將用 . 作基本材料的未硫化橡膠、清潔劑、硫化劑及其他添加劑 . 混合,且將混合物經分批型捏合機捏合,且接著使用擠壓 機或輥使其形成片狀或帶狀,藉此獲得模具清潔組成物。 纟模具清潔組成物以片形式使用的情況下,片的厚度通常 設為3 mm至1〇 mm。 _ 必需將由此獲得之模具清潔組成物整體的重量平均分子 量(河你)調整為200,〇〇〇至46〇,〇〇〇,其係藉由凝膠滲透層析 法(GPC)里測。其重量平均分子量(Mw)尤其較佳為 至430,〇00。當—小於2〇〇,〇〇〇時,模具清潔組成物之黏度 降低,且在模製過程中,壓力自模具間隙溢出,使得模具 清潔組成物無法散布於模具的各個部分,因為模具腔内部 壓力降低,從而導致形成未填充部分。當其Mw超過 460,000時,模具清潔組成物之黏度增大降低模具清潔 _ 組成物與模具腔的配合性,從而導致形成未填充部分。 (例如)如下所述進行GPC量測。將所得模具清潔組成物 浸泡於氣仿令且靜置3天。接著,將氣仿可溶部分於熱板 • 上加熱以使其乾燥及凝固。藉由使用0.1重量%四氫呋喃 , (THF)溶液調整所得經乾燥及凝固的物質以使其靜置丨天。 接著,藉由使用0.45 μπι膜過濾器將溶液過濾,且藉由使 用預定分析儀在預定條件下對濾出液進行Gpc量測◊在 :PC量測中,所用溶劑不限於溶液且可根據量測對象 清潔組成物之組成適當地選擇。 121307.doc :具清潔組成物可較佳具有淺色,諸如白色及接近白色 目^色^藉由調整顏色,在模具清潔後,可能容易地用肉 定π染物自模具移除且黏附於模具清潔組成物上藉 此實現可能容易地確定模具清潔狀態的效果。The content of the releasing agent may preferably be in the range of 1% by weight to 1% by weight based on the total weight of the mold cleaning composition. When the content of the release agent is less than i weight ° /. It is difficult to demonstrate sufficient release effect. When the content exceeds 1% by weight, the cleaning ability may be lowered and the appearance of the molded article manufactured by using the mold after repeated use is affected. Examples of the reinforcing agent include inorganic reinforcing agents (fillers) such as cerium oxide, aluminum oxide, carbon black, calcium carbonate, calcium silicate, aluminum hydroxide, titanium oxide, and titanium oxide. The content of the reinforcing agent may preferably be in the range of 10 parts by weight to 50 parts by weight based on 100 parts by weight of the unvulcanized rubber. Further, when the cleaning composition contains an unvulcanized rubber paste as a base material, water may be added to the undeuterated rubber. The water content can preferably be set relative to the total weight of the mold cleaning composition! Range of % by weight to 2% by weight 121307.doc 16 1373521 Internal 0 The mold cleaning composition of the present invention can be produced, for example, as follows. The unvulcanized rubber, detergent, vulcanizing agent and other additives used as the base material are mixed, and the mixture is kneaded by a batch type kneader, and then formed into a sheet or a belt by using an extruder or a roller. This obtains a mold cleaning composition. In the case where the mold cleaning composition is used in the form of a sheet, the thickness of the sheet is usually set to 3 mm to 1 mm. _ The weight average molecular weight of the mold cleaning composition thus obtained (the river) must be adjusted to 200, 〇〇〇 to 46 〇, 〇〇〇, which is measured by gel permeation chromatography (GPC). The weight average molecular weight (Mw) thereof is particularly preferably from 430 to 〇00. When - less than 2 〇〇, 黏, the viscosity of the mold cleaning composition is reduced, and during the molding process, the pressure overflows from the mold gap, so that the mold cleaning composition cannot be dispersed in various parts of the mold because the inside of the mold cavity The pressure is reduced, resulting in the formation of an unfilled portion. When its Mw exceeds 460,000, the viscosity of the mold cleaning composition is increased to reduce the mold cleaning _ composition and mold cavity compatibility, resulting in the formation of unfilled portions. (For example) GPC measurement is performed as described below. The resulting mold cleaning composition was immersed in a gas embossing and allowed to stand for 3 days. Next, the gas-soluble soluble portion is heated on the hot plate to dry and solidify. The resulting dried and solidified material was adjusted to stand overnight by using a 0.1% by weight tetrahydrofuran, (THF) solution. Next, the solution is filtered by using a 0.45 μπι membrane filter, and the Gpc amount is measured on the filtrate under predetermined conditions by using a predetermined analyzer. In the PC measurement, the solvent used is not limited to the solution and may be based on the amount. The composition of the object cleaning composition is appropriately selected. 121307.doc: The cleaning composition may preferably have a light color, such as white and near white color. By adjusting the color, after the mold is cleaned, it may be easily removed from the mold and adhered to the mold after the mold is cleaned. The cleaning composition thereby achieves an effect that the mold cleaning state can be easily determined.
