TWI500734B - Adhesive composition having improved reliability at high voltage condition and adhesive tape for semiconductor packaging using the same - Google Patents
Adhesive composition having improved reliability at high voltage condition and adhesive tape for semiconductor packaging using the same Download PDFInfo
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- TWI500734B TWI500734B TW102121144A TW102121144A TWI500734B TW I500734 B TWI500734 B TW I500734B TW 102121144 A TW102121144 A TW 102121144A TW 102121144 A TW102121144 A TW 102121144A TW I500734 B TWI500734 B TW I500734B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02002—Preparing wafers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Description
本發明有關一種在高電壓情況時具有增進電氣可靠度之黏著劑組合物及使用此種組合物之半導體封裝用膠帶，尤其有關一種在高電壓情況時具有電氣可靠度之黏著劑組合物及使用此種組合物之半導體封裝用膠帶；此種黏著劑組合物係於一種環氧基樹脂中包含最適量的環氧硬化劑，藉由增加交聯密度而增進硬化網絡的斷裂韌性，進而可在30V或更高之高電壓時確保其電氣可靠度；同時，由於分子在硬化網絡內高度交聯，因此可於200℃或更高的溫度下獲得優異的高溫黏著性。The present invention relates to an adhesive composition having improved electrical reliability at high voltage and a semiconductor packaging tape using the same, and more particularly to an adhesive composition having electrical reliability and a use in a high voltage condition. A tape for semiconductor encapsulation of such a composition; the adhesive composition comprising an optimum amount of an epoxy hardener in an epoxy resin, which increases the fracture toughness of the hardened network by increasing the crosslinking density, and further High electrical voltage of 30V or higher ensures electrical reliability; at the same time, because of the high degree of cross-linking of molecules in the hardened network, excellent high-temperature adhesion can be obtained at 200 ° C or higher.
用於安裝半導體的導線架，係依半導體封裝的寬度、厚度及面積，引腳的長度，晶粒座面積等而定，製成各種不同的形狀。導線架的典型架構包括一導線架本體、從本體延伸的外引腳、從外引腳延伸至本體內側的內引腳、位於內引腳內側中心並供半導體晶粒安裝於其頂面的晶粒座、以及與晶粒座連接的聯結桿。The lead frame for mounting the semiconductor is formed into various shapes depending on the width, thickness and area of the semiconductor package, the length of the lead, the die pad area, and the like. A typical architecture of the leadframe includes a leadframe body, an outer lead extending from the body, an inner lead extending from the outer lead to the inner side of the body, a center inner side of the inner lead, and a semiconductor die mounted on the top surface thereof. a die pad and a tie bar coupled to the die pad.
隨著半導體高效率整合及封裝處理成本降低的趨勢，導線架也改成多樣化的半導體封裝結構。With the trend of high-efficiency semiconductor integration and reduced packaging processing costs, the leadframe has also been modified into a variety of semiconductor package structures.
然而，導線架的類型雖然根據各種封裝結構而多樣化，但是 導線架的引腳通常都極為纖細，因此需要進行各種製程，諸如打線(焊線)等；此外，當引腳受其他外部因素而搖動時，易發生電性連接失敗。因此，需要貼設引腳固定膠帶將引腳固定穩妥。However, the type of lead frame is diversified according to various package structures, but The leads of the lead frame are usually extremely thin, so various processes such as wire bonding (bonding wire) are required; in addition, when the pin is shaken by other external factors, electrical connection failure is liable to occur. Therefore, it is necessary to attach the pin fixing tape to secure the pins.
導線架與引腳固定膠帶的貼合製程中，經由打線而在半導體與導線架之間形成金屬線的步驟可簡述如下：首先，經由沖壓將引腳固定膠帶裁切；緊接沖壓後，在130至260℃的壓縮溫度下將引腳固定膠帶貼合於導線架，持續0.1至1.0秒。In the bonding process of the lead frame and the pin fixing tape, the step of forming a metal wire between the semiconductor and the lead frame via wire bonding can be briefly described as follows: First, the pin fixing tape is cut by punching; immediately after punching, The pin fixing tape is attached to the lead frame at a compression temperature of 130 to 260 ° C for 0.1 to 1.0 seconds.
其次，使用一晶粒貼合薄膜，將半導體晶粒貼合在已貼設引腳固定膠帶的導線架晶粒座上。Next, a die attach film is used to bond the semiconductor die to the leadframe die pad on which the pin fixing tape has been attached.
第三，進行熱處理，通常是在130至180℃的溫度下進行5至90分鐘，以使貼合於半導體晶粒與導線架的晶粒貼合薄膜硬化。Third, the heat treatment is carried out, usually at a temperature of 130 to 180 ° C for 5 to 90 minutes to harden the die-bonding film bonded to the semiconductor die and the lead frame.
最後，在第四步，經由打線完成半導體晶粒與通過熱處理的導線架整體之引腳間的佈線。其中，打線是在200至260℃的高溫下進行的。Finally, in the fourth step, the wiring between the semiconductor die and the lead of the lead frame through the heat treatment is completed by wire bonding. Among them, the wire is made at a high temperature of 200 to 260 °C.
雖然引腳固定膠帶是透過自發熱與壓力而貼合於導線架，但因引腳固定膠帶必須能在200℃或更高溫度下進行的打線製程中將引腳固定，所以引腳固定膠帶通常是一種B階(半硬化)製品；因此，在設計上，它經由施加自發熱與壓力而貼合到導線架後，再透過130至180℃的熱處理而達到C階(完全硬化)。Although the pin fixing tape is attached to the lead frame by self-heating and pressure, since the pin fixing tape must be able to fix the pin in the wire bonding process at 200 ° C or higher, the pin fixing tape is usually It is a B-stage (semi-hardened) product; therefore, it is designed to adhere to the lead frame by applying self-heating and pressure, and then pass through a heat treatment at 130 to 180 ° C to achieve a C-stage (complete hardening).
然而，儘管導線架的各引腳貼上了引腳固定膠帶，但在進行打線製程時，引腳固定膠帶的黏著劑因高溫而變成一種橡膠態，使各引腳對偏移的抗力降低。However, although the lead pins of the lead frame are affixed with the pin fixing tape, the adhesive of the pin fixing tape becomes a rubbery state due to the high temperature during the wire bonding process, so that the resistance of each pin to the offset is lowered.
因此，引腳偏移會帶來電性連接的問題；當導線架的引腳寬 度細微時，極有可能發生這種問題。Therefore, the pin offset brings about the problem of electrical connection; when the lead frame is wide This problem is most likely to occur when the degree is subtle.
通常，對導線架整體覆以環氧塑封料(epoxy mold compound,EMC)而完成封裝後，會施加一電壓以便操作；若導線架是用銅料形成時，由於在某些情況中會發生電氣短路，所以引腳間的絕緣可靠度是一項重要的議題。Usually, after the lead frame is entirely covered with an epoxy mold compound (EMC), a voltage is applied for operation; if the lead frame is formed of copper material, electrical conditions may occur in some cases. Short circuit, so insulation reliability between pins is an important issue.
以下說明發生電氣短路的機制。首先，銅離子從一引腳流出；隨後，施於導線架封裝的電壓就像是驅動力，使析出的銅離子往另一引腳遷移。The mechanism for generating an electrical short is described below. First, copper ions flow out from a pin; subsequently, the voltage applied to the leadframe package acts like a driving force, causing the precipitated copper ions to migrate to the other pin.
此時，抵達另一引腳的銅離子沉澱為銅，沉澱銅聚集而發展成枝晶。At this time, the copper ions reaching the other pin are precipitated as copper, and the precipitated copper aggregates to develop dendrites.
最後，若枝晶抵達另一引腳，由於引腳間會經由銅形成電性連接，於是發生電氣短路。Finally, if the dendrites reach the other pin, an electrical short circuit occurs because the pins are electrically connected via copper.
亦即，由於施加的電壓形成使銅離子遷移的驅動力，因而造成電氣短路。尤其，若在應用高電壓的情況時，諸如電梯、車輛、半導體封裝等，此種問題會更加嚴重。That is, since the applied voltage forms a driving force for migrating copper ions, an electrical short circuit is caused. In particular, such problems can be exacerbated when high voltage applications are applied, such as elevators, vehicles, semiconductor packages, and the like.
因此，亟需一種可在打線製程中對引腳偏移具有高度抗力，在高電壓下確保絕緣可靠度，並在導線架組裝完成時確保高溫黏著性的黏著劑組合物。Therefore, there is a need for an adhesive composition which is highly resistant to pin offset during the wire bonding process, ensures insulation reliability at high voltages, and ensures high temperature adhesion when the lead frame is assembled.
然而，高溫黏著性與絕緣可靠度通常難以共存。However, high temperature adhesion and insulation reliability are often difficult to coexist.
亦即，為了改進高溫黏著性與絕緣可靠度，會使用一種具有小分子量的熱固性樹脂來增加反應速率，並可使用具有小當量的熱固性樹脂改進交聯密度。然而，由於僅以具有小當量熱固性樹脂形成的熱固性網 絡，其性質脆而易碎，所以在高溫時的黏著性較弱。That is, in order to improve high-temperature adhesion and insulation reliability, a thermosetting resin having a small molecular weight is used to increase the reaction rate, and a crosslinking resin having a small equivalent weight can be used to improve the crosslinking density. However, due to the thermoset network formed only with a small equivalent of thermosetting resin The network is brittle and brittle, so it has weak adhesion at high temperatures.
因此，本發明之發明人努力改進先前技術中的問題，結果提供一種黏著劑組合物而完成本發明。透過在一種以環氧基樹脂為基礎的硬化網絡中包含的特定環氧硬化劑，此種黏著劑組合物的交聯密度增加而可強化其電氣可靠度；同時，藉由增加硬化網絡的斷裂韌性，可改進此種黏著劑在高溫下的流動性。本發明並確認，使用所述黏著劑組合物的半導體封裝用膠帶，在打線製程中對引腳偏移具有高度抗力，可於導線架組裝完成時，同時滿足高電壓下的絕緣可靠度及高溫下的黏著性。Accordingly, the inventors of the present invention have endeavored to solve the problems in the prior art, and as a result, provide an adhesive composition to complete the present invention. By increasing the crosslink density of the adhesive composition by a specific epoxy hardener contained in an epoxy resin-based hardening network, the electrical reliability can be enhanced; at the same time, by increasing the fracture of the hardened network Toughness improves the fluidity of such adhesives at high temperatures. The present invention also confirms that the tape for semiconductor packaging using the adhesive composition has high resistance to pin offset in the wire bonding process, and can simultaneously satisfy insulation reliability and high temperature at high voltage when the lead frame is assembled. Adhesion underneath.
因此，鑑於先前技術中會發生前述問題，乃有本發明之提出。本發明之目的係提供一種黏著劑組合物，它在打線製程中具有高度的引腳偏移抗力，並於導線架組裝完成時確保高電壓時的絕緣可靠度與高溫下的黏著性。Therefore, in view of the foregoing problems that may occur in the prior art, there is a proposal of the present invention. SUMMARY OF THE INVENTION It is an object of the present invention to provide an adhesive composition which has a high degree of pin offset resistance in a wire bonding process and ensures insulation reliability at high voltage and adhesion at high temperatures when the lead frame is assembled.
