KR101103407B1 - Adhensive composition for semiconductor device and multi-layer adhensive film consisting of the same - Google Patents

Adhensive composition for semiconductor device and multi-layer adhensive film consisting of the same Download PDF

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Publication number
KR101103407B1
KR101103407B1 KR1020080133849A KR20080133849A KR101103407B1 KR 101103407 B1 KR101103407 B1 KR 101103407B1 KR 1020080133849 A KR1020080133849 A KR 1020080133849A KR 20080133849 A KR20080133849 A KR 20080133849A KR 101103407 B1 KR101103407 B1 KR 101103407B1
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South Korea
Prior art keywords
adhesive
transition metal
film
weight
manufactured
Prior art date
Application number
KR1020080133849A
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Korean (ko)
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KR20100075213A (en
Inventor
최한님
송기태
정철
임수미
김상진
홍용우
박백성
Original Assignee
제일모직주식회사
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Priority to KR1020080133849A priority Critical patent/KR101103407B1/en
Priority to PCT/KR2009/007746 priority patent/WO2010074518A2/en
Priority to TW098144743A priority patent/TWI359853B/en
Publication of KR20100075213A publication Critical patent/KR20100075213A/en
Application granted granted Critical
Publication of KR101103407B1 publication Critical patent/KR101103407B1/en

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    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • 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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  • Adhesives Or Adhesive Processes (AREA)
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Abstract

본 발명은 반도체용 접착제 조성물 및 이를 이용하여 제조된 복층구조 접착 필름에 관한 것으로, 전이금속 및 전이금속 이온의 이동으로 인해 야기되는 반도체 칩의 신뢰성 저하를 해결하기 위하여, 전이금속 이온과 결합을 통하여 또는 전이금속 이온을 산화 또는 환원시키고, 전이금속의 이동도를 현저히 감소시킬 수 있는 기능기를 포함하는 접착제 조성물을 사용하되, 후속의 와이어 본딩 공정을 고려하여 유동성을 확보할 수 있는 접착필름을 더 형성함으로써, 반도체 작동의 안정성을 높일 수 있고, 접착 필름의 치수 안정성을 확보함과 동시에 인장강도를 증가시켜 반도체 칩 접합 공정의 신뢰도를 높일 수 있도록 하는 발명에 관한 것이다.The present invention relates to an adhesive composition for semiconductors and a multilayer structure adhesive film prepared using the same, in order to solve the degradation of the reliability of the semiconductor chip caused by the transfer of the transition metal and transition metal ions, through the combination with the transition metal ions Or by using an adhesive composition comprising a functional group capable of oxidizing or reducing transition metal ions and remarkably reducing the mobility of the transition metal, and further forming an adhesive film to ensure fluidity in consideration of a subsequent wire bonding process. By doing so, it is possible to increase the stability of the semiconductor operation, to ensure the dimensional stability of the adhesive film and to increase the tensile strength, and to the invention for increasing the reliability of the semiconductor chip bonding process.

접착필름, 반도체용 접착제, 조성물, 다이싱, 전이금속 Adhesive film, semiconductor adhesive, composition, dicing, transition metal

Description

반도체용 접착제 조성물 및 이를 이용하여 제조된 복층구조 접착 필름{ADHENSIVE COMPOSITION FOR SEMICONDUCTOR DEVICE AND MULTI-LAYER ADHENSIVE FILM CONSISTING OF THE SAME}Adhesive composition for semiconductors and multilayer structure adhesive film manufactured using the same {ADHENSIVE COMPOSITION FOR SEMICONDUCTOR DEVICE AND MULTI-LAYER ADHENSIVE FILM CONSISTING OF THE SAME}

본 발명은 전이금속 및 전이금속 이온을 환원시키거나 또는 전이금속 및 전이금속의 이동성을 저하시킬 수 있는 기능기를 가지고 있는 조성물을 포함하는 접착제 조성물 및 이를 이용하여 제조한 복층구조 접착 필름에 관한 기술이다. The present invention relates to an adhesive composition comprising a composition having a functional group capable of reducing the transition metal and the transition metal ion or reducing the mobility of the transition metal and the transition metal, and a technique related to a multilayer structure adhesive film prepared using the same. .

일반적으로, 반도체용 접착 필름이 고 신뢰도를 발휘하게 하기 위하여 접착제 조성물에서 종래 반도체 소자와 반도체 소자 또는 반도체 소자와 지지 부재의 접합에는 은 페이스트(paste)가 주로 사용되어 왔다.In general, silver paste has been mainly used for bonding a semiconductor element and a semiconductor element or a semiconductor element and a support member in the adhesive composition in order to make the adhesive film for semiconductor exhibit high reliability.

최근에는 반도체 소자의 소형화, 대용량화 경향에 따라 이에 사용되는 지지 부재 또한 소형화와 세밀화가 요구되고 있다. 이에 은 페이스트는 적합하지 못하게 되어 미세 반도체 소자에서 돌출되거나 또는 반도체 소자가 경사지게 되는 원인이 되고, 이에 따라 와이어 본딩(wire bonding)시 이상발생, 기포발생 및 두께의 제어 가 어렵게 되었다. 따라서, 최근에는 은 페이스트를 대신하여 접착 필름이 주로 사용되고 있는 추세이다.In recent years, with the tendency of miniaturization and large-capacity semiconductor devices, the support members used therein are also required to be miniaturized and refined. Therefore, the silver paste is not suitable to protrude from the fine semiconductor device or to cause the semiconductor device to be inclined, thereby making it difficult to control abnormality, bubble generation, and thickness during wire bonding. Therefore, in recent years, the adhesive film is mainly used instead of silver paste.

반도체 조립에 사용되는 접착 필름은 주로 다이싱 필름(dicing film)과 함께 사용된다. 상기 다이싱 필름은 일련의 반도체 칩 제조공정에서의 다이싱 공정에서 반도체 웨이퍼를 고정하기 위해 사용되는 필름을 말한다. 다이싱 공정은 반도체 웨이퍼로부터 개개의 칩으로 절단하는 공정으로서, 상기 다이싱 공정에 연속해서 익스팬드 공정, 픽업공정 및 마운팅 공정이 수행된다. 이러한 다이싱 필름은 통상 염화비닐이나 폴리올레핀 구조의 기재 필름 위에 자외선 경화형 또는 일반 경화형의 점착제를 코팅하고 그 위에 PET재질의 커버필름을 접착하는 것으로 구성된다. Adhesive films used in semiconductor assembly are mainly used with dicing films. The dicing film refers to a film used to fix a semiconductor wafer in a dicing process in a series of semiconductor chip manufacturing processes. The dicing process is a process of cutting into individual chips from a semiconductor wafer, and an expand process, a pick-up process and a mounting process are performed successively to the dicing process. Such a dicing film is usually composed of coating a UV-curable or general curable pressure-sensitive adhesive on a vinyl chloride or polyolefin base film and adhering a cover film of PET material thereon.

한편, 일반적인 반도체용 접착 필름의 사용법은 반도체 웨이퍼(wafer)에 접착 필름을 부착하고 여기에 상기와 같은 구성을 갖는 다이싱 필름을 커버필름이 제거된 다이싱 필름에 겹쳐 바른 뒤 다이싱 공정에 따라 조각화하는 것이다.On the other hand, the general usage of the adhesive film for semiconductors is to adhere the adhesive film to the semiconductor wafer (wafer) and apply a dicing film having the configuration as described above to the dicing film from which the cover film is removed, followed by the dicing process To fragment.

최근에는 다이싱 다이본딩용 반도체용 접착제로서 PET 커버필름을 제거한 다이싱 필름과 접착 필름을 서로 합지시켜 하나의 필름으로 만든 뒤 그 위에 반도체 웨이퍼를 부착하고 다이싱 공정에 따라 조각화하는 추세이다. 하지만 이러한 경우 기존의 다이싱(Dicing)만을 목적으로 한 다이싱 필름(Dicing film)과는 달리 픽업 공정(pick-up)시 다이(Die)와 다이접착 필름(die adhesive film)을 동시에 떨어뜨려야 한다는 어려움이 있으며, 반도체 웨이퍼 후면에 다이접착 필름을 접착시키는 과정에서 거친 표면으로 인하여 회로패턴 사이에 많은 갭 또는 보이드(Void)가 발생할 수 있다. 이는 조립 후 칩과 계면사이에 보이드가 잔존하여 고온의 환경에 노 출되었을 경우 갭이나 보이드가 부피팽창을 일으키고 결국 크랙(crack) 되어 신뢰성 과정에서 소자의 불량을 초래한다. 그리하여 반도체 조립의 모든 공정중에 계면 사이 보이드 발생을 최소화 하는 것이 필요하게 된다. 일반적인 방법으로 경화부분의 함량을 높이게 되는데 이로 인하여 필름의 인장강도가 감소하게 되어 반도체 웨이퍼에 맞는 크기로 자르는 프리컷팅(Precutting) 과정에서 필름이 끊어지거나 반도체 조립공정인 칩조각화(sawing) 과정에서 버(Burr) 또는 칩핑(Chipping) 현상이 발생할 수 있으며, 자체의 낮은 모듈러스에 의한 점착제와의 높은 부착력으로 인하여 접착 필름이 변형되어 픽업 성공률이 감소할 가능성이 크다. 특히, 동 사이즈(same size)의 반도체 칩을 2개 이상 사용하는 반도체 소재의 경우, 와이어에 기인하는 요철을 갖는 하부 반도체 칩 위에 별도의 접착 필름을 가진 반도체 칩을 더 적층하게 되는데 이때 와이어의 요철을 매립하여 갭이나 보이드 형성을 최소화 하면서 상부의 반도체 칩과의 절연성을 확보하는 것이 가능한 접착필름의 중요성 또한 요청되고 있다.Recently, as an adhesive for dicing die-bonding semiconductors, a dicing film from which a PET cover film has been removed and an adhesive film are laminated to each other to form a single film, and then a semiconductor wafer is attached thereon and fragmented according to a dicing process. In this case, however, unlike a dicing film intended only for dicing, the die and the die adhesive film must be simultaneously dropped during the pick-up process. In the process of adhering the die-bonding film to the back surface of the semiconductor wafer, there are many gaps or voids between circuit patterns due to the rough surface. When voids remain between chips and interfaces after assembly and are exposed to high-temperature environments, gaps or voids cause volume expansion and eventually crack, resulting in device failure in the reliability process. Thus, it is necessary to minimize the generation of voids between interfaces during all processes of semiconductor assembly. In general, the content of the hardened portion is increased, which causes the tensile strength of the film to decrease, which causes the film to break in the precutting process to be cut to a size suitable for the semiconductor wafer, or in the chip sawing process of the semiconductor assembly process. (Burr) or chipping (Chipping) may occur, the adhesive film is deformed due to its high adhesion to the pressure-sensitive adhesive due to its low modulus is likely to reduce the pickup success rate. In particular, in the case of a semiconductor material using two or more same size semiconductor chips, a semiconductor chip having a separate adhesive film is further stacked on a lower semiconductor chip having irregularities caused by wires. There is also a need for an adhesive film capable of securing insulation with an upper semiconductor chip while filling gaps and minimizing gaps or voids.