在使用本發明之模具清潔組成物的情況下,較佳使用經 模製成片形的模具清潔組成物。在使用片狀模具清潔組成 物時’就藉由使用>1狀模具清潔㈣物來進行模具清潔工 作的容易性及其類似性能的角度而言,適合使用如圖^ 所示片表面具有複數個以預定間距且彼此平行設置的線性 縫隙11以使得片10可折疊的片1〇。更佳地,片1〇具有一帶 有條紋圖案的片表面。藉由使用該等縫隙11折疊片10,可 能將片10整齊堆疊。In the case of using the mold cleaning composition of the present invention, it is preferred to use a mold-molded mold to clean the composition. When using a sheet mold to clean the composition, it is suitable to use the surface of the sheet as shown in Fig. 2 by using the <1 mold cleaning (4) for the ease of mold cleaning work and the like. The linear slits 11 are disposed at predetermined intervals and in parallel with each other such that the sheets 10 are foldable. More preferably, the sheet 1 has a sheet surface with a striped pattern. By folding the sheets 10 using the slits 11, it is possible to stack the sheets 10 neatly.
具有縫隙11的片10可如下所述製造。將如上所述得到的 軋製片切割成預定形狀及尺寸得到片10,且於每一片10之 上表面上形成縫隙U ^縫隙丨〗的形成係(例如)如圖2中所 示’藉由使用盤紙分切機(ribbon slitter)進行,其中圓形切 割刀片13連接於旋轉軸12上,且移動切割刀片13,切割刀 片13自片1〇之上表面且在片1〇之橫向方向上***片1〇中預 定深度以形成彼此平行的缝隙丨丨。藉由重複上述操作,於 片10之整個上表面上形成以怪定間距且彼此平行設置的縫 隙11。片10經縫隙u分割成相同尺寸的塊狀片段10a。由 於缝隙11係以恆定間距形成,所以當折疊片時,縫隙i t具 有標尺功能,因此可能根據待清潔之模具或腔的尺寸切割 或折疊片10。 121307.doc • 18 · 1373521 此外’如圖3中所示’每一縫隙u之末端與朝向缝隙u 之該末端之片表面之間的距離D可較佳設為約O.i mm至0.8 mm,更佳為約0.2而至〇 5随。當距離小於〇」麵時, 塊狀片段10a趨向於容易地分離,且當距離超過〇 8爪以 時’折疊較不順暢。 藉由使用本發明之形成為片狀之模具清潔組成物來清潔 模具的方法係對欲用於模製半導體器件之模具進行。舉例 而言,將處於未硫化狀態的片置放於模具中,且接著使其 熱硫化以使污染物整體式黏附於片上。接著藉由自模具移 除經硫化之片來進行模具清潔。 以下將根據事件順序來詳細描述使用片狀模具清潔組成 物的模具清潔方法。 以製備本發明之片狀模具清潔組成物開始。接著,如圖 4中所示,將片狀模具清潔組成物1〇置放於形成有凹陷“ 的上模具1與形成有凹陷儿的下模具2之間,且如圖5中所 不,將上模具1與下模具2夾緊以將片狀模具清潔組成物1〇 夾於其中進行壓力模製。使片10填充於由形成於上模具1 中的凹陷3a與形成於下模具2中的凹陷31?形成的腔3中且 用於模製之壓力使其與模具表面壓力接觸。在此狀態下, 用於模製之熱將未硫化橡膠熱硫化成硫化橡膠,由此使腔 3中形成之氧化降解脫模劑層及其類似層與硫化橡膠結 合°在某些情況下,腔3周圍的毛邊亦與硫化橡膠結合。 接著,如圖6中所示,經預定時間週期後,打開上模具1與 下模具2以自上模具1與下模具2剝離已成為硫化橡膠的片 121307.doc -19· 狀模具清潔經成物10,藉此自上模具丨與下模具2的表面剝 離與片10結合的氧化降解層及其類似層。由此進行模具清 潔》 對於片狀模具清潔組成物,可能使用如圖1中所示,具 有複數個以預定間距且彼此平行形成於片表面上的線性縫 隙11以使得片1〇可折疊的片狀模具清潔組成物。 在使用該片狀清潔組成物的情況下,如圖7所示,沿缝 隙11自片切割所要數目之塊狀片段i 〇a。可藉由用手指挑 起片10且沿缝隙U重複折疊或藉由使用小刀或其類似物來 進行該切割。接著’如圖8中所示,沿縫隙丨丨折疊片丨〇, 其中片10之上表面(形成有縫隙11之表面)朝外(此處,在圖 8中切割下4個塊狀片段10a),且將片1〇連續折疊,直至其 下表面彼此接觸以將塊狀片段1〇 a堆疊,如圖8所示。在折 疊過程中,10a並未彼此分離,因為塊狀片段l〇a在縫隙U 之底部11a彼此連接。因此’僅藉由簡單的折疊操作,便 可能將塊狀片段l〇a整齊堆疊’其中塊狀片段l〇a沿縱向方 向及橫向方向對齊且塊狀片段10a之間並不彼此交又。因 此,可能省去量測片1〇尺寸以將片10切割成具有相同尺寸 之片段或使分離塊狀片段l〇a對齊的勞動。 雖然圖8中展示藉由將4個自片切割的塊狀片段1 〇a在該 等阻塊10a之中心處折疊來將2個塊狀片段1〇a堆疊於另2個 塊狀片段10a上的狀態,但本發明並不限於此,且可能根 據待清潔之模具及腔的尺寸,切割並折疊適當數目之塊狀 片段10a以將該等塊狀片段1〇a堆疊成適當尺寸(舉例而 121307.doc •20· 1373521 5,將3個塊狀片段1〇a堆疊於另3個塊狀片段i〇a上以使用 6個塊狀片段l〇a)。 • 欲使用本發明之模具清潔組成物的模具之一實例為(例 >)用於模製半導體器件的模具,藉由使用熱固性樹脂組 成物以該模具進行重複模製。 • 纟肖於模製半導體器件的模具(其為使用本發明之模具 清潔組成物之模具的實例)中,欲用作成形樹脂材料的熱 • ®性樹脂組成物的實例包括含有作為主要成份之環氧樹脂 的環氧樹脂組成物。 在熱固性樹脂組成⑮中,固化劑通常與用作±要成份之 環氧樹脂一起使用。 由於用本發明之模具清潔組成物清潔的模具不含污染物 且恢復至初始狀態的模具表面,因此通常在使用用作模具 材料的熱固性樹脂組成物來模製半導體包裝之前於模具^ 面上塗覆脫模劑。