本發明另一目的係提供一種黏著劑組合物，它在環氧基樹脂中包含一種與環氧樹脂進行硬化反應的環氧硬化劑，藉由增加交聯密度而增進硬化網絡的斷裂韌性。Another object of the present invention is to provide an adhesive composition comprising an epoxy hardener which undergoes a hardening reaction with an epoxy resin in an epoxy resin, which enhances the fracture toughness of the hardened network by increasing the crosslinking density.
本發明再一目的係提供一種使用前述黏著劑組合物的半導體封裝用膠帶。Still another object of the present invention is to provide an adhesive tape for a semiconductor package using the above adhesive composition.
為達成上述目的，根據本發明一層面提供的黏著劑組合物包括：(a)100重量份的環氧基樹脂；(b)30至100重量份的第一環氧硬化劑，其包含一種多功能酚樹脂；(c)20至250重量份的第二環氧硬化劑，其包含一種胺類環氧硬化劑、一種酸酐基環氧硬化劑、或前二者之混合物；(d)0.1至10 重量份的硬化促進劑；及(e)30至150重量份由熱塑性樹脂形成的改質劑。To achieve the above object, an adhesive composition according to one aspect of the present invention comprises: (a) 100 parts by weight of an epoxy resin; (b) 30 to 100 parts by weight of a first epoxy hardener comprising a plurality of a functional phenol resin; (c) 20 to 250 parts by weight of a second epoxy hardener comprising an amine epoxy hardener, an acid anhydride based epoxy hardener, or a mixture of the foregoing; (d) 0.1 to 10 a part by weight of a hardening accelerator; and (e) 30 to 150 parts by weight of a modifier formed of a thermoplastic resin.
在本發明之黏著劑組合物中，組成份(b)之第一環氧硬化劑與組成份(c)之第二環氧硬化劑，其環氧反應當量較佳為300或更低。此外，組成份(b)之第一環氧硬化劑與組成份(c)之第二環氧硬化劑，以數目平均分子量而言，其分子量較佳為3000或更高。In the adhesive composition of the present invention, the first epoxy hardener of the component (b) and the second epoxy hardener of the component (c) preferably have an epoxy reaction equivalent of 300 or less. Further, the first epoxy hardener of the component (b) and the second epoxy hardener of the component (c) have a molecular weight of preferably 3,000 or more in terms of a number average molecular weight.
其中，構成本發明黏著劑組合物之組成份(b)的多功能酚樹脂，其單一分子內具有二個或多個酚性羥基，且所述羥基的當量為100至300，滿足組成份(b)與組成份(c)的條件；同時，組成份(c)之胺類環氧硬化劑是一種醋酸乙烯酯-馬來酸酐共聚物或是一種苯乙烯-馬來酸酐共聚物。Wherein the multifunctional phenol resin constituting the component (b) of the adhesive composition of the present invention has two or more phenolic hydroxyl groups in a single molecule, and the hydroxyl group has an equivalent weight of from 100 to 300, which satisfies the component part ( b) with the condition of component (c); at the same time, the amine epoxy hardener of component (c) is a vinyl acetate-maleic anhydride copolymer or a styrene-maleic anhydride copolymer.
在本發明之黏著劑組合物中，組成份(e)之熱塑性樹脂可為單一樹脂或為多種樹脂的混合物；所述樹脂係選自包含聚酯多元醇、分散在環氧樹脂內的丙烯酸橡膠、核殼型橡膠、端羧基丁腈橡膠、丙烯腈-丁二烯-苯乙烯、聚二甲基矽氧烷及苯氧樹脂之群組。In the adhesive composition of the present invention, the thermoplastic resin of the component (e) may be a single resin or a mixture of a plurality of resins; the resin is selected from the group consisting of polyester polyols and acrylic rubber dispersed in an epoxy resin. Group of core-shell rubber, carboxyl-terminated nitrile rubber, acrylonitrile-butadiene-styrene, polydimethyloxane and phenoxy resin.
此外，本發明之黏著劑組合物，可進而包括(f)0.001至1重量份的氟系表面活性劑。Further, the adhesive composition of the present invention may further comprise (f) 0.001 to 1 part by weight of a fluorine-based surfactant.
所述黏著劑組合物之清漆較佳在一有機溶劑中包含10至50%重量比的固形物含量。The varnish of the adhesive composition preferably contains a solid content of 10 to 50% by weight in an organic solvent.
本發明亦提供一種半導體封裝用膠帶，作為所述黏著劑組合物的一種用途。The present invention also provides an adhesive tape for a semiconductor package as one use of the adhesive composition.
本發明之第一較佳實施例中提供一種引腳固定膠帶，此種膠帶係在一基膜上具有所述黏著劑組合物形成的黏著層。In a first preferred embodiment of the present invention, there is provided a pin fixing tape which is provided with an adhesive layer formed of the adhesive composition on a base film.
此外，本發明之第二較佳實施例中提供一種雙面膠帶，此種 膠帶係在一離型膜上具有所述黏著劑組合物形成的黏著層。Furthermore, in a second preferred embodiment of the present invention, a double-sided tape is provided. The tape is provided with an adhesive layer formed of the adhesive composition on a release film.
當所述黏著層之製作厚度為20μm時，本發明的膠帶具有以下特性：(a)在30V或更高電壓下進行高加速應力測試時，其絕緣特性可維持500小時以上的電氣短路抗性；以及(b)當膠帶被貼合於一印刷電路板之銅箔粗糙面上後，在200℃或更高溫度下，以180°角剝除膠帶時，其韌性滿足1.0至2.5N/cm(牛頓/公分)的高溫黏著性。When the adhesive layer is formed to have a thickness of 20 μm, the tape of the present invention has the following characteristics: (a) The electrical short-circuit resistance of the insulating property can be maintained for more than 500 hours when subjected to a high accelerated stress test at a voltage of 30 V or higher. And (b) when the tape is attached to the rough surface of the copper foil of a printed circuit board, the toughness satisfies 1.0 to 2.5 N/cm when the tape is peeled at an angle of 180° at 200 ° C or higher. (Newton/cm) high temperature adhesion.
本發明可提供一種黏著劑組合物，係於一種環氧基樹脂中包含最適量的環氧硬化劑，藉由增加交聯密度而增進硬化網絡的斷裂韌性，因此可在30V或更高之高電壓時確保其電氣可靠度；同時，由於分子在硬化網絡內高度交聯，因而可於200℃或更高溫度下獲得優異的高溫黏著性。The present invention can provide an adhesive composition comprising an optimum amount of an epoxy hardener in an epoxy resin, which improves the fracture toughness of the hardened network by increasing the crosslinking density, and thus can be at 30 V or higher. The electrical reliability is ensured at the voltage; at the same time, because the molecules are highly crosslinked in the hardened network, excellent high temperature adhesion can be obtained at 200 ° C or higher.
此外，由於此種黏著劑組合物具有高溫黏著性與高電壓時的增進絕緣可靠度，適合作為半導體封裝用膠帶，因此可使用此種黏著劑組合物提供引腳固定膠帶或雙面膠帶。Further, since such an adhesive composition has high-temperature adhesion and improved insulation reliability at a high voltage, it is suitable as a tape for semiconductor packaging, and thus such an adhesive composition can be used to provide a pin-fixing tape or a double-sided tape.
本發明的引腳固定膠帶或雙面膠帶在打線製程中具有高度的引腳偏移抗力，並可在導線架組裝完成後，滿足高電壓時的絕緣可靠度與高溫下的黏著性。The pin fixing tape or the double-sided tape of the invention has high pin offset resistance in the wire bonding process, and can satisfy the insulation reliability at high voltage and the adhesion at high temperature after the lead frame is assembled.
1‧‧‧聚醯胺薄膜1‧‧‧ Polyamide film
2‧‧‧鋁板2‧‧‧Aluminum plate
3‧‧‧黏劑層3‧‧‧Adhesive layer
4‧‧‧滑移並分開的部份4‧‧‧Sliding and separate parts
第一圖：顯示用於測試本發明引腳固定膠帶高電壓絕緣可靠度之測試片，其中係在一聚醯胺薄膜上形成一銅電路。First: A test piece for testing the high voltage insulation reliability of the pin fixing tape of the present invention, in which a copper circuit is formed on a polyimide film.
第二圖：顯示經由熱貼合將一片引腳固定膠帶沿其黏著方向貼在第一圖所示測試片的銅電路上，製成一個樣品。The second figure shows that a piece of pin fixing tape is attached to the copper circuit of the test piece shown in the first figure in the adhesive direction by heat bonding to prepare a sample.
第三圖：顯示本發明引腳固定膠帶進行高電壓絕緣可靠度測試的結果。Third: shows the results of the high voltage insulation reliability test of the pin fixing tape of the present invention.
第四圖：顯示本發明引腳固定膠帶於高電壓絕緣可靠度測試後，使用顯微鏡對樣品上的電路單元進行觀察的結果。Fig. 4 is a view showing the result of observing the circuit unit on the sample using a microscope after the high-voltage insulation reliability test of the pin fixing tape of the present invention.
第五圖：顯示一種高溫韌性量測方法，用以測試本發明引腳固定膠帶之高溫可靠度。Figure 5: shows a high temperature toughness measurement method to test the high temperature reliability of the pin fixing tape of the present invention.
本發明提供一種黏著劑組合物，其包含(a)100重量份之環氧基樹脂；(b)30至100重量份之第一環氧硬化劑，其包含一種多功能酚樹脂；(c)20至250重量份之第二環氧硬化劑，其包含一種胺類環氧硬化劑、一種酸酐基環氧硬化劑、或前二者之混合物；(d)0.1至10重量份之硬化促進劑；及(e)30至150重量份由熱塑性樹脂形成之改質劑。The present invention provides an adhesive composition comprising (a) 100 parts by weight of an epoxy resin; (b) 30 to 100 parts by weight of a first epoxy hardener comprising a multifunctional phenol resin; (c) 20 to 250 parts by weight of a second epoxy hardener comprising an amine epoxy hardener, an acid anhydride based epoxy hardener, or a mixture of the foregoing; (d) 0.1 to 10 parts by weight of a hardening accelerator And (e) 30 to 150 parts by weight of a modifier formed of a thermoplastic resin.
本發明之黏著劑組合物係在一種環氧基樹脂內包含一種特定的環氧硬化劑作為硬化劑，其環氧反應當量為300或更低並具有高分子量；此種環氧硬化劑與環氧樹脂進行硬化反應，藉由增加交聯密度而增加硬化網絡的斷裂韌性。因此，B階的交聯密度增加，並經由改善熱固性網絡的脆性而獲得增進的斷裂韌性。The adhesive composition of the present invention comprises a specific epoxy hardener as a hardener in an epoxy resin, having an epoxy reaction equivalent of 300 or less and having a high molecular weight; the epoxy hardener and the ring The oxyresin undergoes a hardening reaction to increase the fracture toughness of the hardened network by increasing the crosslinking density. Therefore, the crosslinking density of the B-stage is increased, and improved fracture toughness is obtained by improving the brittleness of the thermosetting network.