상기와 같은 조건을 만족하는 접착 필름으로 에폭시(epoxy)계 수지를 주요 조성물로 하는 것이 주로 사용되고 있다. 이때, 에폭시계 수지는 비교적 흡수성이 높은 수지이기 때문에, 반도체 칩 적층 공정 시 접착 계면에 많은 이온(ion)성 불순물들이 침투될 위험이 있다.As an adhesive film satisfying the above conditions, epoxy resins are mainly used as main compositions. At this time, since the epoxy resin is a resin having a relatively high absorption, there is a risk that many ionic impurities penetrate into the adhesive interface during the semiconductor chip stacking process.

이온성 불순물 중 특히 전이금속 이온은 열전도성 및 전기전도성을 가지므로 반도체 칩에 손상을 가하거나, 회로의 이상 작동을 유발시킬 수 있는 문제가 있다. 따라서, 전이금속을 제거할 수 있는 물질을 첨가하는 것이 중요하나, 상술한 바와 같이 복잡한 접착 필름의 특성을 저해시키기 않으면서도 전이금속을 제거시키기 위한 획기적인 방법은 아직까지 개발되지 못하고 있는 실정이다.Among the ionic impurities, transition metal ions, in particular, have thermal and electrical conductivity, which may cause damage to the semiconductor chip or cause abnormal operation of the circuit. Therefore, it is important to add a material capable of removing the transition metal, but as described above, a groundbreaking method for removing the transition metal without impairing the properties of the complex adhesive film has not been developed yet.

본 발명은 반도체 칩의 표면에 불순물로 잔류하는 전이금속 또는 접착 계면에 침투되는 전이금속 이온으로 인해 야기되는 반도체 칩의 신뢰성 저하를 해결할 수 있는 반도체용 접착제 조성물을 제공하는 것을 그 목적으로 한다.An object of the present invention is to provide an adhesive composition for a semiconductor that can solve the degradation of the reliability of the semiconductor chip caused by the transition metal remaining as impurities on the surface of the semiconductor chip or the transition metal ions penetrating into the adhesive interface.

아울러, 본 발명은 상기 접착제 조성물로 구비되어 전이금속 환원력 및 유동성 조절기능을 동시에 확보하고 필름의 인장강도 특성을 만족시켜 필름이 끊어지지 않고 단단하게 형성될 수 있으며, 고 신뢰도를 가지는 반도체용 접착 필름을 제공하는 것을 그 목적으로 한다.In addition, the present invention is provided with the adhesive composition to ensure the transition metal reducing power and fluidity control function at the same time and satisfy the tensile strength characteristics of the film can be formed without breaking the film, the adhesive film for a semiconductor having high reliability To provide that purpose.

본 발명에 따른 반도체용 복층구조 접착 필름은 기재 필름 상부에 형성되며, 전이 금속을 산화 또는 환원시키거나, 전이 금속의 이동성을 저해하는 전이금속 포착용 기능기를 갖는 바인더를 전체 고분자 바인더의 함량 기준으로 50 ~ 90중량%만큼 포함하는 접착제 조성물로 구비된 제 1 접착층 및 상기 제 1 접착층 상부에 구비되며, 전이 금속을 산화 또는 환원시키거나, 전이 금속의 이동성을 저해하는 전이금속 포착용 기능기를 갖는 바인더를 전체 고분자 바인더의 함량 기준으로 15 ~ 30중량%만큼 포함하는 접착제 조성물로 구비된 제 2 접착층을 포함한다.The multilayer structure adhesive film for semiconductors according to the present invention is formed on the base film, the binder having a transition metal capture functional group for oxidizing or reducing the transition metal, or inhibits the mobility of the transition metal based on the content of the total polymer binder A binder having a first adhesive layer provided with an adhesive composition comprising as much as 50 to 90% by weight and a functional group for capturing a transition metal to oxidize or reduce the transition metal or inhibit the mobility of the transition metal, provided on the first adhesive layer. It includes a second adhesive layer provided with an adhesive composition containing 15 to 30% by weight based on the content of the total polymer binder.

여기서, 상기 전이금속 포착용 기능기는 -CN, -COOH, -NCO, -SH 또는 -NH 중 선택된 하나 이상을 포함하는 것을 특징으로 하고, 상기 전이 금속을 산화 또는 환 원시키거나, 전이 금속의 이동성을 저해하는 전이금속 포착용 기능기를 갖는 모노머는 상기 각 접착층의 고분자 바인더 중량을 기준으로 20 ~ 40% 포함되는 것을 특징으로 하고, 상기 제 1 접착층의 두께는 전체 접착 필름 두께의 8 ~ 25%이고, 제 2 접착층의 두께는 전체 접착 필름 두께의 75 ~ 98%가 되도록 형성되는 것을 특징으로 한다.Here, the functional group for capturing transition metals includes at least one selected from -CN, -COOH, -NCO, -SH or -NH, and oxidizes or reduces the transition metal, or transfers the mobility of the transition metal. Monomer having a transition metal trapping functional group for inhibiting is characterized in that it comprises 20 to 40% based on the weight of the polymer binder of each adhesive layer, the thickness of the first adhesive layer is 8 to 25% of the total adhesive film thickness , The thickness of the second adhesive layer is characterized in that it is formed to be 75 to 98% of the total adhesive film thickness.

아울러, 본 발명에 따른 반도체용 접착제 조성물은 상술한 상기 제 1 접착층 또는 상기 제 2 접착층을 구성하는 접착제 조성물은 각각 바인더 수지 2 ~ 50중량%, 에폭시 수지 4 ~ 50 중량%, 페놀 경화형 수지 3 ~ 50 중량%, 경화 촉매 0.1 ~ 10 중량%, 실란 커플링제 0.1 ~ 10 중량%, 충진제 0.1 ~ 50중량% 및 잔부의 첨가제를 포함하고, 상기 접착제 조성물은 전이금속 포착용 첨가제를 더 포함하는 것을 특징으로 한다.In addition, in the adhesive composition for a semiconductor according to the present invention, the adhesive composition constituting the first adhesive layer or the second adhesive layer is 2 to 50% by weight of binder resin, 4 to 50% by weight of epoxy resin, and 3 to phenol curable resin, respectively. 50 wt%, 0.1 to 10 wt% of curing catalyst, 0.1 to 10 wt% of silane coupling agent, 0.1 to 50 wt% of filler and the balance of additives, the adhesive composition further comprises an additive for capturing transition metals It is done.

아울러, 본 발명은 상기 복층구조 접착 필름을 포함하는 다이싱 다이본딩 필름을 포함 한다.In addition, the present invention includes a dicing die-bonding film comprising the multilayer structure adhesive film.

본 발명에 따른 반도체용 접착제 조성물 및 이를 이용하여 제조된 복층형 접착 필름은 접착제 조성물에 전이금속 이온과 결합되거나, 전이금속 이온을 산화 또는 환원시킴으로써, 전이금속의 이동도를 현저히 감소시킬 수 있는 기능기를 포함 시킨다. 따라서, 반도체 공정중 또는 공정이 끝난 후 반도체 소자의 작동 효율을 극대화 시킬 수 있는 효과를 제공하고, 반도체 칩의 표면에 불순물로 잔류하는 전이금속 또는 접착 계면에 침투되는 전이금속 이온으로 인해 야기되는 반도체 칩의 신뢰성 저하 문제를 해결할 수 있는 효과를 제공 한다.Adhesive composition for semiconductors and a multilayer adhesive film prepared using the same according to the present invention is a functional group that can significantly reduce the mobility of the transition metal by bonding or transition metal ions to the adhesive composition, or by oxidizing or reducing the transition metal ions. Include it. Therefore, it provides an effect to maximize the operating efficiency of the semiconductor device during or after the semiconductor process, and the semiconductor caused by the transition metal ions penetrating into the adhesive interface or the transition metal remaining as impurities on the surface of the semiconductor chip It provides the effect that can solve the problem of deterioration of chip.

아울러, 본 발명은 필름의 인장강도 증가와 동시에 접착력, 표면 에너지 및 흡습률 등을 향상시킴으로써, 고 신뢰도를 가지는 반도체용 접착 필름을 제공하는 효과를 제공 한다.In addition, the present invention provides an effect of providing an adhesive film for semiconductors having high reliability by increasing the tensile strength of the film and improving adhesion, surface energy, and moisture absorption rate.

아울러, 본 발명은 와이어 본딩 시 와이어 충진이 용이하며 보이드 발생을 최소화 할 수 있기 때문에 반도체 조립시 칩의 박리화 정도에 상관없이 높은 신뢰성을 확보할 수 있는 효과를 제공 한다.In addition, the present invention provides an effect of ensuring high reliability regardless of the degree of peeling of the chip during semiconductor assembly because it is easy to wire filling and minimize the generation of voids during wire bonding.

본 발명의 반도체용 접착제 조성물은 고분자 바인더부, 경화부 및 유기용매를 포함한다. The adhesive composition for semiconductors of this invention contains a polymeric binder part, a hardening part, and an organic solvent.

여기서, 고분자 바인더부로는 아크릴계 고분자, NCO 첨가 고분자, 에폭시 첨가 고분자 등이 사용될 수 있다. 본 발명에서는 상기 바인더부에 전이 금속을 산화 또는 환원시키거나 이동성을 저해할 수 있는 기능기를 첨가함으로써, 전체적인 접착 필름 기능을 유지시키면서 전이 금속의 이동을 제어하는 기능을 부여한다.Here, an acrylic polymer, an NCO-added polymer, an epoxy-added polymer, or the like may be used as the polymer binder part. In the present invention, by adding a functional group capable of oxidizing or reducing the transition metal or inhibiting mobility in the binder portion, a function of controlling the movement of the transition metal is provided while maintaining the overall adhesive film function.