舉例而言,在模製含有作為脫模劑之褐 _ ㈣堰的模具材料,較佳塗覆褐㈣t對於在模具表 面上塗覆褐煤酸蠟的方法,較佳使用含有褐煤酸蠟且形成 W狀的未硫化橡膠組絲,諸如可藉由將前述未硫化橡 .夥與脫模劑品合獲得之片。以與使用片狀模具清潔組成物 . 料潔方法^所用方式相同的方式,將由含有褐煤酸壤的 未硫化橡膠組成物形成之月置放於模具中且加熱,由此將 其令所含有的褐煤酸蟻塗覆於模具表面上。認為未硫化橡 膠組成物中之褐煤酸壤藉由熱硫化而溶融且渗出至模具表 面上,從而在該表面上形成均勻的脫模劑膜。 121307.doc -21· 1373521 未硫化橡膠組成物中’相對於100重量份的橡膠材料, 褐煤酸蠟的含量可較佳設為15重量份至35重量份、更佳20 重量份至30重量份之比率。當褐煤酸蠟之含量小於15重量 份時,未展示出足夠的脫模效果。當其含量超過35重量份 時’過量褐煤酸蠟塗覆於模具表面上從而影響藉由使用清 潔及重複利用之後的模具獲得的模製物品外觀。 以下描述實例及比較實例。The sheet 10 having the slits 11 can be manufactured as follows. The rolled sheet obtained as described above is cut into a predetermined shape and size to obtain a sheet 10, and a formation of a slit U ^ slit is formed on the surface of each sheet 10 (for example, as shown in FIG. 2) The use of a ribbon slitter is attached to the rotary shaft 12, and the cutting blade 13 is moved from the upper surface of the sheet 1 in the lateral direction of the sheet 1 A predetermined depth is inserted into the sheet 1 to form slits parallel to each other. By repeating the above operation, the slits 11 which are disposed at a strange pitch and which are disposed in parallel with each other are formed on the entire upper surface of the sheet 10. The sheet 10 is divided into the block segments 10a of the same size via the slit u. Since the slits 11 are formed at a constant pitch, when the sheets are folded, the slits have a scale function, so that the sheets 10 may be cut or folded depending on the size of the mold or cavity to be cleaned. 121307.doc • 18 · 1373521 Furthermore, as shown in Fig. 3, the distance D between the end of each slit u and the sheet surface facing the end of the slit u can preferably be set to about Oi mm to 0.8 mm, Good for about 0.2 and to 〇5 with. When the distance is smaller than the 〇" face, the block segments 10a tend to be easily separated, and when the distance exceeds 〇 8 claws, the folding is less smooth. The method of cleaning the mold by using the mold-forming mold cleaning composition of the present invention is carried out on a mold to be used for molding a semiconductor device. For example, a sheet in an unvulcanized state is placed in a mold and then thermally vulcanized to cause the contaminants to adhere integrally to the sheet. The mold is then cleaned by removing the vulcanized sheet from the mold. The mold cleaning method using the sheet mold cleaning composition will be described in detail below based on the sequence of events. The preparation begins with the preparation of the sheet mold cleaning composition of the present invention. Next, as shown in FIG. 4, the sheet-shaped mold cleaning composition 1 is placed between the upper mold 1 in which the depression is formed and the lower mold 2 in which the depression is formed, and as shown in FIG. The upper mold 1 is clamped with the lower mold 2 to sandwich the sheet-shaped mold cleaning composition 