此外，在熱固性網絡中額外包含一種熱塑性樹脂時，可使熱固性網絡獲得韌性；或者，藉由使用具有大當量的熱固性樹脂，可以調整黏著劑在高溫下的流動性。In addition, when a thermoplastic resin is additionally included in the thermosetting network, the thermosetting network can be made tough; or, by using a thermosetting resin having a large equivalent, the fluidity of the adhesive at a high temperature can be adjusted.
以下詳細說明本發明黏著劑組合物的每一種組成份。Each component of the adhesive composition of the present invention will be described in detail below.
在本發明的黏著劑組合物中，組成份(a)的環氧基樹脂並無特別限制，但是在分子量為200或更高並具有脂肪系、脂環系或芳香系之環 形或線形主鏈的各種分子中，較佳使用二種或多種於單一分子中具有二個或多個縮水甘油基團的環氧樹脂。In the adhesive composition of the present invention, the epoxy resin of the component (a) is not particularly limited, but has a molecular weight of 200 or more and has a fat, alicyclic or aromatic ring. Among the various molecules of the shape or linear backbone, it is preferred to use two or more epoxy resins having two or more glycidyl groups in a single molecule.
舉例而言，所述環氧基樹脂可包含一種在單一主鏈中具有一個縮水甘油基團的環氧樹脂，諸如雙酚A環氧樹脂、雙酚F環氧樹脂、雙酚AD環氧樹脂、雙酚S環氧樹脂、脂環族環氧樹脂、脂環族鏈環氧樹脂、酚系酚醛清漆環氧樹脂、甲酚酚醛環氧樹脂、萘系環氧樹脂、含氟環氧樹脂、含亞醯胺基環氧樹脂等；或可包含一種經由不同物理特性的樹脂或橡膠與主鏈產生反應而得到的環氧樹脂，諸如表鹵代醇改性環氧樹脂、丙烯酸系改性環氧樹脂、乙烯改性環氧樹脂、彈性體改性環氧樹脂、胺改性環氧樹脂等。For example, the epoxy resin may comprise an epoxy resin having a glycidyl group in a single main chain, such as bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin. , bisphenol S epoxy resin, cycloaliphatic epoxy resin, cycloaliphatic chain epoxy resin, phenolic novolac epoxy resin, cresol novolac epoxy resin, naphthalene epoxy resin, fluorine-containing epoxy resin, a ruthenium-containing epoxy resin or the like; or an epoxy resin obtained by reacting a resin or a rubber having different physical properties with a main chain, such as an epihalool-modified epoxy resin or an acrylic modified ring Oxygen resin, ethylene modified epoxy resin, elastomer modified epoxy resin, amine modified epoxy resin, and the like.
其中，環氧基樹脂的當量較佳為470或更低，更佳為300或更低，以確保硬化後的玻璃轉化溫度與機械強度。此外，從硬化產品的較佳物理特性等方面而言，最好使用芳香族環氧樹脂作為環氧基樹脂。Among them, the epoxy resin preferably has an equivalent weight of 470 or less, more preferably 300 or less, to ensure glass transition temperature and mechanical strength after hardening. Further, from the viewpoint of preferable physical properties of the cured product, etc., it is preferred to use an aromatic epoxy resin as the epoxy resin.
本發明中，芳香族環氧樹脂是指一種在單一分子中具有芳環骨架的環氧樹脂，因此，所述組成份(a)在單一分子中具有二個或多個環氧基團，並使用當量為470或更小的芳香族環氧樹脂。此外，可使用一種環氧樹脂或使用二種或多種環氧樹脂的混合物。In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring skeleton in a single molecule, and therefore, the component (a) has two or more epoxy groups in a single molecule, and An aromatic epoxy resin having an equivalent weight of 470 or less is used. Further, an epoxy resin or a mixture of two or more epoxy resins may be used.
在本發明之黏著劑組合物中，組成份(b)是一種第一環氧硬化劑，較佳是單一分子中具有二個或多個酚性羥基的酚樹脂，更佳是一種羥基當量為100至300的多功能酚樹脂。其中，若酚樹脂的羥基當量低於100，由於環氧基樹脂的硬化產物具脆性，會使半導體封裝的緩衝特性退化；但若羥基當量超過300，由於交聯密度降低，所以此種組合物的絕緣可 靠度及耐熱性會在高電壓時趨於劣化。In the adhesive composition of the present invention, component (b) is a first epoxy hardener, preferably a phenol resin having two or more phenolic hydroxyl groups in a single molecule, more preferably a hydroxyl equivalent. 100 to 300 multifunctional phenolic resin. Wherein, if the hydroxyl equivalent of the phenol resin is less than 100, since the hardened product of the epoxy resin is brittle, the buffering property of the semiconductor package is degraded; but if the hydroxyl equivalent exceeds 300, the composition is lowered due to a decrease in crosslinking density. Insulation The degree of reliability and heat resistance tend to deteriorate at high voltages.
因此，較適合作為組成份(b)第一環氧硬化劑的多功能酚樹脂，可為單一樹脂或為二或多種樹脂的混合物；此等樹脂可選自包括聯苯類酚樹脂、新酚酚醛清漆樹脂、雙酚F酚醛清漆樹脂、雙酚F樹脂、雙酚A樹脂、酚系酚醛清漆樹脂、甲酚酚醛環氧樹脂、雙酚A酚醛清漆樹脂、酚醛芳烷基樹脂、多功能酚醛清漆樹脂、二環戊二烯酚系酚醛清漆樹脂、氨基三氮雜苯酚系酚醛清漆樹脂、及聚丁二烯酚系酚醛清漆樹脂之群組。Therefore, the multifunctional phenol resin which is more suitable as the component (b) first epoxy hardener may be a single resin or a mixture of two or more resins; these resins may be selected from the group consisting of biphenyl phenol resins and neophenols. Novolac resin, bisphenol F novolac resin, bisphenol F resin, bisphenol A resin, phenolic novolac resin, cresol novolac epoxy resin, bisphenol A novolac resin, phenolic aralkyl resin, multifunctional phenolic A group of a varnish resin, a dicyclopentadiene phenol novolak resin, an aminotriaza phenol novolak resin, and a polybutadiene phenol novolak resin.
此外，以數目平均分子量而言，所述多功能酚樹脂係使用分子量為3000或更高之組成份，以使本發明之黏著劑組合物可在200℃或更高溫度下維持黏著性。其中，分子量為3000或更高的聚合物會誘發聚合物鏈之間的纏結，因而可在200℃或更高溫度下充分維持黏著性。Further, in terms of the number average molecular weight, the multifunctional phenol resin is a component having a molecular weight of 3,000 or more, so that the adhesive composition of the present invention can maintain adhesion at 200 ° C or higher. Among them, a polymer having a molecular weight of 3,000 or more induces entanglement between polymer chains, and thus the adhesiveness can be sufficiently maintained at 200 ° C or higher.
因此，本發明實施例中雖然使用雙酚A酚醛清漆樹脂(美國Momentive公司出品之SD-1508酚樹脂)作為滿足上述條件的多功能酚樹脂，但也可使用滿足上述條件的其他商品或合成複合劑。Therefore, in the examples of the present invention, although bisphenol A novolak resin (SD-1508 phenol resin produced by Momentive Co., Ltd.) is used as the multifunctional phenol resin satisfying the above conditions, other products or synthetic composites satisfying the above conditions may be used. Agent.
在本發明之黏著劑組合物中，當組成份(b)以多功能酚樹脂作為一種環氧硬化劑時，環氧官能團與酚性羥基間的當量比通常被調整到1：1.2與1：0.6之間。然而，由於本發明中額外使用組成份(c)之第二環氧硬化劑，所以較佳降低酚樹脂的份量，以便限制酚的硬化反應而可增加B階的交聯密度。In the adhesive composition of the present invention, when the component (b) is a multifunctional phenol resin as an epoxy hardener, the equivalent ratio between the epoxy functional group and the phenolic hydroxyl group is usually adjusted to 1:1.2 and 1: Between 0.6. However, since the second epoxy hardener of the component (c) is additionally used in the present invention, it is preferred to reduce the amount of the phenol resin so as to limit the hardening reaction of the phenol to increase the crosslinking density of the B-stage.
因此，上述當量比較佳調整到1：0.6或更低；同時，從重量比方面來看，相對於100重量份之組成份(a)之環氧基樹脂，較佳包含30至100重量份的多功能酚樹脂，亦即組成份(b)之第一環氧硬化劑。其中，若多功 能酚樹脂的含量少於30重量份，整體黏著劑組合物內留下的環氧樹脂或未反應的硬化劑會降低，且其交聯也會降低。若多功能酚樹脂的含量超過100重量份，則黏著劑組合物內可能會發生在原定硬化反應及分解反應之外的副反應。Therefore, the above equivalent is preferably adjusted to 1:0.6 or less; and, in terms of weight ratio, it is preferably 30 to 100 parts by weight based on 100 parts by weight of the epoxy resin of the component (a). A multifunctional phenolic resin, that is, a first epoxy hardener of component (b). Among them, if you do more work When the content of the phenol resin is less than 30 parts by weight, the epoxy resin or the unreacted hardener remaining in the overall adhesive composition is lowered, and the crosslinking thereof is also lowered. When the content of the multifunctional phenol resin exceeds 100 parts by weight, side reactions other than the original hardening reaction and the decomposition reaction may occur in the adhesive composition.
在本發明之黏著劑組合物中，組成份(c)是一種第二環氧硬化劑，可使用任何已公知且能與環氧官能團進行硬化反應的環氧硬化劑。因此，最好可使用胺類硬化劑或酸酐基硬化劑。In the adhesive composition of the present invention, component (c) is a second epoxy hardener, and any epoxy hardener which is known to be hardenable with an epoxy functional group can be used. Therefore, it is preferred to use an amine hardener or an acid anhydride based hardener.
較佳是使用酸酐基硬化劑，而且酸酐基硬化劑與本類技術中用作引腳固定膠帶基膜的聚醯亞胺(PI)薄膜間，具有高度的界面黏著性。使用酸酐基硬化劑作為引腳固定膠帶的黏著劑時(此乃本發明黏著劑組合物的目的之一)，它對尺寸的變化較不敏感，而且，由於其初始反應溫度較高，所以具有極佳的絕緣性。It is preferred to use an acid anhydride-based hardener, and the acid anhydride-based hardener has a high degree of interfacial adhesion with a polyimide film (PI) film used as a base film for a pin-fixing tape in the prior art. When an acid anhydride-based hardener is used as an adhesive for a pin-fixing tape (this is one of the purposes of the adhesive composition of the present invention), it is less sensitive to dimensional changes and, because of its higher initial reaction temperature, Excellent insulation.