다음에는, 경화부로는 에폭시 수지, 우레탄 수지, 실리콘 수지, 폴리에스테르 수지, 폐놀형 경화수지, 아민계 경화수지, 멜라닌 경화수지, 요소 경화 수지, 산무수물계 경화수지 등을 포함하는 것이 사용될 수 있다.Next, the hardening part may include an epoxy resin, a urethane resin, a silicone resin, a polyester resin, a waste hardening resin, an amine curing resin, a melanin curing resin, a urea curing resin, an acid anhydride curing resin, or the like. .

그 외에 본 발명에 따른 접착제 조성물에는 경화촉매, 실란커플링제 및 충진제 등이 포함될 수 있다.In addition, the adhesive composition according to the present invention may include a curing catalyst, a silane coupling agent and a filler.

본 발명은 바인더부, 경화부 및 유기용매 중 선택된 하나 이상의 조성에 전이금속 포착용 기능기(-CN, -COOH, -NCO, -SH 및 -NH 등)를 포함시킴으로써, 전이금속의 이동도를 현저히 감소시킬 수 있도록 하되, 후속의 와이어 본딩 공정을 고려하여 유동성을 확보할 수 있는 접착필름을 더 형성한 복층구조의 접착제 필름을 제공한다.The present invention includes the transition metal capture functional groups (-CN, -COOH, -NCO, -SH and -NH, etc.) in at least one selected from the binder portion, the hardening portion and the organic solvent, thereby improving the mobility of the transition metal. It is possible to significantly reduce, but in consideration of the subsequent wire bonding process to provide an adhesive film having a multi-layer structure further formed an adhesive film to ensure the fluidity.

이하, 본 발명의 접착제 조성물을 구성하는 상기 바람직한 각 성분에 관하여 상세하게 설명하면 다음과 같다.Hereinafter, the said preferable each component which comprises the adhesive composition of this invention is demonstrated in detail as follows.

유기 용매Organic solvent

본 발명의 유기 용매는 반도체용 접착제 조성물의 점도를 낮추어 필름 제조를 용이하게 한다. 이때, 잔류 유기 용매가 존재하여 필름의 물성에 영향을 미칠 수 있으므로 필름 내에 2% 미만으로 잔류되도록 하는 것이 바람직하다.The organic solvent of the present invention lowers the viscosity of the adhesive composition for semiconductors to facilitate film production. At this time, the residual organic solvent may be present to affect the physical properties of the film, it is preferable to remain less than 2% in the film.

본 발명에 사용될 수 있는 유기용매는 벤젠, 아세톤, 메틸에틸키톤, 테트라히드로 퓨란, 디메틸포름알데히드, 사이클로헥산으로, 프로필렌 글리콜 모노메틸 에테르 아세테이트 또는 시클로헥사논 이루어지는 군에서 선택된 1종 이상인 것이 바람직하나, 이에 반드시 제한되는 것은 아니다. The organic solvent that can be used in the present invention is benzene, acetone, methyl ethyl ketone, tetrahydrofuran, dimethylformaldehyde, cyclohexane, preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate or cyclohexanone, It is not necessarily limited thereto.

이러한 유기 용매는 접착제 필름 형성시 균일한 혼합물 조성을 유도하여 공정상 발생할 수 있는 보이드를 완화시키는 역할을 한다. 아울러, 접착 필름 형성 후 필름 내에 소량 잔류하여 필름을 부드럽게 하는 기능을 수행한다. Such organic solvents induce a uniform mixture composition in forming the adhesive film and serve to alleviate voids that may occur in the process. In addition, by forming a small amount in the film after the adhesive film to perform a function to soften the film.

고분자 바인더Polymer binder

본 발명의 구현예들에서 사용 가능한 고분자 바인더로는 아크릴계 고분자 수지가 있다. 이는 필름 형성에 필요한 고무 성분으로서, 수산기, 카르복시기 또는 에폭시기를 함유할 수 있다. Polymer binders that can be used in the embodiments of the present invention include an acrylic polymer resin. It is a rubber component necessary for film formation and may contain a hydroxyl group, a carboxyl group or an epoxy group.

특히, 본 발명에서는 전이 금속을 제어할 수 있는 -CN, -COOH, -NCO, -SH 또는 -NH 와 같은 전이금속 포착용 기능기를 고분자 바인더에 함유시킨 실시예를 제공함으로써, 접착 공정시 반도체 소자의 신뢰성을 더 향상될 수 있음을 증명하는 것으로 하나, 이에 제한되는 것은 아니다.In particular, the present invention provides an embodiment in which a polymer binder contains a functional group for capturing a transition metal, such as -CN, -COOH, -NCO, -SH or -NH, which can control the transition metal, in the polymer binder, thereby providing a semiconductor device during the adhesion process. To prove that the reliability can be further improved, but is not limited thereto.

아크릴계 고분자 수지는 중합하는 모노머들을 선정하는 것에 의해 유리전이온도나 분자량 조절이 용이하고 특히 측쇄에 관능기를 도입하기 쉬운 장점이 있다. 모노머로는 아크릴로니트릴, 부틸아크릴레이트, 부틸 메타아크릴레이트, 2-에틸헥실아크릴레이트, 아크릴산, 2-히드록시에틸(메타)크릴레이트, 메틸(메타)아크릴레이트, 스타이렌 모노머, 글리시딜(메타)아크릴레이트, 이소옥틸아크릴레이트, 스테아릴메타크릴레이트 등의 모노머 들이 공중합에 사용된다The acrylic polymer resin has advantages in that it is easy to control the glass transition temperature or molecular weight by selecting monomers to polymerize, and particularly to introduce functional groups into the side chain. As the monomer, acrylonitrile, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, acrylic acid, 2-hydroxyethyl (meth) acrylate, methyl (meth) acrylate, styrene monomer, glycidyl Monomers such as (meth) acrylate, isooctyl acrylate and stearyl methacrylate are used for copolymerization

상기 아크릴계 고분자 수지는 에폭시 당량, 유리 전이온도 및 분자량별로 구분되어질 수 있다. 에폭시 당량이 10,000을 넘는 시판제품으로는 나가세 켐텍스의 SG-80H가 있으며 에폭시 당량이 10,000 이하인 것은 SG-P3계, SG-800H계등이 사용될 수 있다.The acrylic polymer resin may be classified by epoxy equivalent, glass transition temperature and molecular weight. Commercially available epoxy equivalents over 10,000 are Nagase Chemtex's SG-80H, and epoxy equivalents below 10,000 may be SG-P3 or SG-800H.

본 발명에서는 전이금속 포착용 기능기를 갖는 모노머의 양을 아크릴계 고분자 수지를 이루는 전체 모노머의 중량을 기준으로 50 ~ 90중량% 만큼 함유하는 제 1 고분자 바인더와, 전체 모노머의 중량을 기준으로 15 ~ 30중량% 만큼 함유하는 제 2 고분자 바인더를 사용한다. 이때, 제 1 고분자 바인더 및 제 2 고분자 바인더에 포함되는 전기금속 포착용 기능기는 전체 기능기의 20 ~ 40%이 되도록 조절하는 것이 바람직하다. 전이금속 포착용 기능기가 20 중량% 미만일 경우 전이 금속과의 반응성이 저하되며, 40중량%를 초과하는 경우 유기용매에서의 용해성이 저하되어 필름의 균일도포성이 저하되거나, Tg(유리전이온도)를 증가시켜 실온에서의 필름의 깨지는 등(brittleness) 작업성이 저하될 수 있고, 다이 접착력을 저하시켜 신뢰성이 떨어질 수 있다. In the present invention, the first polymer binder containing the amount of the monomer having a transition metal capture functional group by 50 to 90% by weight based on the weight of the total monomer constituting the acrylic polymer resin, and 15 to 30 based on the weight of the total monomer A second polymer binder containing by weight% is used. At this time, it is preferable to adjust the functional group for capturing the electrometal included in the first polymer binder and the second polymer binder to be 20 to 40% of the total functional groups. If the functional group for the transition metal capture is less than 20% by weight, the reactivity with the transition metal is lowered. If it exceeds 40% by weight, the solubility in the organic solvent is lowered, so that the uniform coating property of the film is reduced or Tg (glass transition temperature) is increased. The increase in brittleness of the film at room temperature can be reduced, and the die adhesion can be lowered, resulting in poor reliability.

아울러, 상기 아크릴계 고분자 수지는 실온에서의 필름의 깨짐(brittleness)을 방지하고, 반도체 조립공정인 칩조각화(sawing) 과정에서 버(Burr) 또는 칩핑(Chipping) 현상이 발생하지 않도록 하기 위하여 0℃ ~ 30℃ 범위의 Tg(유리전이 온도)를 가지는 것이 바람직하다.In addition, the acrylic polymer resin is 0 ℃ ~ in order to prevent the brittleness of the film at room temperature (Burr) or chipping (chip) phenomenon in the chip assembly (sawing) process of the semiconductor assembly process It is preferable to have Tg (glass transition temperature) in the range of 30 ° C.

상기 아크릴계 고분자 수지는 분자량이 10만에서 70만의 범위인 것이 좋다.The acrylic polymer resin is preferably in the range of 100,000 to 700,000 molecular weight.

상기 아크릴계 고분자 수지의 함량은 반도체용 접착제 조성물 전체 중량에 대하여 2 ~ 50중량%인 것이 바람직하다. 더 바람직하게는 2 ~ 25중량%인 것이 좋다. 상기 접착 고분자 수지의 함량이 2중량% 미만일 경우에는 필름형성이 어렵고 50중량% 초과인 경우에는 신뢰성이 저하될 수 있다.The content of the acrylic polymer resin is preferably 2 to 50% by weight based on the total weight of the adhesive composition for semiconductors. More preferably, it is 2-25 weight%. When the content of the adhesive polymer resin is less than 2% by weight, it is difficult to form a film, and when it is more than 50% by weight, reliability may be lowered.