1 therein for pressure molding. The sheet 10 is filled in a recess 3a formed in the upper mold 1 and formed in the lower mold 2 The pressure formed in the cavity 3 formed by the recess 31 is brought into pressure contact with the surface of the mold. In this state, the heat for molding thermally vulcanizes the unvulcanized rubber into vulcanized rubber, thereby forming the cavity 3. The oxidative degradation release agent layer and the like are combined with the vulcanized rubber. In some cases, the burrs around the cavity 3 are also combined with the vulcanized rubber. Next, as shown in FIG. 6, after a predetermined period of time, the upper mold 1 is opened. The lower mold 2 is peeled from the upper mold 1 and the lower mold 2 to form a vulcanized rubber sheet 121307.doc -19. The mold cleaning the resultant 10, whereby the surface of the lower mold 2 is peeled off from the upper mold 2 and bonded to the sheet 10. Oxidative degradation layer and its similar layer. For the sheet mold cleaning composition, it is possible to use a plurality of linear slits 11 formed at a predetermined pitch and parallel to each other on the sheet surface as shown in Fig. 1 to make the sheet 1 foldable sheet mold cleaning composition. In the case of using the sheet-like cleaning composition, as shown in Fig. 7, a desired number of block segments i 〇a are cut from the sheet along the slit 11. The sheet 10 can be picked up by fingers and repeatedly folded along the slit U or This cutting is performed by using a knife or the like. Then, as shown in Fig. 8, the sheet bundle is folded along the slit, wherein the upper surface of the sheet 10 (the surface on which the slit 11 is formed) faces outward (here) The four block segments 10a) are cut in Fig. 8, and the sheets 1〇 are continuously folded until their lower surfaces are in contact with each other to stack the block segments 1〇a as shown in Fig. 8. During the folding process, 10a are not separated from each other because the block segments l〇a are connected to each other at the bottom 11a of the slit U. Therefore, it is possible to stack the block segments l〇a neatly by simple folding operation, in which the block segments l〇 a aligned in the longitudinal and lateral directions and block The segments 10a do not intersect each other. Therefore, it may be possible to omit the size of the sheet 1 to cut the sheet 10 into pieces having the same size or to align the separated block segments 10a. Although shown in FIG. The state in which two block segments 1〇a are stacked on the other two block segments 10a by folding four block segments 1 〇a cut from the sheet at the center of the block 10a, but The invention is not limited thereto, and it is possible to cut and fold an appropriate number of block segments 10a according to the size of the