雖然酸酐基硬化劑具有高初始反應溫度與低硬化反應速率，但是本發明組成份(d)內包含之硬化促進劑的反應，可以改進硬化反應速率。Although the acid anhydride-based hardener has a high initial reaction temperature and a low hardening reaction rate, the reaction of the hardening accelerator contained in the component (d) of the present invention can improve the hardening reaction rate.
因此，藉由包含組成份(d)之硬化促進劑，可以調整硬化溫度與速率。所述酸酐基硬化劑最好具有較長的“可使用時間”(pot life)；而其較佳實例可選自包括甲基六氫苯酐、甲基四氫苯酐、均苯四甲酸二酐、二苯酮四甲酸二酐、及鄰苯二甲酸酐之群組。Therefore, the hardening temperature and rate can be adjusted by the hardening accelerator containing the component (d). The acid anhydride-based hardener preferably has a longer "pot life"; and preferred examples thereof may be selected from the group consisting of methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, pyromellitic dianhydride, a group of benzophenone tetracarboxylic dianhydride and phthalic anhydride.
本發明黏著劑組合物中所含組成份(c)之第二環氧硬化劑，係使用一種，以數目平均分子量而言，分子量為3000或更高的組成份；其比值與組成份(b)之多功能酚樹脂的比值相同，以便在高溫下維持高黏著性。The second epoxy hardener of the component (c) contained in the adhesive composition of the present invention is a component having a molecular weight of 3000 or more in terms of number average molecular weight; ratio and composition (b) The ratio of the multifunctional phenolic resin is the same in order to maintain high adhesion at high temperatures.
與以上例舉之單分子環氧硬化劑不同的是，數目平均分子量為3000或更高的環氧硬化劑，通常會經由與其他聚合物的共聚作用而增加分子量。Unlike the single-molecule epoxy hardener exemplified above, an epoxy hardener having a number average molecular weight of 3,000 or more generally increases the molecular weight by copolymerization with other polymers.
滿足本發明中數目平均分子量為3000或更高分子量的酸酐基硬化劑，其較佳實例可從醋酸乙烯酯-馬來酸酐共聚物及苯乙烯-馬來酸酐共聚物中選取，但不限於此等共聚物。An acid anhydride-based hardener having a molecular weight average molecular weight of 3000 or more in the present invention is satisfied, and preferred examples thereof are selected from the group consisting of vinyl acetate-maleic anhydride copolymer and styrene-maleic anhydride copolymer, but are not limited thereto. Copolymer.
苯乙烯-馬來酸酐共聚物更適於用作第二環氧硬化劑。由於具有大體積側鏈結構的共聚物鏈會產生空間位阻效應，所以苯乙烯-馬來酸酐共聚物較之其他各種具有類似分子量的硬化劑，更能在分子鏈間形成良好的纏結，如此可有效控制黏著劑在高溫時的流動性。因此，最好使用苯乙烯-馬來酸酐共聚物作為第二環氧硬化劑。Styrene-maleic anhydride copolymers are more suitable for use as the second epoxy hardener. Since the copolymer chain having a large-volume side chain structure produces a steric hindrance effect, the styrene-maleic anhydride copolymer can form a good entanglement between the molecular chains than other various hardeners having a similar molecular weight. This can effectively control the fluidity of the adhesive at high temperatures. Therefore, it is preferred to use a styrene-maleic anhydride copolymer as the second epoxy hardener.
使用胺類硬化劑作為本發明黏著劑組合物內所含組成份(c)之第二環氧硬化劑時，最好從聚乙烯胺與聚醚胺中選取；並且，使用此種第二環氧硬化劑時，較佳是與上述酸酐基硬化劑一同混合之形式。When an amine hardener is used as the second epoxy hardener of the component (c) contained in the adhesive composition of the present invention, it is preferably selected from the group consisting of polyvinylamine and polyetheramine; and, the second ring is used. In the case of the oxygen hardener, it is preferably a form mixed with the above acid anhydride-based hardener.
本發明黏著劑組合物內所含組成份(c)之第二環氧硬化劑，相對於100重量份的環氧樹脂【即組成份(a)】而言，其含量較佳為20至250重量份。其中，第二環氧硬化劑的含量若少於20重量份，整體黏著劑組合物內留下的環氧樹脂或未反應的硬化劑會降低，且其交聯密度也會降低。第二環氧硬化劑的含量若超過250重量份，則黏著劑組合物內可能會發生在原定硬化反應及分解反應之外的副反應。The second epoxy hardener of the component (c) contained in the adhesive composition of the present invention preferably has a content of 20 to 250 with respect to 100 parts by weight of the epoxy resin [i.e., component (a)]. Parts by weight. Wherein, if the content of the second epoxy hardener is less than 20 parts by weight, the epoxy resin or the unreacted hardener remaining in the overall adhesive composition is lowered, and the crosslinking density thereof is also lowered. When the content of the second epoxy curing agent exceeds 250 parts by weight, side reactions other than the original hardening reaction and the decomposition reaction may occur in the adhesive composition.
本發明黏著劑組合物內所含的組成份(d)是一種硬化促進劑，用以增加組成份(a)之環氧基樹脂被組成份(b)之第一環氧硬化劑及組成 份(c)之第二環氧硬化劑硬化的速率。The component (d) contained in the adhesive composition of the present invention is a hardening accelerator for increasing the first epoxy hardener and composition of the epoxy resin component (b) of the component (a) The rate at which the second epoxy hardener of part (c) is hardened.
若將本發明之黏著劑組合物用作半導體封裝用的膠帶，諸如引腳固定膠帶，由於所述黏著劑組合物內含有組成份(d)之硬化促進劑，所以當引腳固定膠帶貼合於印刷電路板或電子裝配組件時，可以縮短硬化時間。If the adhesive composition of the present invention is used as a tape for semiconductor encapsulation, such as a pin fixing tape, since the adhesive composition contains the hardening accelerator of the component (d), when the pin fixing tape is attached Hardening time can be shortened when printing circuit boards or electronic assembly components.
較佳是，儘管本發明硬化劑的硬化促進作用在溫度100℃或更低的情況時會受到限制，以免對黏著劑的可使用時間產生不良效應，但是硬化反應在溫度100℃或更高時會加速，以改進交聯密度。Preferably, although the hardening promoting action of the hardener of the present invention is limited at a temperature of 100 ° C or lower to avoid an adverse effect on the usable time of the adhesive, the hardening reaction is at a temperature of 100 ° C or higher. Will accelerate to improve crosslink density.
諸如三苯基膦之有機膦類化合物，諸如2-乙基-4-甲基咪唑之咪唑類化合物，或三元胺，都可作為較佳的硬化促進劑。An organic phosphine compound such as triphenylphosphine, an imidazole compound such as 2-ethyl-4-methylimidazole, or a triamine can be used as a preferred hardening accelerator.
本發明組成份(d)之硬化促進劑，相對於100重量份的環氧基樹脂【即組成份(a)】而言，其含量較佳為0.1至10重量份。其中，硬化促進劑的含量若少於0.1重量份，將無法預期硬化促進劑的促進效應；但若硬化促進劑的含量超過10重量份，由於會使製程中快速發生硬化反應而產生過於堅硬的黏著劑層，因而難以獲得貼合所需的黏著特性，並對尺寸穩定性有不良影響。The hardening accelerator of the component (d) of the present invention is preferably contained in an amount of from 0.1 to 10 parts by weight based on 100 parts by weight of the epoxy resin (i.e., component (a)). Wherein, if the content of the hardening accelerator is less than 0.1 parts by weight, the promoting effect of the hardening accelerator may not be expected; but if the content of the hardening accelerator exceeds 10 parts by weight, it may be too hard due to a rapid hardening reaction in the process. The adhesive layer is difficult to obtain the adhesive properties required for the bonding and has an adverse effect on the dimensional stability.
本發明黏著劑組合物內所含的組成份(e)是一種由熱塑性樹脂形成的改質劑，它可改善環氧樹脂的脆性以增加斷裂韌性並減輕內應力。The component (e) contained in the adhesive composition of the present invention is a modifier formed of a thermoplastic resin which improves the brittleness of the epoxy resin to increase the fracture toughness and reduce the internal stress.
本發明黏著劑組合物內所含組成份(e)之改質劑，相對於100重量份的環氧基樹脂【即組成份(a)】而言，其含量較佳為30至150重量份。其中，改質劑的含量若少於30重量份，將不利於增加斷裂韌性及減輕內應力；但若改質劑的含量超過150重量份，所述黏著劑組合物內的硬化組成份 含量將大幅降低，因此，硬化後的機械及電氣可靠度會降低。The modifying agent of the component (e) contained in the adhesive composition of the present invention preferably has a content of 30 to 150 parts by weight based on 100 parts by weight of the epoxy resin [ie, component (a)]. . Wherein, if the content of the modifier is less than 30 parts by weight, it is disadvantageous for increasing fracture toughness and reducing internal stress; but if the content of the modifier exceeds 150 parts by weight, the hardening component in the adhesive composition The content will be greatly reduced, so the mechanical and electrical reliability after hardening will be reduced.
用作組成份(e)改質劑的熱塑性樹脂，根據黏著劑其他組成份的類型而定，可選自聚酯多元醇、分散在環氧樹脂內的丙烯酸橡膠、核殼型橡膠、端羧基丁腈橡膠(CTBN)、丙烯腈-丁二烯-苯乙烯共聚物(亦即ABS樹脂)、聚二甲基矽氧烷、苯氧樹脂等。The thermoplastic resin used as the component (e) modifier is selected from the group consisting of polyester polyols, acrylic rubber dispersed in epoxy resin, core-shell rubber, and terminal carboxyl group depending on the type of other components of the adhesive. Nitrile rubber (CTBN), acrylonitrile-butadiene-styrene copolymer (also known as ABS resin), polydimethyl siloxane, phenoxy resin, and the like.
較佳是，使用本發明之黏著劑組成物作成半導體封裝用膠帶時，由於被貼合的位置應該是可撓曲的，因此要使用聚酯多元醇或端羧基丁腈橡膠(CTBN)。Preferably, when the adhesive composition of the present invention is used as a tape for semiconductor encapsulation, since the position to be bonded should be flexible, a polyester polyol or a terminal carboxylated nitrile rubber (CTBN) is used.
此外，由於根據本發明之目的，在高溫時必須具有強黏著性特徵，所以較佳是使用具有相當高玻璃轉化溫度的環氧樹脂或使用具有良好相容性的苯氧樹脂。Further, since it is necessary to have a strong adhesive property at a high temperature in accordance with the object of the present invention, it is preferred to use an epoxy resin having a relatively high glass transition temperature or to use a phenoxy resin having good compatibility.
更佳是，可與苯氧樹脂一同使用聚酯多元醇或端羧基丁腈橡膠。More preferably, a polyester polyol or a terminal carboxylated nitrile rubber can be used together with the phenoxy resin.