에폭시 수지Epoxy resin

본 발명의 구현예들에서 사용될 수 있는 에폭시 수지는 강한 경화 및 접착 작용을 나타낼 수 있는 강한 가교밀도를 가지고 있는 에폭시 수지가 적당하다. 하지만 가교밀도가 높은 에폭시 단독 경화 시스템의 경우 필름의 깨짐 현상이 나타날 수 있으므로 기본적으로 액상에 가까운 에폭시나 가교밀도가 최소인 단관능 또는 이관능 에폭시의 혼합을 기본으로 한다. Epoxy resins that can be used in the embodiments of the present invention are suitable epoxy resins having a strong crosslink density that can exhibit a strong curing and adhesive action. However, in the case of epoxy single curing system having a high crosslinking density, cracking of the film may occur, and basically, a mixture of epoxy close to liquid phase or monofunctional or bifunctional epoxy having a minimum crosslinking density is used.

상기와 같은 에폭시 수지는 당량이 100 ~ 1500g/eq 인 것이 바람직하고, 150 ~ 800g/eq인 것이 보다 바람직하고, 150 ~ 400g/eq인 것이 가장 바람직하다. 에폭시 당량이 100g/eq 미만이면 경화물의 접착성이 저하되는 경향이 있고, 1500g/eq를 넘는다면 유리전이온도가 저하되고, 내열성이 나쁜 경향이 있다. 에폭시수지는 경화 및 접착 작용을 나타내는 것이면 특별히 한정되지 않으나, 필름의 형상을 고려하면 고상 혹은 고상에 근접한 에폭시로서, 하나 이상의 관능기를 가지고 있는 에폭시 수지가 바람직하다.It is preferable that the equivalent epoxy resin is 100-1500 g / eq, It is more preferable that it is 150-800 g / eq, It is most preferable that it is 150-400 g / eq. If epoxy equivalent is less than 100 g / eq, the adhesiveness of hardened | cured material will fall, and if it exceeds 1500 g / eq, glass transition temperature will fall and it exists in the tendency for heat resistance to be bad. The epoxy resin is not particularly limited as long as it exhibits curing and adhesive action. However, in consideration of the shape of the film, an epoxy resin having at least one functional group is preferable as the solid phase or the epoxy near the solid phase.

상기 에폭시 수지로는 비스페놀계, 오르쏘 크레졸 노볼락(ortho-Cresol novolac)계, 다관능 에폭시, 아민계 에폭시, 복소환 함유 에폭시, 치환형 에폭시, 나프톨계 에폭시를 예시할 수 있으며, 현재 시판되고 있는 제품으로서는 비스페놀계로서는 대일본 잉크화학의 에피클론 830-S, 에피클론 EXA-830CRP, 에피클론 EXA 850-S, 에피클론 EXA-850CRP, 에피클론 EXA-835LV, 유카 쉘에폭시 주식회사의 에피 코트 807, 에피코트 815, 에피코트 825, 에피코트 827, 에피코트 828, 에피코트 834, 체피코트 1001, 에피코트 1004, 에피코트 1007, 에피코트 1009, 다우케미컬사의 DER-330, DER-301, DER-361, 국도화학의 YD-128, YDF-170등이 있고, 오르쏘 크레졸 노볼락(ortho-Cresol novolac)계로서는 국도화학의 YDCN-500-1P, YDCN-500-4P, YDCN-500-5P, YDCN-500-7P, YDCN-500-80P, YDCN-500-90P, 일본화약주식회사의 EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027 등이 있고, 다관능 에폭시 수지로서는 유카쉘 에폭시 주식회사 Epon 1031S, 시바스페샬리티케미칼주식회사의 아랄디이토 0163, 나가섭씨온도화성 주식회사의 데타콜 EX-611, 데타콜 EX-614, 데타콜 EX-614B, 데타콜 EX-622, 데타콜 EX-512, 데타콜 EX-521, 데타콜 EX-421, 데타콜 EX-411, 데타콜 EX-321 등이 있으며, 아민계 에폭시 수지로서는 유카쉘에폭시 주식회사 에피코트 604, 독도화학주식회사의 YH-434, 미쓰비시가스화학 주식회사의 TETRAD-X, TETRAD-C, 스미토모화학주식회사의 ELM-120 등이 있고, 복소환 함유 에폭시수지로는 시바스페샬리티케미칼주식회사의 PT-810, 치환형 에폭시로는 UCC사의 ERL-4234, ERL-4299, ERL-4221, ERL-4206, 나프톨계 에폭시로는 대일본 잉크화학의 에피클론 HP-4032, 에피클론 HP-4032D, 에피클론 HP-4700, 에피클론 4701등을 들 수 있고, 이것들은 단독으로 또는 2종류 이상을 혼합하여 사용할 수 있다. Examples of the epoxy resin include bisphenol-based, ortho-Cresol novolac-based, polyfunctional epoxy, amine-based epoxy, heterocyclic-containing epoxy, substituted epoxy, naphthol-based epoxy, and are currently commercially available. As a bisphenol-based product, Epicor 830-S, Epiclones EXA-830CRP, Epiclones EXA 850-S, Epiclones EXA-850CRP, Epiclones EXA-835LV, and Epicoat 807 from Yuka Shell Epoxy Co., Ltd. Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, Epicoat 1007, Epicoat 1009, DER-330, DER-301, DER- 361, YD-128, YDF-170, etc. of Kukdo Chemical Co., Ltd. include YDCN-500-1P, YDCN-500-4P, YDCN-500-5P, Kukdo Chemical Co., Ltd. of ortho-Cresol novolac. YDCN-500-7P, YDCN-500-80P, YDCN-500-90P, EOCN-102S, EOCN-103S, EOCN-104S, EOC of Nippon Kayaku Co., Ltd. N-1012, EOCN-1025, EOCN-1027, and the like.As a polyfunctional epoxy resin, Yucca Shell Epoxy Co., Ltd. Detacall EX-614, Detacall EX-614B, Detacall EX-622, Detacall EX-512, Detacall EX-521, Detacall EX-421, Detacall EX-411, Detacall EX-321 And amine epoxy resins include Yucatel Epoxy Epicoat 604, Dokdo Chemical Co., Ltd. YH-434, Mitsubishi Gas Chemical Co., Ltd. TETRAD-X, TETRAD-C, Sumitomo Chemical Co., Ltd. As resin, PT-810 from Ciba Specialty Chemicals Co., Ltd., ERL-4234, ERL-4299, ERL-4221, ERL-4206, Naphthol-based epoxy as UCP's Eplon HP- 4032, epiclon HP-4032D, epiclon HP-4700, epiclon 4701, etc. It can be mixed with poison, or two or more kinds.

상기 에폭시 수지는 다관능성 에폭시를 50 중량% 이상 포함할 수 있다. 다관능성 에폭시가 50 중량% 미만이면 가교밀도가 낮아 구조체의 내부 결합력이 저하되어 신뢰성의 문제가 야기될 수 있다.The epoxy resin may include at least 50% by weight of a multifunctional epoxy. If the polyfunctional epoxy is less than 50% by weight, the crosslinking density is low, thereby lowering the internal bonding strength of the structure, which may cause reliability problems.

본 발명의 구현예들에서 상기 에폭시 수지의 함량은 반도체용 접착제 조성물 전체 중량에 대하여 4 ~ 50중량%인 것이 바람직하고, 4 ~ 35중량%인 것이 더욱 바람직하다. 상기 에폭시 수지의 함량이 4중량% 미만일 경우 경화부 부족으로 인하여 신뢰성이 저하되고 50중량% 초과인 경우 필름의 상용성이 저하될 수 있으며, 더욱 바람직하게는 상온에서 접착 필름의 표면 끈적임(tack)성을 줄여 픽업공정 시 점착제와의 부착력을 감소시켜 픽업을 용이하게 하기 위하여 35중량%이하인 것이 좋다.In embodiments of the present invention, the content of the epoxy resin is preferably 4 to 50% by weight, more preferably 4 to 35% by weight based on the total weight of the adhesive composition for semiconductors. If the content of the epoxy resin is less than 4% by weight, the reliability is lowered due to lack of hardened portion, and if the content is more than 50% by weight, the compatibility of the film may be lowered, and more preferably, the surface tack of the adhesive film at room temperature. In order to reduce the adhesiveness and to reduce the adhesive force with the adhesive during the pick-up process, it is preferable that the weight be less than 35% by weight.

페놀형 경화수지Phenolic Curing Resin

본 발명의 구현예들에서 사용할 수 있는 페놀형 경화수지는 통상적으로 알려진 것을 사용할 수 있으나, 바람직하게는 페놀성 수산기를 1 분자 중에 2개 이상 가지는 화합물로서 흡습시의 내전해부식성이 우수한 비스페놀 A, 비스페놀 F, 비스페놀 S계 페놀형 경화수지 수지 및 페놀 노볼락 수지, 비스페놀 A계 노볼락 수지 또는 크레졸 노볼락, 자일록계, 비페닐계 등의 페놀계 수지를 사용하는 것이 좋다.The phenol-type curable resin that can be used in the embodiments of the present invention may be a conventionally known one, but preferably a bisphenol A having excellent resistance to electrolytic corrosion at the time of absorption as a compound having two or more phenolic hydroxyl groups in one molecule, It is preferable to use bisphenol F, bisphenol S-based phenol-type cured resins and phenol novolac resins, bisphenol A-based novolac resins or phenolic resins such as cresol novolacs, xyloxis and biphenyls.

이러한 페놀형 에폭시 수지 페놀형 경화수지로서 현재 시판되고 있는 제품의 예를 들면, 단순 페놀계의 페놀형 경화수지로는 메이와화성주식회사의 H-1, H-4, HF-1M, HF-3M, HF-4M, HF-45 등이 있고 파라 자일렌계열의 메이와화성주식회사의 MEH-78004S, MEH-7800SS, MEH-7800S, MEH-7800M, MEH-7800H, MEH-7800HH, MEH-78003H, 코오롱 유화주식회사의 KPH-F3065, 비페닐 계열의 메이와화성주식회사의 MEH-7851SS, MEH-7851S, MEH7851M, MEH-7851H, MEH-78513H, MEH-78514H, 코오롱유 화주식회사의 KPH-F4500, 트리페닐메틸계의 메이와화성주식회사의 MEH-7500, MEH-75003S, MEH-7500SS, MEH-7500S, MEH-7500H 등을 들 수 있고, 이것들은 단독으로 또는 2종류 이상을 혼합하여 사용할 수 있다.Examples of products currently commercially available as such phenolic epoxy resin phenolic curing resins include simple phenolic phenolic curing resins such as H-1, H-4, HF-1M and HF-3M of Meiwa Chemical Co., Ltd. MEH-78004S, MEH-7800SS, MEH-7800S, MEH-7800M, MEH-7800H, MEH-7800HH, MEH-78003H, Kolon KPH-F3065 of Emulsion Co., Ltd., MEH-7851SS, MEH-7851S, MEH7851M, MEH-7851H, MEH-78513H, MEH-78514H, KP-F4500, Triphenylmethyl MEH-7500, MEH-75003S, MEH-7500SS, MEH-7500S, MEH-7500H etc. of Meiwa Chemical Co., Ltd. of these systems are mentioned, These can be used individually or in mixture of 2 or more types.