mold and cavity to be cleaned to stack the block segments 1〇a into appropriate sizes (for example, 121307.doc • 20 · 1373521 5, 3 block segments 1〇a are stacked on the other 3 block segments i〇a to use 6 block segments l〇a). An example of a mold for cleaning a composition using the mold of the present invention is (Example >) a mold for molding a semiconductor device, which is repeatedly molded by using a mold using a thermosetting resin composition. • In the case of a mold for molding a semiconductor device which is an example of a mold for cleaning a composition using the mold of the present invention, an example of a composition of a thermal resin to be used as a molding resin material includes containing as a main component Epoxy resin composition of epoxy resin. In the thermosetting resin composition 15, a curing agent is usually used together with an epoxy resin used as a component. Since the mold cleaned by the mold cleaning composition of the present invention contains no contaminants and returns to the mold surface in the initial state, it is usually coated on the mold surface before molding the semiconductor package using the thermosetting resin composition used as the mold material. Release agent. For example, in molding a mold material containing brown _ (tetra) hydrazine as a release agent, preferably coating brown (tetra) t. For the method of coating a lignite wax on the surface of the mold, it is preferred to use a lignite wax and form a W shape. An unvulcanized rubber component such as a sheet obtainable by combining the aforementioned unvulcanized rubber and a release agent. The month in which the unvulcanized rubber composition containing the lignite soil is formed in the mold and heated in the same manner as in the method of cleaning the composition using the sheet mold cleaning method, thereby causing the brown coal contained therein The acid ants are applied to the surface of the mold. It is considered that the lignite acid in the unvulcanized rubber composition is melted by thermal vulcanization and exuded to the surface of the mold to form a uniform release agent film on the surface. 121307.doc -21· 1373521 In the unvulcanized rubber composition, the content of the montanic acid wax is preferably from 15 parts by weight to 35 parts by weight, more preferably from 20 parts by weight to 30 parts by weight, per 100 parts by weight of the rubber material. ratio. When the content of the montanic acid wax is less than 15 parts by weight, a sufficient release effect is not exhibited. When the content exceeds 35 parts by weight, the excess montanic acid wax is applied to the surface of the mold to affect the appearance of the molded article obtained by using the mold after cleaning and recycling. The following describes examples and comparative examples.