核殼型橡膠的微粒是具有一核層與一殼層的橡膠微粒。舉例而言，它可為一種雙層結構，其中之外殼層為一種玻璃狀聚合物，而其內殼層為一種橡膠狀聚合物；或者可為一種三層結構，其外殼層為一種玻璃狀聚合物，其中間層為一種橡膠狀聚合物，而其內核層為一種玻璃狀聚合物。其中，所述玻璃狀聚合物為一種甲基丙烯酸甲酯聚合物，而所述橡膠狀聚合物包括一種丙烯酸丁酯聚合物。The particles of the core-shell type rubber are rubber particles having a core layer and a shell layer. For example, it may be a two-layer structure in which the outer shell layer is a glassy polymer and the inner shell layer is a rubbery polymer; or it may be a three-layer structure in which the outer shell layer is a glassy A polymer wherein the intermediate layer is a rubbery polymer and the inner core layer is a glassy polymer. Wherein the glassy polymer is a methyl methacrylate polymer and the rubbery polymer comprises a butyl acrylate polymer.
本發明之黏著劑組合物可進而包含一種添加劑，諸如一種前述組合物各種組成份不同的表面活性劑、偶聯劑、無機充填劑等。其中，相對於100重量份的環氧基樹脂【即組成份(a)】而言，可包含0.001至1重量 份的氟系表面活性劑作為添加劑。The adhesive composition of the present invention may further comprise an additive such as a surfactant having a different composition of the foregoing composition, a coupling agent, an inorganic filler, and the like. Wherein, it may contain 0.001 to 1 weight with respect to 100 parts by weight of the epoxy resin [ie, component (a)] A portion of a fluorine-based surfactant is used as an additive.
尤其，使用表面活性劑時，可給予基膜適當的塗佈性能。舉例而言，較佳可使用聚合物矽氧烷，諸如有機丙烯酸類聚合物、多元醇等；或使用氟系化合物，諸如3M公司出品的FC-4430。In particular, when a surfactant is used, appropriate coating properties can be imparted to the base film. For example, a polymer siloxane, such as an organic acrylic polymer, a polyol, or the like, or a fluorine-based compound such as FC-4430 available from 3M Company can be preferably used.
本發明黏著劑組合物之清漆，係於一種有機溶劑中，包含較佳10至50%(重量比)的前述組成份固形物含量。其中，所述固形物含量若少於10%(重量比)，在乾燥過程中將不易去除殘餘的有機溶劑；但若所述固形量含量超過50%(重量比)，則不易確保各種黏著劑組合物間的充分相容性。The varnish of the adhesive composition of the present invention is contained in an organic solvent, and preferably contains 10 to 50% by weight of the aforementioned component solid content. Wherein, if the solid content is less than 10% by weight, the residual organic solvent is not easily removed during the drying process; however, if the solid content exceeds 50% by weight, it is difficult to ensure various adhesives. Adequate compatibility between the compositions.
如上所述的本發明黏著劑組合物，因為在B階中即形成高交聯密度，所以能在30V或更高之高電壓下具有優異的絕緣特性；復因為各分子在硬化網絡內高度交聯，所以可在200℃或更高之高溫下維持高黏著性。The adhesive composition of the present invention as described above has excellent insulating properties at a high voltage of 30 V or higher because it forms a high crosslinking density in the B-stage; It is linked, so it can maintain high adhesion at a high temperature of 200 ° C or higher.
此外，本發明提供一種使用前述黏著劑組合物的半導體封裝用膠帶；由於半導體封裝領域內伴隨200℃以上的高溫製程，諸如打線、軟焊等，所以可利用此種膠帶。Further, the present invention provides a tape for semiconductor packaging using the above-described adhesive composition; such a tape can be utilized because of a high-temperature process of 200 ° C or higher, such as wire bonding, soldering, etc., in the field of semiconductor packaging.
本發明之半導體封裝用膠帶，其功能有如半導體封裝體中，單一組件各個構成元件間的接面、充填劑與絕緣層；其中，所述黏著面可為雙面或單面。The tape for semiconductor packaging of the present invention functions as a junction, a filler and an insulating layer between the constituent elements of a single component in a semiconductor package; wherein the adhesive surface may be double-sided or single-sided.
黏著面一經形成後，在它被用到半導體封裝製程前，都必須加以保護，以免接觸外部大氣或受到實體損傷。因此，黏著面上通常會黏貼具有剝離特性的保護膜；其中，所述保護膜可選自聚烯烴、聚酯、或離型紙。聚烯烴諸如聚乙烯、聚氯乙烯、聚丙烯等；聚酯諸如聚對苯二甲酸乙二酯(PET)等。Once the adhesive surface is formed, it must be protected from contact with the outside atmosphere or physical damage before it is used in the semiconductor packaging process. Therefore, the protective film is usually adhered to the adhesive surface; wherein the protective film may be selected from polyolefin, polyester, or release paper. Polyolefins such as polyethylene, polyvinyl chloride, polypropylene, etc.; polyesters such as polyethylene terephthalate (PET) and the like.
保護膜較佳具有10至150微米(μm)的厚度，且可透過異於泥漿法與壓紋法的剝離法而獲得令人滿意的處理。此種保護膜可於黏著製程一開始前移除之。The protective film preferably has a thickness of 10 to 150 micrometers (μm) and is satisfactorily processed by a peeling method different from the mud method and the embossing method. This protective film can be removed before the adhesive process begins.
本發明於其半導體封裝用膠帶之第一較佳實施例中，係提供一種設於一基膜上的半導體封裝用引腳固定膠帶，其黏著層即是以本發明之黏著劑組合物形成的。In a first preferred embodiment of the tape for semiconductor packaging of the present invention, a pin fixing tape for a semiconductor package provided on a base film is provided, and the adhesive layer is formed by the adhesive composition of the present invention. .
在本發明之實施例中，所述引腳固定膠帶之物理特性測試結果顯示優異的正常溫度黏著性；從表1所示之樹脂流動性測試可以確認，此種引腳固定膠帶即使在180至230℃的高溫下受壓，仍可限制其黏著樹脂的流動性。In an embodiment of the present invention, the physical property test result of the pin fixing tape shows excellent normal temperature adhesion; from the resin fluidity test shown in Table 1, it can be confirmed that the pin fixing tape is even at 180 to The pressure at 230 ° C can still limit the fluidity of the adhesive resin.
此外，對本發明之引腳固定膠帶進行高加速應力測試(HAST)之結果，亦即，在30V或更高之高電壓下每小時測量電阻之結果，如第一圖至第三圖所示，由於在高達500小時的實驗條件下並未觀察到阻降，所以可解決高電壓下電氣短路的問題。Further, as a result of performing a high accelerated stress test (HAST) on the pin fixing tape of the present invention, that is, the result of measuring the resistance per hour at a high voltage of 30 V or higher, as shown in the first to third figures, Since no drop is observed under the experimental conditions of up to 500 hours, the problem of electrical short circuit at high voltage can be solved.
第四圖顯示進行高加速應力測試後，使用顯微鏡對所述引腳固定膠帶的電路單元進行觀察之結果；由於本發明之引腳固定膠帶不會在銅電路上產生枝晶，所以可確認此種引腳固定膠帶在高電壓下的絕緣特性。The fourth figure shows the result of observing the circuit unit of the pin fixing tape using a microscope after performing the high acceleration stress test; since the pin fixing tape of the present invention does not generate dendrites on the copper circuit, it can be confirmed The insulation properties of the pin fixing tape at high voltage.
此外，由於本發明引腳固定膠帶之高溫可靠度量測結果，確認其具有優異的滑移抗力[表2]與高溫黏著性(剝離強度)[表3]，因此可以確定，藉由控制高溫下的流動性，本發明之黏著劑組合物可確保充分的韌性。In addition, due to the high-temperature reliable measurement results of the pin-fixed tape of the present invention, it was confirmed that it has excellent slip resistance [Table 2] and high-temperature adhesion (peel strength) [Table 3], and thus it can be determined by controlling the high temperature. Under the fluidity, the adhesive composition of the present invention can ensure sufficient toughness.
在本發明半導體封裝用膠帶第一較佳實施例之引腳固定膠帶中，其基膜可用含有聚苯硫醚(PPS)或聚醯亞胺的工程塑料形成；同時， 顧及電氣絕緣與物理剛性，較佳使用聚醯亞胺薄膜。其中，聚醯亞胺薄膜的厚度較佳為10到150μm。所述基膜上，除了泥漿法與電暈法，尚可額外進行一種表面處理法。更明確地說，若在基膜上敷設本發明黏著劑組合物之清漆來形成一黏著層，且於所述清漆乾燥後，即可製成半導體封裝用的B階膠帶。其中，可在獲得黏著劑組合物清漆的過程中使用一種有機溶劑，以便易於獲得多種組成份的混合物；較佳可以使用一般溶劑或氯溶劑或二者之混合物，諸如二氯甲烷等。一般溶劑包括各種酮類，乙酸酯類及芳烴類；酮類諸如丙酮、丁酮、環己酮等；乙酸酯類諸如乙酸乙酯、乙酸丁酯、乙酸甘醇酯、丙二醇甲醚乙酸酯等；芳烴類諸如甲苯、二甲苯等。此外，所述黏著劑組合物清漆敷設到基膜上之後，經由加熱、烘乾及熟化(aging)可形成不含有機溶劑與揮發性物質的黏著層(揮發性物質諸如水份，其可經由水份吸收等而產生)。加熱與烘乾是一種高溫乾燥處理，其執行溫度為200℃或更低，較佳為180℃或更低；若是使用有機溶劑時，黏著劑內的有機溶劑可經由加熱而蒸發。熟化是一種低溫乾燥處理，其執行溫度為70℃或更低，較佳為50℃或更低；透過熟化處理，可進而減少經由水份吸收而產生的揮發性物質。In the pin fixing tape of the first preferred embodiment of the tape for semiconductor package of the present invention, the base film may be formed of an engineering plastic containing polyphenylene sulfide (PPS) or polyimine; Considering electrical insulation and physical rigidity, it is preferred to use a polyimide film. Among them, the thickness of the polyimide film is preferably from 10 to 150 μm. On the base film, in addition to the mud method and the corona method, an additional surface treatment method can be performed. More specifically, if a varnish of the adhesive composition of the present invention is applied to a base film to form an adhesive layer, and after the varnish is dried, a B-stage adhesive tape for semiconductor packaging can be obtained. Among them, an organic solvent may be used in the process of obtaining the varnish of the adhesive composition so that a mixture of a plurality of component parts can be easily obtained; preferably, a general solvent or a chlorine solvent or a mixture of the two, such as dichloromethane or the like, can be used. Typical solvents include various ketones, acetates and aromatics; ketones such as acetone, methyl ethyl ketone, cyclohexanone, etc.; acetates such as ethyl acetate, butyl acetate, glycol acetate, propylene glycol methyl ether acetate Etc.; aromatic hydrocarbons such as toluene, xylene, and the like. In addition, after the adhesive composition varnish is applied to the base film, an adhesive layer containing no organic solvent and volatile substances (such as moisture) can be formed via heating, drying and aging. Produced by moisture absorption, etc.). The heating and drying is a high-temperature drying treatment, and the execution temperature is 200 ° C or lower, preferably 180 ° C or lower; if an organic solvent is used, the organic solvent in the adhesive can be evaporated by heating. The aging is a low-temperature drying treatment which is performed at a temperature of 70 ° C or lower, preferably 50 ° C or lower; and through the aging treatment, the volatile matter generated by moisture absorption can be further reduced.