상기 페놀형 경화수지의 수산기 당량은 바람직한 것은 100 ~ 600g/eq, 보다 바람직한 것은 170 ~ 300g/eq 이다. 수산기 당량이 100g/eq 미만이면 흡수율이 높고, 내리플로우성이 악화되는 경향이 있고, 600g/eq 를 넘으면 유리전이온도가 저하되고 내열성이 악화되는 경향이 있다.The hydroxyl equivalent of the phenol-type cured resin is preferably 100 to 600 g / eq, more preferably 170 to 300 g / eq. If the hydroxyl equivalent is less than 100 g / eq, the absorption rate is high and the reflow property tends to be deteriorated. If the hydroxyl equivalent is more than 600 g / eq, the glass transition temperature is lowered and the heat resistance tends to be deteriorated.

상기 페놀형 경화수지가 페놀 노볼락을 50 중량% 이상 포함하는 것이 바람직하다. 페놀 노볼락을 50 중량% 이상을 포함하면 경화 후 가교 밀도가 높아져 분자간 응집력의 증가로 내부 결합력이 증가하여 접착력을 향상시킬 수 있으며, 외부 응력에 대한 변형력이 작아 일정 두께를 유지할 수 있다는 면에서 유리하다. It is preferable that the said phenol type hardening resin contains 50 weight% or more of phenol novolaks. When the phenol novolak is contained in an amount of 50% by weight or more, the crosslinking density increases after curing, thereby increasing the internal bonding force due to the increase of the intermolecular cohesive force, thereby improving the adhesive force, and in view of maintaining a constant thickness due to the small strain against external stress. Do.

본 발명의 상기 페놀형 경화수지가 반도체용 접착제 조성물 전체 중량에 대하여 3 ~ 50중량%인 것이 바람직하고, 3 ~ 30중량%인 것이 더욱 바람직하다.It is preferable that it is 3-50 weight% with respect to the total weight of the adhesive composition for semiconductors, and, as for the said phenol type hardening resin of this invention, it is more preferable that it is 3-30 weight%.

경화촉매Curing catalyst

본 발명의 구현예들에서 사용할 수 있는 경화촉매는 경화속도를 조절하는 첨가제로써 포스핀 또는 보론계 경화촉매와 이미다졸계의 촉매를 사용할 수 있다.The curing catalyst that can be used in the embodiments of the present invention may use a phosphine or boron curing catalyst and an imidazole catalyst as an additive to control the curing rate.

본 발명의 구현예들에서 사용할 수 있는 포스핀계 경화촉매는 트리페닐포스핀(Triphenylphosphine), 트리-o-토일포스핀(Tri-o-tolylphosphine), 트리-m-토일포스핀(Tri-m-tolylphosphine), 트리-p-토일포스핀(Tri-p-tolylphosphine), 트리- 2,4-자일포스핀(Tri-2,4-xylylphosphine), 트리-2, 5-자일포스핀(Tri-2, 5-xylylphosphine), 트리-3, 5-자일포스핀(Tri-3, 5-xylylphosphine), 트리벤질포스핀(Tribenzylphosphine), 트리스(p-메톡시페닐)포스핀(Tris(p-methoxyphenyl)phosphine), 트리스(p-tert-부톡시페닐)포스핀(Tris(p-tert-butoxyphenyl)phosphine), 디페닐시클로헥실포스핀(Diphenylcyclohexylphosphine), 트리시클로포스핀(Tricyclohexylphosphine), 트리부틸포스핀(Tributylphosphine), 트리-tett-부틸포스핀(Tri-tert-butylphosphine), 트리-n-옥틸포스핀(Tri-n-octylphosphine), 디페닐포스피노스타이렌(Diphenylphosphinostyrene), 디페닐포스피노어스클로라이드(Diphenylphosphinouschloride), 트리-n-옥틸포스핀옥사이드(Tri-n-octylphosphine oxide), 디페닐포스피닐히드로퀴논(Diphenylphosphinyl hydroquinone), 테트라부틸포스포늄히드록시드(Tetrabutylphosphonium hydroxide), 테트라부틸포스피니움아세테이트(Tetrabutylphosphonium acetate), 벤질트리페닐포스피늄헥사플루오로안티모네이트(Benzyltriphenylphosphonium hexafluoroantimonate), 테트라페닐포스피늄테트라페닐보레이트(Tetraphenylphosphonium tetraphenylborate), 테트라페닐포스포늄테트라-p-토일보레이트(Tetraphenylphosphonium tetra-p-tolylborate), 벤질트리페닐포스포늄테트라페닐보레이트(Benzyltriphenylphosphonium tetraphenylborate), 테트라페닐포스포늄테트라플루오로보레이트(Tetraphenylphosphonium tetrafluoroborate), p-토일트리페닐포스포늄테트라-p-토일보레이트(p-Tolyltriphenylphosphonium tetra-p-tolylborate), 트리페닐포스핀트리페닐보레인(Triphenylphosphine triphenylborane), 1,2-비스(디페닐포스피노)에탄(1,2-Bis(diphenylphosphino)ethane), 1,3-비스(디페닐포스피노)프로판(1,3-Bis(diphenylphosphino)propane), 1,4-비스(디페닐포스피노)부탄(1,4-Bis(diphenylphosphino)butane), 1,5-비스(디페닐포스피노)펜탄(1,5-Bis(diphenylphosphino)pentane)등이 있고 보론계 경화촉매로는 페닐보로닉산(Phenyl boronic acid), 4-메틸페닐보로닉산(4-Methylphenyl boronic acid), 4-메톡시페닐보로닉산(4-Methoxyphenyl boronic acid), 4-트리프루오로메톡시페닐보로닉산(4-Trifluoromethoxyphenyl boronic acid), 4-tert-부톡시페닐보로닉산(4-tert-Butoxyphenyl boronic acid), 3-플루오로-4-메톡시페닐보로닉산(3-Fluoro-4-methoxyphenyl boronic acid), 피리딘-트리페닐보렌(Pyridine-triphenylborane), 2-에틸-4-메틸이미다졸륨테트라페닐보레이트(2-Ethyl-4-methyl imidazolium tetraphenylborate), 1,8-디아자바이시클로[5.4.0]언데센-7-테트라페닐보레이트(1,8-Diazabicyclo[5.4.0]undecene-7-tetraphenylborate) 중 하나 이상을 사용할 수 있다.The phosphine-based curing catalyst that can be used in the embodiments of the present invention is triphenylphosphine (Triphenylphosphine), tri-o-tolylphosphine (Tri-o-tolylphosphine), tri-m-toylphosphine (Tri-m- tolylphosphine), Tri-p-tolylphosphine, Tri-2,4-xylylphosphine, Tri-2, 5-xylphosphine , 5-xylylphosphine), tri-3, 5-xylphosphine (Tri-3, 5-xylylphosphine), tribenzylphosphine, tris (p-methoxyphenyl) phosphine (Tris (p-methoxyphenyl) phosphine, tris (p-tert-butoxyphenyl) phosphine (tris (p-tert-butoxyphenyl) phosphine), diphenylcyclohexylphosphine, tricyclophosphine (tricyclohexylphosphine), tributylphosphine ( Tributylphosphine), Tri-tert-butylphosphine, Tri-n-octylphosphine, Diphenylphosphinostyrene, Diphenylphosphinophosphate Diphenylphos phinouschloride, Tri-n-octylphosphine oxide, Diphenylphosphinyl hydroquinone, Tetrabutylphosphonium hydroxide, Tetrabutylphosphinium acetate acetate), benzyltriphenylphosphonium hexafluoroantimonate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, Benzyltriphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrafluoroborate, p-toyllphenylphosphonium tetra-p-toylborate, p-Tolyltriphenylphosphonium tetra-p-tolylborate Triphenyl phosphine triphenyl borane (Triphe nylphosphine triphenylborane), 1,2-bis (diphenylphosphino) ethane (1,2-Bis (diphenylphosphino) ethane), 1,3-bis (diphenylphosphino) propane (1,3-Bis (diphenylphosphino) propane ), 1,4-bis (diphenylphosphino) butane (1,4-Bis (diphenylphosphino) butane), 1,5-bis (diphenylphosphino) pentane (1,5-Bis (diphenylphosphino) pentane) Boron curing catalysts include phenyl boronic acid, 4-Methylphenyl boronic acid, 4-Methoxyphenyl boronic acid, 4- 4-Trifluoromethoxyphenyl boronic acid, 4-tert-Butoxyphenyl boronic acid, 3-fluoro-4-methoxyphenylboronic acid (3-Fluoro-4-methoxyphenyl boronic acid), Pyridine-triphenylborane, 2-Ethyl-4-methyl imidazolium tetraphenylborate, 1, 8-diazabicyclo [5.4.0] undecene-7-tet One or more of the phenyl borate (1,8-Diazabicyclo [5.4.0] undecene-7-tetraphenylborate) may be used.

본 발명에서 상기 경화촉매 함량은 반도체용 접착제 조성물 전체 중량에 대하여 0.01 ~ 10중량%인 것이 바람직하다. 더욱 바람직하게는 경화촉매의 함량이 반도체용 접착제 조성물 전체 중량에 대하여 0.01 ~ 2중량%인 것이 바람직하다. 10중량% 초과인 경우 저장안정성이 떨어질 가능성이 있다. In the present invention, the curing catalyst content is preferably 0.01 to 10% by weight based on the total weight of the adhesive composition for semiconductors. More preferably, the content of the curing catalyst is 0.01 to 2% by weight based on the total weight of the adhesive composition for a semiconductor. If it is more than 10% by weight, the storage stability may be reduced.