實例1至6及比較實例1至5 將表1至2中所示的組份按比例混合,且藉由使用捏合機 捏合各混合物且使用壓力輥進行輥軋以得到厚度為5 mm的 片’藉此獲得所要片狀模具清潔組成物。Examples 1 to 6 and Comparative Examples 1 to 5 The components shown in Tables 1 to 2 were mixed in proportion, and each mixture was kneaded by using a kneader and rolled using a pressure roll to obtain a sheet having a thickness of 5 mm. Thereby, the desired sheet-like mold cleaning composition is obtained.
如下所述量測每一片狀模具清潔組成物的重量平均分子 量(Mw)。將片狀模具清潔組成物浸泡於氣仿中以靜置3 天。接著,將氯仿可溶部分於熱板上於5〇〇c下加熱以使其 乾燥及凝固,且藉由使用〇.1重量%四氫呋喃(THF)溶液調 整所得經乾燥及凝固的物質以使其靜置丨天。接著,藉由 使用0.45 μηι膜過濾器將溶液過濾,且藉由使用Gpc分析儀 (HLC-8120GPC’ 由 Tosoh Corporation 製造)在以下量測條 件下量測濾出液的重量平均分子量(Mw) ^ 量測條件: 管柱:GMHXL+GMHXL+G3000HXL,由 Tosoh Corporation 製造 管柱尺寸.各自具有7.8 mmx 30 cm之直徑,總尺寸:90 cm 121307.doc •22- 1373521 管柱溫度:40°C 溶離溶液:THF 流動速率:0.8 ml/min 入口壓力:2.3 MPa 注入量:100 μΐ 偵測器:示差折射器(RI) 標準樣本:聚苯乙烯(PS)The weight average molecular weight (Mw) of each of the sheet mold cleaning compositions was measured as described below. The sheet mold cleaning composition was immersed in the air sample to stand for 3 days. Next, the chloroform-soluble portion was heated on a hot plate at 5 ° C to dry and solidify, and the obtained dried and solidified substance was adjusted by using a solution of 0.1% by weight of tetrahydrofuran (THF) to make it Resting in the sky. Next, the solution was filtered by using a 0.45 μm membrane filter, and the weight average molecular weight (Mw) of the filtrate was measured under the following measurement conditions by using a Gpc analyzer (HLC-8120GPC' manufactured by Tosoh Corporation). Measurement conditions: Column: GMHXL+GMHXL+G3000HXL, manufactured by Tosoh Corporation. Column size. Each has a diameter of 7.8 mm x 30 cm, total size: 90 cm 121307.doc • 22- 1373521 Column temperature: 40 °C Dissolution Solution: THF Flow rate: 0.8 ml/min Inlet pressure: 2.3 MPa Injection volume: 100 μΐ Detector: Differential refractor (RI) Standard sample: Polystyrene (PS)
數據處理裝置:GPC-8020,由Tosoh Corporation製造 如下所述評價實例、比較實例及習知實例之每一由此獲 得之片狀模具清潔組成物的填充性能。藉由使用用於填充 性能評價的模具[模具尺寸:24 mmX91 mm :模具腔尺 寸:4 mmx5 mmx2.0 mm(上腔與下腔的總深度)],評價16 個腔中填充性能最差的腔的填充率。結果展示於表1與表2 中〇 填充率係藉由什算模具腔之底表面’積及所得模製物品之Data Processing Apparatus: GPC-8020, manufactured by Tosoh Corporation The filling performance of each of the thus obtained sheet-like mold cleaning compositions was evaluated by the evaluation examples, comparative examples, and conventional examples described below. Evaluation of the worst filling performance in 16 cavities by using a mold for filling performance evaluation [mold size: 24 mm X 91 mm: mold cavity size: 4 mm x 5 mm x 2.0 mm (total depth of upper and lower chambers)] The filling rate of the cavity. The results are shown in Tables 1 and 2. The filling rate is calculated by the bottom surface of the mold cavity and the resulting molded article.