此外，本發明於其半導體封裝用膠帶之第二較佳實施例中，係提供一種半導體封裝用雙面膠帶，其中係使用所述黏著劑組合物在一離型膜上形成黏著層。Further, the present invention provides a double-sided tape for semiconductor encapsulation in a second preferred embodiment of the tape for semiconductor encapsulation, wherein the adhesive composition is used to form an adhesive layer on a release film.
第二實施例與前述半導體封裝用引腳固定膠帶不同的是，它使用一種具有剝離特性的離型膜作為基膜；較佳是，所述離型膜可選自聚烯烴、聚酯或一種離型紙。聚烯烴諸如聚乙烯、聚氯乙烯、聚丙烯等；聚 酯諸如聚對苯二甲酸乙二酯等。所述雙面膠帶係以機械方式壓縮製作，亦即在100℃或更低溫度下施加8百帕(MPa)或更低的壓力，施壓時間少於5分鐘；取下作為基膜的離型膜，最後再使用原先與離型膜緊密貼合的黏著面。The second embodiment is different from the above-mentioned pin-bonding tape for semiconductor package in that it uses a release film having a peeling property as a base film; preferably, the release film may be selected from polyolefin, polyester or a kind Release paper. Polyolefins such as polyethylene, polyvinyl chloride, polypropylene, etc.; Esters such as polyethylene terephthalate and the like. The double-sided tape is mechanically compressed, that is, a pressure of 8 hectopascals (MPa) or less is applied at a temperature of 100 ° C or lower, and the pressing time is less than 5 minutes; the separation as a base film is removed. The film is finally used, and the adhesive surface which is originally adhered to the release film is used.
本發明實施例中雖然僅說明引腳固定膠帶的物理特性，但是此等物理特性係根據所述黏著劑組合物之特徵；此外，由於所述雙面膠帶是本發明半導體封裝用膠帶之典型用途，而它亦採用所述黏著劑組合物，所以自然可以理解所述雙面膠帶能確保高電壓下的優異絕緣性與高溫下的優異黏著性。In the embodiment of the present invention, although only the physical properties of the pin fixing tape are described, the physical properties are based on the characteristics of the adhesive composition; moreover, since the double-sided tape is a typical use of the tape for semiconductor packaging of the present invention. While it also employs the adhesive composition, it is naturally understood that the double-sided tape can ensure excellent insulation at high voltage and excellent adhesion at high temperatures.
亦即，當製作的黏著層厚度為20μm時，本發明之半導體封裝用膠帶可滿足以下條件：(a)使用條寬與間距為200μm的測試片進行30V或更高電壓的高加速應力測試時，在相對濕度85%與130℃或更高溫度的情況下，其絕緣特性可維持500小時以上的電氣短路抗性；(b)當膠帶被貼合於一印刷電路板之銅箔粗糙面上後，在200℃或更高溫度下，以180°角剝除膠帶時，其韌性滿足1.0至2.5N/cm(牛頓/公分)的高溫黏著性。That is, when the thickness of the adhesive layer to be formed is 20 μm, the tape for semiconductor package of the present invention satisfies the following conditions: (a) When a test piece having a strip width and a pitch of 200 μm is used for a high-acceleration stress test of 30 V or higher. In the case of relative humidity of 85% and 130 ° C or higher, the insulation properties can maintain electrical short circuit resistance of more than 500 hours; (b) when the tape is attached to the rough surface of the copper foil of a printed circuit board Thereafter, when the tape is peeled off at an angle of 180° at 200 ° C or higher, the toughness satisfies the high-temperature adhesion of 1.0 to 2.5 N/cm (Newton/cm).
此外，當本發明之半導體封裝用膠帶貼在一鋁板上的長度為5mm(公厘)，並在200℃或更高溫度下，以180°角拉它時，可滿足20至35N(牛頓)的滑移抗力。Further, when the tape for semiconductor package of the present invention is attached to an aluminum plate to have a length of 5 mm (mm) and is pulled at a temperature of 200 ° C or higher at a temperature of 180 °, it can satisfy 20 to 35 N (Newton). Slip resistance.
以下將透過實施例進一步詳細說明本發明。Hereinafter, the present invention will be described in further detail by way of examples.
其目的是進一步具體說明本發明，然而本發明之範圍並不限於此等實施例。It is intended to further clarify the invention, but the scope of the invention is not limited to such embodiments.
<實例1>製作黏著劑合成物<Example 1> Making an adhesive composition
相對於作為組成份(a)環氧基樹脂的100重量份的二環戊二 烯環氧樹脂(日本Nippon Kayaku公司出品之XD-1000)，使用50重量份的雙酚A酚醛清漆樹脂(美國Momentive公司出品之SD-1508，其數目平均分子量為3100，環氧當量為120)作為組成份(b)之第一環氧硬化劑，使用40重量份的苯乙烯-馬來酸酐(其數目平均分子量為4500，環氧當量為260)作為組成份(c)之第二環氧硬化劑，使用0.1重量份的2-甲基咪唑作為組成份(d)之硬化促進劑，使用80重量份的丁腈橡膠作為組成份(e)中以熱塑性樹脂形成之改質劑，並使用0.1重量份的氟系表面活性劑【組成份(f)】(美國3M公司出品的FC4430)作為添加劑；將這些組成份添加到丁酮溶劑內，然後在室溫與大氣壓力的條件下將其混合5小時，以製作所述黏著劑組合物之清漆，其中，在整體組合物內的固形物含量濃度為28%(重量比)。100 parts by weight of dicyclopentane as a component (a) epoxy resin Epene epoxy resin (XD-1000 from Nippon Kayaku Co., Japan), using 50 parts by weight of bisphenol A novolak resin (SD-1508 from Momentive, USA, having a number average molecular weight of 3,100 and an epoxy equivalent of 120) As the first epoxy hardener of the component (b), 40 parts by weight of styrene-maleic anhydride (having a number average molecular weight of 4500 and an epoxy equivalent of 260) was used as the second epoxy of the component (c). As the hardener, 0.1 part by weight of 2-methylimidazole is used as the hardening accelerator of the component (d), and 80 parts by weight of the nitrile rubber is used as the modifier formed of the thermoplastic resin in the component (e), and used. 0.1 part by weight of a fluorine-based surfactant [composition (f)] (FC4430 from 3M Company, USA) is used as an additive; these components are added to a methyl ethyl ketone solvent, and then they are subjected to room temperature and atmospheric pressure. The varnish of the adhesive composition was prepared by mixing for 5 hours, wherein the solid content concentration in the entire composition was 28% by weight.
<實例2>製作黏著劑組合物<Example 2> Making an adhesive composition
相對於作為組成份(a)環氧基樹脂的100重量份的雙酚A環氧樹脂(Kukdo化學公司出品之KDS-8128)，使用50重量份的酚醛清漆樹脂(日本Myungsung Hwasung公司出品之MEH-7500H，其數目平均分子量為290，環氧當量為97)作為組成份(b)之第一環氧硬化劑，使用40重量份的苯乙烯-馬來酸酐(其數目平均分子量為4500，環氧當量為260)作為組成份(c)之第二環氧硬化劑，使用0.1重量份的2-甲基咪唑作為組成份(d)之硬化促進劑，使用70重量份的丁腈橡膠與10重量份的苯氧樹脂作為組成份(e)中以熱塑性樹脂形成之改質劑，並使用0.1重量份的氟系表面活性劑【組成份(f)】(美國3M公司出品的FC4430)作為添加劑；將這些組成份添加到丁酮溶劑內，然後在室溫與大氣壓力的條件下將其混合5小時，以製作所述黏著劑組合物之清漆，其中，在整體組合物內的固形物含量濃度為28%(重量比)。50 parts by weight of novolak resin (MEH produced by Japan Myungsung Hwasung Co., Ltd.) was used with respect to 100 parts by weight of bisphenol A epoxy resin (KDS-8128 manufactured by Kukdo Chemical Co., Ltd.) as a component (a) epoxy resin. -7500H, having a number average molecular weight of 290 and an epoxy equivalent of 97) as the first epoxy hardener of component (b), using 40 parts by weight of styrene-maleic anhydride (the number average molecular weight thereof is 4500, the ring The oxygen equivalent is 260) as the second epoxy hardener of the component (c), 0.1 part by weight of 2-methylimidazole is used as the hardening accelerator of the component (d), and 70 parts by weight of the nitrile rubber and 10 are used. A part by weight of a phenoxy resin is used as a modifier formed of a thermoplastic resin in the component (e), and 0.1 part by weight of a fluorine-based surfactant [component (f)] (FC4430 produced by 3M Company, USA) is used as an additive. These components were added to a methyl ethyl ketone solvent, and then mixed at room temperature under atmospheric pressure for 5 hours to prepare a varnish of the adhesive composition, wherein the solid content in the overall composition The concentration was 28% by weight.
<實例3>製作黏著劑組合物<Example 3> Making an adhesive composition
相對於作為組成份(a)環氧基樹脂的100重量份的雙酚A環氧樹脂(Kukdo化學公司出品之KDS-8128)，使用60重量份的酚醛清漆樹脂(日本Myungsung Hwasung公司出品之MEH-7500H，其數目平均分子量為290，環氧當量為97)作為組成份(b)之第一環氧硬化劑，使用40重量份的聚醚胺(美國Huntsman公司出品之T-5000)與苯乙烯-馬來酸酐(其數目平均分子量為4500，環氧當量為260)以重量比1：1混合之混合物，作為組成份(c)之第二環氧硬化劑，使用0.1重量份的2-甲基咪唑作為組成份(d)之硬化促進劑，使用70重量份的丁腈橡膠與10重量份的苯氧樹脂作為組成份(e)中以熱塑性樹脂形成之改質劑，並使用0.1重量份的氟系表面活性劑【組成份(f)】(美國3M公司出品的FC4430)作為添加劑；將這些組成份添加到丁酮溶劑內，然後在室溫與大氣壓力的條件下將其混合5小時，以製作所述黏著劑組合物之清漆，其中，在整體組合物內的固形物含量濃度為28%(重量比)。60 parts by weight of novolac resin (MEH produced by Japan Myungsung Hwasung Co., Ltd.) was used with respect to 100 parts by weight of bisphenol A epoxy resin (KDS-8128 manufactured by Kukdo Chemical Co., Ltd.) as a component (a) epoxy resin. -7500H, having a number average molecular weight of 290 and an epoxy equivalent of 97) as the first epoxy hardener of component (b), using 40 parts by weight of polyetheramine (T-5000 from Huntsman, USA) and benzene Ethylene-maleic anhydride (having a number average molecular weight of 4,500, an epoxy equivalent of 260) in a mixture of 1:1 by weight, as a second epoxy hardener of component (c), using 0.1 part by weight of 2- Methylimidazole as a hardening accelerator of component (d), using 70 parts by weight of nitrile rubber and 10 parts by weight of phenoxy resin as a modifier formed of a thermoplastic resin in component (e), and using 0.1 weight a fluorine-based surfactant [composition (f)] (FC4430 from 3M Company, USA) is used as an additive; these components are added to a methyl ethyl ketone solvent, and then mixed at room temperature under atmospheric pressure. Hours to make a varnish of the adhesive composition, wherein The entire solid content concentration in the composition is 28% (by weight).