실란 커플링제Silane coupling agent

본 발명에서 실란 커플링제는 조성물 배합시 실리카와 같은 무기물질의 표면과 접착필름의 수지간의 접착력을 증진시키기 위한 접착증진제로서 특별히 제한은 없고 통상적으로 사용되는 실란 커플링제를 사용할 수 있다.In the present invention, the silane coupling agent is not particularly limited as an adhesion enhancer for enhancing the adhesion between the surface of an inorganic material such as silica and the resin of the adhesive film, and a silane coupling agent may be used.

상기 실란 커플링제로서는 에폭시 함유 실란 또는 머캡토 함유 실란인 것을 사용할 수 있으며, 에폭시가 함유된 것으로 2-(3,4 에폭시 사이클로 헥실)-에틸트리메톡시실란, 3-글리시독시트리메톡시실란, 3-글리시독시프로필트리에톡시실란, 3-글리시독시프로필트리에톡시실란이 있고, 아민기가 함유된 것으로 N-2(아미노에틸)3-아미토프로필메틸디메톡시실란, N-2(아미노에틸)3-아미노프로필트리메톡시실란, N-2(아미노에틸)3-아미노프로필트리에톡시실란, 3-아미노프로필트리메톡시실란, 3-아미노프로필트리에톡시실란, 3-트리에톡시실리-N-(1,3-디메틸뷰틸리덴)프로필아민, N-페닐-3-아미노프로필트리메톡시실란이 있으며, 머켑토가 함유된 것으로 3-머켑토프로필메틸디메톡시실란, 3-머켑토프로필트리에톡시실란, 이소시아네이트가 함유된 3-이소시아네이트프로필트리에톡시실란을 예시할 수 있으며, 이들을 단독 또는 2종 이상을 혼합하여 사용할 수 있다. As the silane coupling agent, an epoxy-containing silane or a mercapto-containing silane can be used, and epoxy-containing 2- (3,4 epoxy cyclohexyl) -ethyltrimethoxysilane and 3-glycidoxytrimethoxysilane , 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, containing an amine group, N-2 (aminoethyl) 3-amitopropylmethyldimethoxysilane, N-2 (Aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-tri Ethoxysil-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, containing merceto, 3-mercetopropylmethyldimethoxysilane, 3-mercetopropyltriethoxysilane, 3-isocyanae containing isocyanate It can be exemplified by silane in the profile tree, and can use them by mixing, alone or in combination of two or more.

상기 실란커플링제는 반도체용 접착제 조성물 전체 중량에 대하여 0.01 ~ 10중량%인 것이 바람직하다. The silane coupling agent is preferably 0.01 to 10% by weight based on the total weight of the adhesive composition for a semiconductor.

충진제Filler

본 발명의 조성물은 틱소트로픽성을 발현하여 용융점도를 조절하기 위하여 충진제를 포함한다. 상기 충진제는 필요에 따라 무기 또는 유기 충진제를 사용할 수 있으며, 무기 충진제로는 금속성분인 금가루, 은가루, 동분, 니켈을 사용할 수 있고, 비금속성분인 알루미나, 수산화 일미늄, 수산화 마그네슘, 탄산칼슘, 탄산마그네슘, 규산칼슘, 규산마그네슘, 산화칼슘, 산화마그네슘, 산화 알루미늄, 질화 알루미늄, 실리카, 질화 붕소, 이산화티타늄, 유리, 산화철, 세라믹 등을 사용할 수 있고, 유기 충진제로서는 카본, 고무계 필러, 폴리머계 등을 사용할 수 있다. 상기 충진제의 형상과 크기는 특별히 제한되지 않으나, 본 발명에서는 구형실리카가 바람직하며 용도에 따라 구형 표면이 소수성 특성을 가지는 충진제가 사용될 수 있다. The composition of the present invention includes a filler to control the melt viscosity by expressing thixotropic properties. The filler may be used as an inorganic or organic filler, if necessary, the inorganic filler may be metal powder gold, silver powder, copper powder, nickel, non-metallic alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, carbonic acid Magnesium, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, silica, boron nitride, titanium dioxide, glass, iron oxide, ceramics and the like can be used, and organic fillers include carbon, rubber fillers, polymers, and the like. Can be used. The shape and size of the filler is not particularly limited, but in the present invention, spherical silica is preferable, and a filler having a hydrophobic property on a spherical surface may be used according to the use.

본 발명에서 사용되는 구형 실리카의 크기는 500nm ~ 5㎛의 범위가 바람직하다. 상기 무기 충진제의 입자가 10㎛이상일 경우 반도체 회로와의 충돌로 인하여 회로 손상의 가능성이 있다.The size of the spherical silica used in the present invention is preferably in the range of 500nm to 5㎛. If the particle of the inorganic filler is more than 10㎛ there is a possibility of circuit damage due to the collision with the semiconductor circuit.

본 발명의 구현예들에서 상기 충진제의 사용량은 반도체용 접착제 조성물 전체 중량에 대하여 0.1 ~ 50중량%인 것이 바람직하다. 본 발명에서 사용되는 접착필름은 주로 같은 크기 다이 접착제 필름으로 사용되므로 이 경우 10 ~ 40중량%가 바람직하다. 50중량% 초과인 경우에는 필름형성이 어려워져 필름의 인장강도가 저하될 수 있다.In the embodiments of the present invention, the amount of the filler is preferably 0.1 to 50% by weight based on the total weight of the adhesive composition for a semiconductor. Since the adhesive film used in the present invention is mainly used as the same size die adhesive film 10 to 40% by weight in this case is preferred. If it is more than 50% by weight, it is difficult to form a film, which may lower the tensile strength of the film.

본 발명에 따른 접착제 조성물은 상술한 바와 같으며, 전이금속 포착용 기능기가 고분자 바인더에만 포함되는 것으로 설명하였으나 에폭시 또는 실란커플링제와 같이 기능기를 포함할 수 있는 조성이면 어디에든 포함될 수 있다.The adhesive composition according to the present invention has been described above, and the functional group for capturing the transition metal has been described as being included only in the polymer binder, but may be included in any composition that may include a functional group such as an epoxy or a silane coupling agent.

아울러, 본 발명의 다른 양상은 상기 반도체용 접착제 조성물로 형성된 반도체용 접착 필름에 관한 것으로서, 그 제조 공정에 대해 설명하면 다음과 같다.In addition, another aspect of the present invention relates to a semiconductor adhesive film formed of the adhesive composition for semiconductors, the manufacturing process thereof will be described as follows.

먼저, 상기 조성물을 이용하여 80 ~ 120℃의 온도에서 10 ~ 60분 동안 건조하여 접착필름에 포함된 잔류 용매의 양을 2% 미만으로 조절한 것을 사용하되, 반드시 이에 한정되는 것은 아니다. 상기 건조온도나 시간의 제어를 통해 상기 조성물에 잔류하는 저비점 용매의 양은 제거하고 고비점 용매의 함유량은 2% 미만으로 조절할 수 있다. First, using the composition to dry for 10 to 60 minutes at a temperature of 80 ~ 120 ℃ to adjust the amount of the residual solvent contained in the adhesive film to less than 2%, but is not necessarily limited thereto. By controlling the drying temperature or time, the amount of the low boiling point solvent remaining in the composition may be removed and the content of the high boiling point solvent may be adjusted to less than 2%.

다음으로, 상기 접착필름은 120 ~ 150℃의 온도에서 1 ~ 10 시간 동안 경화된다. 좀더 구체적으로 120℃ ~ 130℃ 온도조건에서 1 ~ 3시간 1차 경화 과정을 거치고 연속으로 130℃ ~ 150℃에서 10 ~ 60분의 2차 경화과정을 거치는 것을 하나의 과정으로 하여 1 ~ 8번 정도 실시할 수 있다. 상기 과정을 통해 잔류 용매에 의한 휘발성 발포 정도를 결정할 수 있다. 상기 경화과정을 거치는 동안 상기 조성물에 잔류하는 용매의 종류와 함유량 및 여러 가지 물리적 특성을 고려하여 용매의 휘발 가능성에 의한 문제를 조절할 수 있다. Next, the adhesive film is cured for 1 to 10 hours at a temperature of 120 ~ 150 ℃. More specifically, 1 to 3 times the first curing process at 120 ℃ ~ 130 ℃ temperature conditions 1 to 8 times in a continuous process of the secondary curing process of 10 to 60 minutes at 130 ℃ ~ 150 ℃ continuously It can be carried out to a degree. Through this process it is possible to determine the degree of volatile foaming due to the residual solvent. During the curing process, the problem due to the volatility of the solvent may be adjusted in consideration of the type and content of the solvent remaining in the composition and various physical properties.

상기 경화 시 필름에 잔류하고 있는 용매를 고비점 용매만 최소화 함으로서 다이 어태치시 발생할 수 있는 휘발 성분에 의한 보이드를 최소화 시킬 수 있으며, 생성된 버블의 부피팽창을 완화시킬 수 있다. By minimizing only the high boiling point solvent of the solvent remaining in the film during the curing, it is possible to minimize the voids due to the volatile components that may occur during die attach, and to reduce the volume expansion of the generated bubbles.

좀 더 구체적으로 살펴보면, 125℃의 경화 온도보다 비점이 낮은 용매만을 사용하는 경우, 경화 시 잔존하는 용매에 의한 휘발성 보이드가 형성될 수 있다. 또한, 비점이 200℃ 이상인 용매를 사용하는 경우, 필름 형성 시 잔존하는 용매의 양이 2% 이상이 되므로, 이는 EMC 몰딩 공정이나 신뢰도 평가과정에서 잔존 용매 함량에 의한 부피팽창을 야기하여 신뢰도 저하에 영향을 미치게 될 수 있다. In more detail, when using only a solvent having a boiling point lower than the curing temperature of 125 ℃, volatile voids due to the solvent remaining during the curing may be formed. In addition, when a solvent having a boiling point of 200 ° C. or more is used, the amount of solvent remaining during film formation becomes 2% or more, which causes volume expansion due to the residual solvent content in the EMC molding process or the reliability evaluation process, thereby affecting the reliability decrease. Can be crazy.