腔部分之底表面積,且接著計算該等底表面積之比率來偵 測。如圖4中所示,在上模具丨與下模具2形成的模具中,8 個腔3成彼此平行的兩列對齊。如上所述彼此平行設置的 腔3之間的間距為1〇 mm,且每一列令8個對齊的腔3係以工 mm之間隔設置。用作樣本之片狀模具清潔組成物ι〇的尺 寸設為10 mm寬度,91 mm長度,及5 mm厚度,且將樣本 设置於模具中腔3之列之間以進行評價,接著關閉模具用 於熱成形。對於成形條件’成形係在175。(:下進行5分鐘, 且夾緊的模具之間的間隙為〇 5 mm。 121307.doc •23- 1373521 低於實例樣木之填充率,且因填充性能差,比較實例難以 實際使用。 以下將描述使用具有缝隙之片狀模具清潔組成物的實 例0 實例7 如圖1中所示,將上述實例1至6中所獲得的每一片狀模 具清潔組成物(厚度(圖i中為τ)為5 mm)切割成各自寬度(圖 1中為A)為230 mm、長度(圖i中為8)為3〇〇 mm的片ι〇。在 片ίο的整個上表面上在片1〇的寬度方向上以15爪以之間隔 (圖1中為c)形成各自深度為4 5 mm的彼此平行的縫隙η ^ 亦即,每一缝隙11之末端與朝向該末端之片1〇的片表面之 間的距離(圖3中為D)為0.5 mm。在該片1〇中,形成2〇個塊 狀月段。根據模具尺寸不同的若干種類型之轉注成形 裝置切割每一具有縫隙11的片狀模具清潔組成物10且在縫 隙11之部分處將其折疊以呈堆疊之方式置放於模具中。之 後,關閉模具進行熱成形以量測填充率。結果,谓測到如 同前述片狀模具清潔組成物,填充率較高且填充性能非常 優良。 本發明之模具清潔組成物適用於清潔及重複利用諸如用 於熱固性樹脂成形材料之模具,例如用於清潔及重複利用 用於轉注成形之模具,命望松 这等模具係用於藉由使用環氧樹脂 成形材料進行轉注成形來模製半導體元件。 雖然本發明已詳細且根據其特定實施例加以描述,但熟 習此項技術者應想到在不‘_本發明之精神及範訂可對. 121307.doc • 26 - 1373521 其作各種改變及修改。 本申請案係基於2006年5月25曰申請之曰本專利申請案 第2006-145 544號,該申請案之全部内容以引用之方式併 入本文中。 【圖式簡單說明】 圖1為展示根據本發明之一實施例的月狀模具清潔組成 物的透視圖。The bottom surface area of the cavity portion is then calculated by calculating the ratio of the bottom surface areas. As shown in Fig. 4, in the mold formed by the upper mold 丨 and the lower mold 2, the eight chambers 3 are aligned in two columns parallel to each other. The spacing between the cavities 3 disposed parallel to each other as described above is 1 〇 mm, and each column causes the eight aligned cavities 3 to be arranged at intervals of mm. The size of the sheet-like mold cleaning composition used as a sample was set to 10 mm width, 91 mm length, and 5 mm thickness, and the sample was placed between the cavities 3 in the mold for evaluation, and then the mold was closed. For hot forming. For the forming conditions, the forming system was at 175. (: 5 minutes under, and the gap between the clamped molds is 〇5 mm. 121307.doc •23- 1373521 The filling rate of the example wood is lower, and the comparison example is difficult to use due to poor filling performance. An example of cleaning a composition using a sheet mold having a slit will be described. Example 7 As shown in Fig. 1, each of the sheet mold cleaning compositions obtained in the above Examples 1 to 6 was cleaned (thickness (τ in the figure i) ) is 5 mm) cut into sheets ι 各自 each having a width (A in Fig. 1) of 230 mm and a length (8 in Fig. i) of 3 〇〇 mm. On the entire upper surface of the sheet ίο in the sheet 1 〇 In the width direction, at intervals of 15 claws (c in Fig. 1), slits η ^ which are parallel to each other having a depth of 4 5 mm are formed, that is, the end of each slit 11 and the sheet facing the end 1 The distance between the surfaces (D in Fig. 3) is 0.5 mm. In the sheet 1 ,, two block-shaped segments are formed. Several types of transfer forming devices according to different mold sizes cut each slit 11 The sheet mold cleaning composition 10 and folding it at a portion of the slit 11 to be placed in a stacked manner in the mold After that, the mold was closed for thermoforming to measure the filling rate. As a result, it was found that the above-mentioned sheet-like mold cleaning composition was high in filling rate and excellent in filling performance. The mold cleaning composition of the present invention is suitable for cleaning and Reusing a mold such as a mold for thermosetting resin molding, for example, for cleaning and reusing a mold for transfer molding, which is used for molding a semiconductor by transfer molding using an epoxy molding material. The present invention has been described in detail and in accordance with the specific embodiments thereof, and it is contemplated by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the present invention. 121307.doc • 26-1373521. This application is based on a patent application No. 2006-145 544, filed May 25, 2006, the entire content of which is hereby incorporated by reference. To show a perspective view of a monthly mold cleaning composition in accordance with an embodiment of the present invention.