<比較例1>製作黏著劑組合物<Comparative Example 1> Preparation of an adhesive composition
相對於作為組成份(a)環氧基樹脂的100重量份的二環戊二烯環氧樹脂(日本Nippon Kayaku公司出品之XD-1000)，使用60重量份的二氨基二苯甲烷(其分子量為198.2，環氧當量為49.6)作為單分子環氧硬化劑，使用100重量份的丁腈橡膠作為組成份(e)中以熱塑性樹脂形成之改質劑，並使用0.1重量份的氟系表面活性劑(美國3M公司出品的FC4430)作為添加劑；將這些組成份添加到丁酮溶劑內，然後在室溫與大氣壓力的條件下將其混合5小時，以製作所述黏著劑組合物之清漆，其中，在整體組合物內的固形物含量濃度為28%(重量比)。60 parts by weight of diaminodiphenylmethane (the molecular weight thereof) is used with respect to 100 parts by weight of dicyclopentadiene epoxy resin (XD-1000 available from Nippon Kayaku Co., Ltd.) as the component (a) epoxy resin. 198.2, epoxy equivalent of 49.6) as a single molecule epoxy hardener, using 100 parts by weight of nitrile rubber as a modifier formed of a thermoplastic resin in component (e), and using 0.1 part by weight of a fluorine-based surface An active agent (FC4430 from 3M Company, USA) was used as an additive; these components were added to a methyl ethyl ketone solvent, and then mixed at room temperature under atmospheric pressure for 5 hours to prepare a varnish of the adhesive composition. Wherein the solid content concentration in the overall composition was 28% by weight.
<比較例2>製作黏著劑組合物<Comparative Example 2> Preparation of an adhesive composition
除了相對於作為組成份(a)環氧基樹脂的100重量份的二環戊二烯環氧樹脂(日本Nippon Kayaku公司出品之XD-1000)，包含50重量份的酚醛清漆樹脂(日本Myungsung Hwasung公司出品之MEH-7500H，其數目平均分子量為290，環氧當量為97)作為組成份(b)之第一環氧硬化劑，及包含60重量份的鄰苯二甲酸酐(其分子量為148.1，環氧當量為79.1)作為組成份(c)之單分子第二環氧硬化劑之外，係使用與實例1相同的組成份與含量來製作黏著劑組合物之清漆。In addition to 100 parts by weight of dicyclopentadiene epoxy resin (XD-1000, manufactured by Nippon Kayaku Co., Ltd.) as a component (a) epoxy resin, 50 parts by weight of novolac resin (Japan Myungsung Hwasung) The company's MEH-7500H has a number average molecular weight of 290, an epoxy equivalent of 97) as the first epoxy hardener of component (b), and 60 parts by weight of phthalic anhydride (its molecular weight is 148.1). The epoxide of the adhesive composition was prepared using the same component parts and contents as in Example 1 except that the epoxy equivalent was 79.1) as the single molecule second epoxy hardener of the component (c).
<實例4>製作引腳固定膠帶<Example 4> Making a pin fixing tape
在厚度50μm之聚醯胺基膜上，敷設實例1中製作的黏著劑組合物達20μm厚度後，於50℃下將基膜放置10分鐘。然後，在170℃的對流加熱爐內加熱3分鐘，形成具有20μm厚黏著層的半導體封裝用引腳固定膠帶。On the polyamidyl film having a thickness of 50 μm, the adhesive composition prepared in Example 1 was applied to a thickness of 20 μm, and then the base film was allowed to stand at 50 ° C for 10 minutes. Then, it was heated in a convection oven at 170 ° C for 3 minutes to form a pin-bonding tape for a semiconductor package having a 20 μm thick adhesive layer.
<實例5>製作引腳固定膠帶<Example 5> Making a pin fixing tape
使用與實例4相同的方式進行製程，但是在厚度50μm之聚醯胺基膜上，敷設實例2中製作的黏著劑組合物，形成具有20μm厚黏著層的半導體封裝用引腳固定膠帶。The process was carried out in the same manner as in Example 4, except that the adhesive composition prepared in Example 2 was applied to a polyimide film having a thickness of 50 μm to form a pin-bonding tape for a semiconductor package having a 20 μm thick adhesive layer.
<實例6>製作引腳固定膠帶<Example 6> Making a pin fixing tape
使用與實例4相同的方式進行製程，但是在厚度50μm之聚醯胺基膜上，敷設實例3中製作的黏著劑組合物，形成具有20μm厚黏著層的半導體封裝用引腳固定膠帶。The process was carried out in the same manner as in Example 4, except that the adhesive composition prepared in Example 3 was applied to a polyimide film having a thickness of 50 μm to form a pin-bonding tape for a semiconductor package having a 20 μm thick adhesive layer.
<比較例3、4>製作引腳固定膠帶<Comparative Example 3, 4> Making a pin fixing tape
使用與實例4相同的方式進行製程，但是在厚度50μm之聚醯胺基膜上，敷設比較例1或2中製作的黏著劑組合物，形成具有20μm厚黏著層的半導體封裝用引腳固定膠帶。The process was carried out in the same manner as in Example 4, but the adhesive composition prepared in Comparative Example 1 or 2 was applied on a polyimide film having a thickness of 50 μm to form a pin-bonding tape for a semiconductor package having a 20 μm thick adhesive layer. .
<實驗例1>測試樹脂流動性<Experimental Example 1>Testing resin fluidity
將實例4-6及比較例3-4中製作的引腳固定膠帶貼合在一1mm厚的鋁板上；其中，引腳固定膠帶係裁切成10mm寬x100mm高的尺寸，黏著層係面向1mm厚鋁板放置。然後，分別在180℃、210℃及230℃下，施加8百帕壓力，將引腳固定膠帶壓向鋁板。在上述壓縮條件下製出數個測試樣本，並量測從引腳固定膠帶流出的黏著劑組成份的寬度。量測係沿垂直方向進行，總共10次，亦即，左、右各5次，並計算其平均值。The pin fixing tapes prepared in Examples 4-6 and Comparative Examples 3-4 were attached to a 1 mm thick aluminum plate; wherein the pin fixing tape was cut into a size of 10 mm wide by 100 mm, and the adhesive layer was oriented to 1 mm. Thick aluminum plate is placed. Then, at 180 ° C, 210 ° C, and 230 ° C, a pressure of 8 PaPa was applied to press the pin fixing tape against the aluminum plate. Several test samples were prepared under the above compression conditions, and the width of the adhesive component flowing out from the pin fixing tape was measured. The measurement system was carried out in the vertical direction for a total of 10 times, that is, 5 times left and right, and the average value was calculated.
從表1所示的樹脂流動性測試結果可以看出，實例4-6及比較例3-4中所製作的引腳固定膠帶都顯示，當壓制溫度增加時，樹脂流動性亦隨之增加。然而，相較於比較例3-4的引腳固定膠帶，實例4-6中製作的引腳固定膠帶在各種溫度條件下，都顯示相對較為限制的樹脂流動性。As can be seen from the results of the resin fluidity test shown in Table 1, the pin-fixed tapes produced in Examples 4-6 and Comparative Examples 3-4 showed that the resin fluidity also increased as the pressing temperature increased. However, the pin fixing tapes produced in Examples 4-6 exhibited relatively limited resin fluidity under various temperature conditions as compared with the pin fixing tape of Comparative Example 3-4.
<實驗例2>高加速應力測試(HAST)<Experimental Example 2> High Accelerated Stress Test (HAST)
為了測試實例4-6及比較例3-4中製作的半導體封裝用引腳 固定膠帶的電氣可靠度，所以使用第一圖與第二圖所示的方法進行高加速應力測試。In order to test the pins for semiconductor packages fabricated in Examples 4-6 and Comparative Examples 3-4 The electrical reliability of the tape was fixed, so the high acceleration stress test was performed using the methods shown in the first and second figures.
第一圖顯示用於測試本發明引腳固定膠帶電氣可靠度的測試片，其中係在聚醯胺薄膜上形成一銅電路，並有接地電極單元位於兩端。銅電路間的距離調為200μm。The first figure shows a test piece for testing the electrical reliability of the pin fixing tape of the present invention, in which a copper circuit is formed on the polyimide film and the ground electrode unit is located at both ends. The distance between the copper circuits was adjusted to 200 μm.
第二圖顯示將實例4-6及比較例3-4中製作的引腳固定膠帶，熱貼合到第一圖所示測試片的銅電路上，藉此所製出的樣本。其中，引腳固定膠帶係沿黏著方向以熱壓縮方式覆蓋測試片的銅電路，而其壓縮溫度、壓縮時間及壓力分別調整為200℃、1秒及8百帕。其次，使用對流加熱爐讓貼合了引腳固定膠帶的測試片在180℃下硬化一小時。使該等電極單元接觸正、負電極後，在溫度130℃及相對濕度85%下，對硬化的測試片施加30V的電壓，並每小時量測一次電阻的變化。The second figure shows the samples prepared by thermally bonding the lead fixing tapes prepared in Examples 4-6 and Comparative Examples 3-4 to the copper circuit of the test piece shown in the first figure. Among them, the pin fixing tape covers the copper circuit of the test piece in a heat compression manner along the adhesive direction, and the compression temperature, compression time and pressure are adjusted to 200 ° C, 1 second and 8 kPa, respectively. Next, the test piece to which the pin fixing tape was attached was hardened at 180 ° C for one hour using a convection oven. After the electrode units were brought into contact with the positive and negative electrodes, a voltage of 30 V was applied to the hardened test piece at a temperature of 130 ° C and a relative humidity of 85%, and the change in resistance was measured every hour.
第三圖顯示本發明引腳固定膠帶之高電壓絕緣可靠度測試結果，其中實例4-6中製作的引腳固定膠帶在實驗條件下長達500小時均未顯示任何阻降。然而，比較例3、4中製作的引腳固定膠帶不到100小時即顯示阻降。The third figure shows the high voltage insulation reliability test results of the pin fixing tape of the present invention, wherein the pin fixing tape prepared in Example 4-6 showed no resistance drop under the experimental conditions for up to 500 hours. However, the pin fixing tapes produced in Comparative Examples 3 and 4 showed a resistance drop in less than 100 hours.