앞에서 상술한 바와 같이 상기 조성물은 저비점 용매와 고비점 용매의 적절한 비율 및 함량을 제시하였다. 이러한 함량의 고비점 용매는 계면상에 형성된 갭이나 보이드의 부피팽창을 완화시켜 칩과 계면의 접착 시 발생되는 보이드를 최소화함과 동시에, 와이어 충전 시 발생할 수 있는 갭이나 보이드에 의한 부피팽창을 완화시켜 고 신뢰성을 발휘하는 반도체용 접착 필름을 제공할 수 있다. 또한, 경화 전 필름의 깨짐의 특성을 완화시켜 소잉(Sawing) 과정이나 마운팅 과정 중에 발생할 수 있는 접착 필름의 부스러기로 인한 오염을 방지할 수 있으며 필름의 조작이 용이한 장점을 지닌다.As described above, the composition suggested an appropriate ratio and content of the low boiling point solvent and the high boiling point solvent. This high boiling point solvent reduces the volume expansion of gaps or voids formed on the interface to minimize voids generated when the chip and the interface are bonded, and at the same time reduces the volume expansion caused by gaps or voids that may occur during wire filling. To provide a semiconductor adhesive film exhibiting high reliability. In addition, it is possible to prevent the contamination due to the debris of the adhesive film that may occur during the sawing (Sawing) process or mounting process by relieving the characteristics of the film before curing, and has the advantage of easy operation of the film.

아울러, 상술한 바와 같이 본 발명에 따른 접착필름에서 잔류 용매의 양이 2% 미만이다. 따라서, 상기 조성물에 의하여 만들어진 접착 필름의 막고형분은 98% 이상이다. 막 고형분이 98%보다 작으면 잔류하는 용매에 의한 발포나 흡습성 특성 때문에 신뢰성 저하를 야기할 수 있기 때문이다.In addition, the amount of the residual solvent in the adhesive film according to the present invention as described above is less than 2%. Therefore, the film solid content of the adhesive film made by the composition is 98% or more. This is because when the film solid content is less than 98%, reliability may be deteriorated due to foaming or hygroscopic properties by the remaining solvent.

다음으로, 상기 접착필름의 신장률이 150 ~ 400%일 수 있다. Next, the stretch ratio of the adhesive film may be 150 to 400%.

상기 접착필름은 25℃에서의 저장탄성율이 0.1 ~ 10 MPa이고, 80℃에서의 저장탄성율이 0.01 ~ 0.10 MPa이고, 상기 접착필름이 25℃에서 1,000,000 ~ 5,000,000P의 용융점도를 가지며, 0.1 gf 미만의 표면 점성(tack)을 가질 수 있다. 이는 필름 내부에 존재하는 용매에 의하여 기존 조성물이 가지는 점도나 표면 점성이 변화하지 않으므로, 반도체 조립 공정 시 요구되는 물성에는 큰 영향을 받지 않 는다. 즉, 경화 전 접착제의 저장 탄성율 및 유동성이나 표면 점성은 고비점 용매의 존재에 따른 영향 없이 일정하게 유지되는 장점을 지닌다. 따라서, 고비점 용매에 의한 상온 저장성에 영향을 받지 않는다. The adhesive film has a storage modulus of 0.1 to 10 MPa at 25 ° C., a storage modulus of 0.01 to 0.10 MPa at 80 ° C., and the adhesive film has a melt viscosity of 1,000,000 to 5,000,000 P at 25 ° C., and is less than 0.1 gf. It may have a surface tack of. This does not change the viscosity or surface viscosity of the existing composition by the solvent present in the film, it is not significantly affected by the physical properties required during the semiconductor assembly process. In other words, the storage modulus and fluidity or surface viscosity of the adhesive before curing has the advantage of being kept constant without being affected by the presence of a high boiling point solvent. Therefore, the shelf life is not affected by the high boiling point solvent.

본 발명에 의한 접착필름은 125℃ 이상 175℃ 이하의 온도에서 휘발 속도와 휘발하려는 양이 저비점의 용매 사용에 의하여 제작된 필름에 비하여 작기 때문에 연 구조성을 가지게 되어 필름이 깨지는 것을 방지할 수 있으며, 보이드(void) 생성 완화 효과를 가지기 때문에 반도체 조립 시 면상 보이드 생성을 5% 미만으로 최소화 하여 신뢰성 저하를 방지할 수 있는 특징을 확보할 수 있다.Since the adhesive film according to the present invention has a soft structure at a temperature of 125 ° C. or more and 175 ° C. or less, compared to a film produced by using a solvent having a low boiling point, the adhesive film has a soft structure to prevent the film from breaking. As a result, the void generation can be reduced, thereby minimizing the surface void generation to less than 5% when assembling the semiconductor, thereby securing a feature that can prevent reliability degradation.

한편, 본 발명은 반도체용 복층형 접착층을 포함하는 다이싱 다이 본딩 필름(Dicing Die Bonding Film)을 포함한다. 기재 필름상에 점착제층과 접착층이 순차로 적층된 다이싱 다이 본딩 필름에 있어서, 먼저, 상기 기재 필름은 방사선 투과성이 있는 것이 바람직하고 자외선 조사에 따라 반응하는 방사선 경화성 점착제를 적용할 경우에 광투과성이 좋은 기재를 선택할 수 있다. 이와 같은 기재로서 선택할 수 있는 폴리머의 예로서는, 폴리에틸렌, 폴리프로필렌, 프로필렌 에틸렌 공중합체, 에틸렌 아크릴산 에틸 공중합체, 에틸렌 아크릴산 메틸 공중합체, 에틸렌 초산비닐 공중합체 등의 폴리올레핀의 단독 중합체 또는 공중합체, 폴리카보네이트. 폴리메틸 메타아크릴레이트, 폴리염화비닐, 폴리우레탄 공중합체 등을 사용할 수 있다. 기재 필름의 두께는 인장강도, 신율, 방사선투과성 등을 고려하여 50 ~ 200 ㎛이 적당하다.On the other hand, the present invention includes a dicing die bonding film (Dicing Die Bonding Film) comprising a multilayer adhesive layer for a semiconductor. In the dicing die bonding film in which the pressure-sensitive adhesive layer and the adhesive layer are sequentially laminated on the base film, first, the base film is preferably radiation-transmissive and is light-transmissive when applying a radiation curable pressure-sensitive adhesive reacting upon ultraviolet irradiation. This good base material can be selected. Examples of the polymer that can be selected as such a substrate include homopolymers or copolymers of polyolefins such as polyethylene, polypropylene, propylene ethylene copolymers, ethylene ethyl acrylate copolymers, ethylene methyl acrylate copolymers, ethylene vinyl acetate copolymers, and polycarbonates. . Polymethyl methacrylate, polyvinyl chloride, polyurethane copolymers and the like can be used. The thickness of the base film is preferably 50 ~ 200 ㎛ in consideration of the tensile strength, elongation, radiolucent.

다음으로, 점착제층은 통상적인 점착제 조성물을 사용할 수 있고, 하나의 예 로서, 점착 특성을 갖는 고분자 바인더 100중량부에 대하여 UV 경화형 아크릴레이트를 20 ~ 150중량부를 포함하고, 및 광개시제를 상기 UV경화형 아크릴레이트 100중량부에 대하여 0.1 ~ 5 중량부 포함하는 것을 사용할 수 있다.Next, the pressure-sensitive adhesive layer may use a conventional pressure-sensitive adhesive composition, as one example, 20 to 150 parts by weight of a UV curable acrylate based on 100 parts by weight of a polymer binder having adhesive properties, and the photoinitiator is UV curable It can use the thing containing 0.1-5 weight part with respect to 100 weight part of acrylates.

그 다음으로, 접착층은 전이금속 이온 포착 기능을 갖는 제 1 접착층과 유동성을 확보한 제 2 접착층의 복층 구조 접착 필름 형태로 구비된다.Next, the adhesive layer is provided in the form of a multilayer structure adhesive film of a first adhesive layer having a transition metal ion trapping function and a second adhesive layer ensuring fluidity.

아울러, 상기 다이싱 다이본딩 필름에서 점착층만 빠진 형태가 되면, 반도체 칩과 반도체 칩의 적층을 위한 접착필름이 되며 하기 도 1과 같이 적용될 수 있다.In addition, if only the adhesive layer in the dicing die-bonding film is missing form, it becomes an adhesive film for laminating the semiconductor chip and the semiconductor chip can be applied as shown in FIG.

도 1은 본 발명에 따른 복층구조의 접착 필름을 나타낸 단면도이다.1 is a cross-sectional view showing an adhesive film of a multilayer structure according to the present invention.

도 1을 참조하면, 인쇄회로 기판(100) 상부에 기저 접착층(110)이 구비된 제 1 반도체 칩(120)이 접착된다. 다음에는, 와이어 본딩(130)이 수행되고, 제 1 반도체 칩(120) 상부에 제 1 및 제 2 접착층을 가진 제 2 반도체 칩(160)이 적층된다. Referring to FIG. 1, a first semiconductor chip 120 having a base adhesive layer 110 is bonded to an upper portion of a printed circuit board 100. Next, wire bonding 130 is performed, and the second semiconductor chip 160 having the first and second adhesive layers is stacked on the first semiconductor chip 120.

이때, 제 2 접착층(140)이 하부에 위치하는 것은 기재필름, 제 2 접착층(140) 및 제 1 접착층(150) 의 적층 순서로 되어 있는 복층구조의 접착 필름을, 제 1 접착층과 제 2 반도체 칩과 라미네이션 과정을 거친 후 픽업과정을 통하여 기재필름으로부터 제거 한 후 제 1 반도체 칩(120)에 붙였기 때문에 나타나는 결과이다.At this time, the second adhesive layer 140 is located below the multilayer film adhesive film in the order of laminating the base film, the second adhesive layer 140 and the first adhesive layer 150, the first adhesive layer and the second semiconductor. After the lamination process with the chip is removed from the base film through the pick-up process and is attached to the first semiconductor chip 120 results.