圖2為在片狀模具清潔組成物上形成缝隙之狀態的說 明。 圖3為展示該等縫隙之一部分的放大側視圖。 圖4為展示使用該片狀模具清潔組成物之狀態的透視 圖。 圖5為展示使用該片狀模具清潔組成物之狀態的透視 圖。Fig. 2 is a view showing a state in which a slit is formed in the sheet-like mold cleaning composition. Figure 3 is an enlarged side elevational view showing a portion of the slits. Fig. 4 is a perspective view showing a state in which the composition is cleaned using the sheet mold. Fig. 5 is a perspective view showing a state in which the composition is cleaned using the sheet mold.
圖ό為展示使用該片狀模具清潔組成物之狀態的透視 圖。 圖7為該片狀模具清潔組成物用於模製半導體器件之效 果的說明。 圖為該片狀模具清潔組成物用於模製半導體器件之效 果的說明。 【主要元件符號說明】 1 上模具 2 下模具 3 腔 121307.doc -27· 1373521Figure ό is a perspective view showing the state in which the composition is cleaned using the sheet mold. Fig. 7 is an illustration of the effect of the sheet mold cleaning composition for molding a semiconductor device. The figure is an illustration of the effect of the sheet mold cleaning composition for molding a semiconductor device. [Main component symbol description] 1 Upper mold 2 Lower mold 3 cavity 121307.doc -27· 1373521
3a 凹陷 3b 凹陷 10 片 10a 塊狀片段 11 缝隙 12 旋轉軸 13 切割刀片 A 寬度 B 長度 C 間距 D 距離 T 厚度3a depression 3b depression 10 piece 10a block segment 11 slit 12 rotating shaft 13 cutting blade A width B length C spacing D distance T thickness
121307.doc -28-121307.doc -28-
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US9999994B2 (en) * | 2010-06-07 | 2018-06-19 | Mitsubishi Chemical Corporation | Method for producing product having uneven microstructure on surface thereof, mold release treatment method, and active energy ray curable resin composition for mold surface release treatment |
JP5741398B2 (en) * | 2011-11-21 | 2015-07-01 | 日立化成株式会社 | Mold cleaning sheet |
CN103205032A (en) * | 2013-03-14 | 2013-07-17 | 西北工业大学 | Mold cleaning rubber for in-place mold cleaning and preparation method of mold cleaning rubber |
CN104450302A (en) * | 2014-11-17 | 2015-03-25 | 厦门市钰林丰橡塑科技有限公司 | Flame-retardant high-temperature resistant environment-friendly cleaning product |
CN105773882A (en) * | 2016-04-19 | 2016-07-20 | 上海东恒化工有限公司 | Composition for die cleaning and die cleaning method |
CN107011553A (en) * | 2017-05-04 | 2017-08-04 | 天津德高化成新材料股份有限公司 | A kind of rubber mould exempts from dismounting mold cleaning material and preparation method thereof with online |
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