第四圖顯示在本發明引腳固定膠帶之高電壓絕緣可靠度測試後，使用顯微鏡對樣品上的電路單元進行觀察之結果。比較例3、4中製作的引腳固定膠帶確定有枝晶生成並觸及對面的電極而產生電氣短路。然而，實例4-6中製作的引腳固定膠帶上則觀察到乾淨的電極表面，因此確定未生成枝晶。The fourth figure shows the results of observing the circuit elements on the sample using a microscope after the high voltage insulation reliability test of the pin fixing tape of the present invention. The pin fixing tapes produced in Comparative Examples 3 and 4 were determined to have dendrites and touched the opposite electrodes to cause an electrical short. However, a clean electrode surface was observed on the pin fixing tape fabricated in Examples 4-6, so that dendrite was not formed.
<實驗例2>高加速應力測試<Experimental Example 2> High Accelerated Stress Test
以下顯示對實例4-6及比較例3-4中製作的引腳固定膠帶進行高溫可靠度測試。The high temperature reliability test of the pin fixing tapes produced in Examples 4-6 and Comparative Examples 3-4 is shown below.
如第五圖所示，將實例4-6及比較例3-4中製作的引腳固定膠帶貼合到鋁板2，其中的膠帶是在基膜1上形成一黏著層3；貼合之後，在溫度200℃下從兩相反方向拉引腳固定膠帶以量測其滑移抗力；此外並量測膠帶在高溫下的韌性。As shown in the fifth figure, the pin fixing tapes prepared in Examples 4-6 and Comparative Examples 3-4 were attached to the aluminum plate 2, wherein the tape formed an adhesive layer 3 on the base film 1; The tape was fixed from two opposite directions at a temperature of 200 ° C to measure the slip resistance; in addition, the toughness of the tape at high temperatures was measured.
依照上述將各層疊置後，在一加壓機上以180℃的溫度及8百帕的壓力將疊合體壓縮一秒鐘，製出一個測試樣本。使用一台具有高溫室的萬能試驗機(UTM)，以每分鐘10℃的速度增加溫度至200℃後，若將測試樣本朝箭頭方向拉扯，測試樣本黏著表面上相當狹窄的貼合面發生滑移，最後終於分離。記錄從開始對測試樣本施力的時間點至貼合面終於分離的時間點所花費的時間，以及貼合面分離時的最大施力。表2顯示量測的結果。After laminating each as described above, the laminate was compressed at a temperature of 180 ° C and a pressure of 8 PaPa for one second on a press machine to prepare a test sample. After using a universal testing machine (UTM) with a high greenhouse to increase the temperature to 200 ° C at a rate of 10 ° C per minute, if the test sample is pulled in the direction of the arrow, the relatively narrow fit surface of the test sample slips. Moved, finally finally separated. Record the time from the point in time when the test sample is applied to the point in time at which the mating surface is finally separated, and the maximum force applied when the mating surface is separated. Table 2 shows the results of the measurements.
從表2所示的滑移抗力量測結果可以確認，雖然對實例4-6及比較例3-4製作的引腳固定膠帶施力的時間長度相同，但是當貼合面滑移與分離時，實例4-6製作的引腳固定膠帶上，其最大施力與比較例3-4製作的 引腳固定膠帶上的最大施力相較時，高出10N或更多。From the results of the slip resistance test shown in Table 2, it was confirmed that although the lengths of the pin fixing tapes produced in Examples 4-6 and Comparative Examples 3-4 were the same, when the bonding surfaces were slipped and separated, , Example 4-6 made on the pin fixing tape, the maximum force applied and compared with the comparison example 3-4 The maximum applied force on the pin fixing tape is 10N or more higher than the time.
此外，將實例4-6及比較例3-4製作的引腳固定膠帶貼合在1/2oz(盎司)的銅箔上，膠帶係裁切成10mm寬x100mm高的尺寸；放置時，係使黏著層接觸銅箔，並在180℃下施加8百帕的壓力一秒鐘，使黏著層貼合於銅箔。使用具有高溫室的萬能試驗機，以每分鐘10℃的速度將溫度增至200℃，然後在拉動聚醯亞胺(PI)表面時，量測貼合於銅箔的樣本的剝離強度。表3顯示量測的結果。Further, the pin fixing tapes prepared in Examples 4-6 and Comparative Examples 3-4 were attached to a 1/2 oz copper foil, and the tape was cut into a size of 10 mm wide by 100 mm high; The adhesive layer was in contact with the copper foil, and a pressure of 8 kPa was applied at 180 ° C for one second to bond the adhesive layer to the copper foil. Using a universal testing machine with a high temperature chamber, the temperature was increased to 200 ° C at a rate of 10 ° C per minute, and then the peel strength of the sample attached to the copper foil was measured while pulling the surface of the polyimide. Table 3 shows the results of the measurements.
此外，從表3所示的剝離強度量測結果看來，由於實例4-6製作的引腳固定膠帶所觀察到的剝離強度，是比較例3-4製作的引腳固定膠帶的四倍或更高，所以確認它們在200℃或更高溫度下具有優異的黏著性。Further, from the results of the peel strength measurement shown in Table 3, the peel strength observed by the pin fixing tape produced in Example 4-6 was four times that of the pin fixing tape produced in Comparative Example 3-4 or It is higher, so it is confirmed that they have excellent adhesion at 200 ° C or higher.
如上所述，本發明提供一種黏著劑組合物，其中係於一種環氧基樹脂內包含最適量的環氧硬化劑，以便藉由增加交聯密度而增進硬化網絡的斷裂韌性，因此所述黏著劑組合物在高電壓下可具有絕緣可靠度，並在高溫下具有優異的滑移抗力與黏著性。As described above, the present invention provides an adhesive composition comprising an optimum amount of an epoxy hardener in an epoxy resin to enhance the fracture toughness of the hardened network by increasing the crosslinking density, and thus the adhesion The composition can have insulation reliability at high voltage and excellent slip resistance and adhesion at high temperatures.
在本發明中，可使用所述黏著劑組合物製作引腳固定膠帶，它可牢靠固定導線架的引腳，同時在高電壓情況下具有優異的絕緣性能。半導體組裝製程中通常包括200℃或更高溫度的高溫組裝製程。本發明之黏着劑組合物可在此種半導體組裝製程中作為雙面黏著劑使用。In the present invention, the adhesive composition can be used to form a pin fixing tape which can securely fix the lead of the lead frame while having excellent insulation properties under high voltage conditions. The semiconductor assembly process typically includes a high temperature assembly process at 200 ° C or higher. The adhesive composition of the present invention can be used as a double-sided adhesive in such a semiconductor assembly process.
尤其，本發明上述的黏著劑組合物，因為在B階中即形成高交聯密度，所以能在30V或更高之高電壓下具有優異的絕緣特性；復因為各分子在硬化網絡內高度交聯，所以可在200℃或更高之高溫下維持高黏著性。因此，對於應用高電壓的情況中，諸如電梯、車輛、半導體封裝等，本發明的黏著劑組合物極為有用。In particular, the above-mentioned adhesive composition of the present invention has excellent insulating properties at a high voltage of 30 V or higher because it forms a high crosslink density in the B-stage; it is because the molecules are highly intertwined in the hardened network. It is linked, so it can maintain high adhesion at a high temperature of 200 ° C or higher. Therefore, the adhesive composition of the present invention is extremely useful in the case of applying a high voltage such as an elevator, a vehicle, a semiconductor package or the like.
以上雖然參照特定的例舉實施例說明本發明，但本發明並不限於此等實施例而僅以所附申請專利範圍為準。可以理解的是，熟悉此類技術之人士可以變化或修飾上述實施例而不脫離本發明範圍與精神。The present invention has been described above with reference to specific exemplary embodiments, but the present invention is not limited to the embodiments but only the scope of the appended claims. It will be appreciated that those skilled in the art can change or modify the embodiments described above without departing from the scope and spirit of the invention.
1‧‧‧聚醯胺薄膜1‧‧‧ Polyamide film
2‧‧‧鋁板2‧‧‧Aluminum plate
3‧‧‧黏劑層3‧‧‧Adhesive layer
4‧‧‧滑移並分開的部份4‧‧‧Sliding and separate parts
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| EP3233438B1 (en) * | 2014-12-18 | 2021-02-17 | Cytec Industries Inc. | Modified resin systems suitable for liquid resin infusion |
| CN104974471B (en) * | 2015-07-14 | 2017-12-05 | 江苏兆鋆新材料股份有限公司 | A kind of high heat-resisting, high-toughness epoxy resin carbon fibre composite preparation method |
| CN106281175A (en) * | 2016-09-22 | 2017-01-04 | 佛山慧创正元新材料科技有限公司 | A kind of PET film epoxyn |
| JP6739390B2 (en) * | 2017-03-30 | 2020-08-12 | 富士フイルム株式会社 | Method for manufacturing organic EL image display device |
| TWI719419B (en) * | 2019-03-11 | 2021-02-21 | 台光電子材料股份有限公司 | Epoxy resin composition and articles made therefrom |
| JP2021161274A (en) * | 2020-03-31 | 2021-10-11 | 株式会社有沢製作所 | Adhesive tape |
| CN114806432A (en) * | 2022-03-23 | 2022-07-29 | 东莞市穗滢新型材料科技有限公司 | Anti-aging high-temperature-resistant polyimide adhesive tape and preparation method thereof |
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| US5863988A (en) * | 1995-12-25 | 1999-01-26 | Tomoegawa Paper Co., Ltd. | Liquid adhesive for electronic parts and adhesive tape |
| JP4577716B2 (en) * | 2005-01-21 | 2010-11-10 | 日本化薬株式会社 | Heat curable epoxy resin composition and article having a cured adhesive layer thereof |
| JP2008074891A (en) * | 2006-09-19 | 2008-04-03 | Daicel-Cytec Co Ltd | Thermosetting or active energy ray curing composition and film |
| CN101210162B (en) * | 2006-12-28 | 2011-11-30 | 西安西电变压器有限责任公司 | Semi-conductor adhesive and preparation method thereof |
| JP5670048B2 (en) * | 2009-12-21 | 2015-02-18 | 株式会社Ｄｎｐファインケミカル | Adhesive composition and method for producing curable adhesive sheet |
| KR101374364B1 (en) * | 2010-12-27 | 2014-03-17 | 제일모직주식회사 | Adhesive composition for semiconductor, adhesive film comprising the same |
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| CN101589465A (en) * | 2006-11-16 | 2009-11-25 | 汉高股份两合公司 | Board on chip package and process for making same |
| TW201016734A (en) * | 2008-10-24 | 2010-05-01 | Sumitomo Bakelite Co | Adhesive composition for semiconductor and semiconductor device manufactured using the same |
| TW201130941A (en) * | 2009-12-21 | 2011-09-16 | Cheil Ind Inc | Adhesive composition for stealth dicing of semiconductor, adhesive film, and semiconductor device including the adhesive film |
| TW201229190A (en) * | 2010-12-27 | 2012-07-16 | Cheil Ind Inc | Adhesive composition for semiconductor and adhesive film comprising the same |
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