상기 구조에서, 본 발명에 따른 제 1 접착층(150)은 전이금속이 오염된 제 2 반도체 칩(160)의 전이금속과 화학적 환원 또는 결합 반응을 통해 전이금속의 상태를 변화시켜 이동성을 억제시키고, 이를 통하여 칩의 작동 효율성을 극대화시키는 역할을 하도록 구비된다. 이와 같은 제 1 접착층(150)은 전이금속을 환원시킬 수 있는 작용기를 다량 포함하도록 구비되는 것이 바람직하다. 그러나, 이 경우 전이금속 환원력은 강하나 고분자의 함량 증가로 유동성은 감소될 수 있다. In the above structure, the first adhesive layer 150 according to the present invention changes the state of the transition metal through a chemical reduction or a coupling reaction with the transition metal of the second semiconductor chip 160 in which the transition metal is contaminated, thereby inhibiting mobility. This is provided to serve to maximize the operational efficiency of the chip. The first adhesive layer 150 is preferably provided to include a large amount of functional groups capable of reducing the transition metal. However, in this case, the transition metal reducing power is strong, but the fluidity may be reduced by increasing the content of the polymer.

따라서, 전이금속을 환원시킬 수 있는 작용기의 함량이 감소된 제 2 접착층(140)을 형성함으로써, 전체적인 접착필름의 유동성이 확보될 수 있도록 하는 것이다. 그러므로 이 두 가지의 특성을 극대화 할 수 있는 복층구조를 가질 경우 두 가지의 장점을 모두 발현할 수 있는 접착 필름을 구현할 수 있다.Therefore, by forming the second adhesive layer 140 is reduced in the content of the functional group capable of reducing the transition metal, it is to ensure the fluidity of the entire adhesive film. Therefore, when the multilayer structure to maximize the two characteristics can be implemented an adhesive film that can express both advantages.

제 2 접착층(140)은 유동성을 증가시켜 어테치 보이드(Attach void)를 최소화 하며, 같은 크기의 칩을 적층할 경우 요구되는 와이어 충진성을 최대화시켜 적층 시 발생하는 보이드를 최소화 시킬 수 있으며 이를 통하여 높은 신뢰성을 확보할 수 있도록 구비된다.The second adhesive layer 140 increases fluidity to minimize attach voids and maximizes wire filling required when stacking chips of the same size, thereby minimizing voids generated during stacking. It is provided to ensure high reliability.

여기서, 제 1 접착층(150)의 두께는 전체 접착 필름 두께의 8 ~ 25%이고, 제 2 접착층(140)의 두께는 전체 접착 필름 두께의 75 ~ 98%가 되도록 형성하는 것이 바람직하다.Here, the thickness of the first adhesive layer 150 is preferably 8 to 25% of the total adhesive film thickness, and the thickness of the second adhesive layer 140 is preferably formed to be 75 to 98% of the total adhesive film thickness.

이하에서는 상기 제 1 및 제 2 접착층 제조를 위한 구체적인 실시예들에 대해 상세히 설명하는 것으로 한다.Hereinafter, specific embodiments for manufacturing the first and second adhesive layers will be described in detail.

여기서, 본 발명의 이점 및 특징 및 그것들을 달성하는 방법은 상세하게 후 술되어 있는 실시예들을 참조하면 명확해질 것이다. 그러나, 본 발명은 이하에서 개시되는 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 것이며, 단지 본 실시예들은 본 발명의 개시가 완전하도록 하며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이며, 본 발명은 청구항의 범주에 의해 정의될 뿐이다.Here, the advantages and features of the present invention and the method of achieving them will be apparent with reference to the embodiments described later in detail. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various different forms, and only the embodiments make the disclosure of the present invention complete, and those skilled in the art to which the present invention pertains. It is provided to fully inform the person having the scope of the invention, which is defined only by the scope of the claims.

실시예 1 ~ 6, 비교예 1 ~ 6Examples 1-6, Comparative Examples 1-6

고속 교반봉을 포함하는 1L 원통형 플라스크에 하기의 성분을 첨가하고 20분간 3000 rpm에서 저속으로 그리고 5분간 4000rpm에서 고속으로 5분간 분산하여 조성물을 제조한 뒤 50㎛ 캡슐 필터를 이용하여 여과한 뒤 어플리케이터로 60㎛ 두께로 코팅하여 접착 필름을 제조하였으며, 80℃에서 20분가 1차 건조한 뒤 90℃에서 20분간 2차 건조한 후 실온에서 1일간 보관하였다.The following components were added to a 1 L cylindrical flask containing a high speed stirring rod and dispersed for 5 minutes at 3000 rpm for 20 minutes at low speed and 5 minutes at 4000 rpm for 5 minutes to prepare a composition, followed by filtration using a 50 μm capsule filter and then applicator. An adhesive film was prepared by coating to a thickness of 60 μm, followed by primary drying for 20 minutes at 80 ° C., followed by secondary drying for 20 minutes at 90 ° C., and storage at room temperature for 1 day.

<실시예 1 ~ 3><Examples 1 to 3>

(1) 제 1 접착층(1) first adhesive layer

ㄱ. 전이금속 포착용 기능기(-CN, -COOH, -NCO, -SH 및 -NH 등) 함유 고분자 수지 (SG-P3계열(기능기 함량 25%), 제조원: 나가세) 384 g,A. 384 g of polymer resin containing functional group (-CN, -COOH, -NCO, -SH and -NH, etc.) for capture transition metal (SG-P3 series (functional group content 25%), manufacturer: Nagase)

ㄴ. 다관능 에폭시 수지(EP-5100R, 제조원: 국도화학) 또는 설퍼기를 가지는 에폭시 수지(YSLV-120TE, 제조원 : 니폰스틸 케미칼) 32 g, N. 32 g of a polyfunctional epoxy resin (EP-5100R, manufactured by Kukdo Chemical) or an epoxy resin having a sulfur group (YSLV-120TE, manufactured by Nippon Steel Chemical),

ㄷ. 페놀 노블락 페놀형 경화수지(DL-92, 제조원:메이와 플라스틱산업주식회 사) 11 g,C. 11 g of phenol noblock phenol type hardening resin (DL-92, a manufacturer: Meiwa Plastic Industry Co., Ltd.),

ㄹ. 포스핀계 경화촉매(TPP-K, TPP, 또는 TPP-MK 제조원: 메이화플라스틱산업주식회사) 0.6 g,D. Phosphine curing catalyst (TPP-K, TPP, or TPP-MK manufacturer: Meihwa Plastic Industry Co., Ltd.) 0.6 g,

ㅁ. 실란 커플링제(KBM-303, 제조원: 신에쯔주식회사) 3.0g,M. Silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 3.0 g,

ㅂ. 무정형 실리카(A200, 제조원: 대구사) 10 g. Iii. 10 g of amorphous silica (A200, manufactured by Daegu).

(2) 제 2 접착층(2) second adhesive layer

ㄱ. 전이금속 포착용 기능기(-CN, -COOH, -NCO, -SH 및 -NH 등) 함유 고분자 수지 (SG-P3계열(기능기 함량 25%), 제조원: 나가세) 220 g,A. 220 g of polymer resin (SG-P3 series (functional group content 25%), containing a functional group for transition metal capture (-CN, -COOH, -NCO, -SH and -NH, etc.)

ㄴ. 다관능 에폭시 수지(EP-5100R, 제조원: 국도화학) 또는 설퍼기를 가지는 에폭시 수지(YSLV-120TE, 제조원 : 니폰스틸 케미칼) 80 g, N. 80 g of a polyfunctional epoxy resin (EP-5100R, manufactured by Kukdo Chemical) or an epoxy resin having a sulfur group (YSLV-120TE, manufactured by Nippon Steel Chemical),

ㄷ. 페놀 노블락 페놀형 경화수지(DL-92, 제조원:메이와 플라스틱산업주식회사) 60 g,C. 60 g of phenol noblock phenol type hardening resin (DL-92, a manufacturer: Meiwa Plastic Industry Co., Ltd.),

ㄹ. 포스핀계 경화촉매(TPP-K, TPP, 또는 TPP-MK 제조원: 메이화플라스틱산업주식회사) 3.8 g,D. Phosphine-based curing catalyst (TPP-K, TPP, or TPP-MK manufacturer: Meihwa Plastic Industry Co., Ltd.) 3.8 g,

ㅁ. 에폭시 실란 커플링제(KBM-303, 제조원: 신에쯔주식회사) 2.2g,M. Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 2.2 g,

ㅂ. 구형 실리카(SC-4500SQ, SC-2500SQ, 제조원: 아드마텍스(Admatechs)) 70 g,Iii. 70 g of spherical silica (SC-4500SQ, SC-2500SQ, Admatechs),

ㅅ. 전이금속 포착용 기능기 가지는 첨가제(아크릴로 니트릴, 제조원 : 알드리치, 또는 Ciba Irgamet계, 제조원 : 시바) 또는 멀켑토 또는 아미노 실란 커플링 제 (KBM-573 또는 KBM-803, 제조원 : 신에쯔 주식회사) 1.0 g.G. Additives having functional groups for capturing transition metals (acrylonitrile, manufactured by Aldrich or Ciba Irgamet, manufactured by Ciba) or merceto or amino silane coupling agents (KBM-573 or KBM-803, manufactured by Shin-Etsu Co., Ltd.) ) 1.0 g.

<실시예 4><Example 4>

(1) 제 1 접착층(1) first adhesive layer

ㄱ. 전이금속 포착용 기능기(-CN, -COOH, -NCO, -SH 및 -NH 등) 함유 고분자 수지 (SG-P3계열(기능기 함량 25%), 제조원: 나가세) 384 g,A. 384 g of polymer resin containing functional group (-CN, -COOH, -NCO, -SH and -NH, etc.) for capture transition metal (SG-P3 series (functional group content 25%), manufacturer: Nagase)

ㄴ. 다관능 에폭시 수지(EP-5100R, 제조원: 국도화학) 또는 설퍼기를 가지는 에폭시 수지(YSLV-120TE, 제조원 : 니폰스틸 케미칼) 32 g, N. 32 g of a polyfunctional epoxy resin (EP-5100R, manufactured by Kukdo Chemical) or an epoxy resin having a sulfur group (YSLV-120TE, manufactured by Nippon Steel Chemical),

ㄷ. 페놀 노블락 페놀형 경화수지(DL-92, 제조원:메이와 플라스틱산업주식회사) 11 g,C. 11 g of phenol noblock phenol type hardening resin (DL-92, a manufacturer: Meiwa Plastic Industry Co., Ltd.),

ㄹ. 포스핀계 경화촉매(TPP-K, TPP, 또는 TPP-MK 제조원: 메이화플라스틱산업주식회사) 0.6 g,D. Phosphine curing catalyst (TPP-K, TPP, or TPP-MK manufacturer: Meihwa Plastic Industry Co., Ltd.) 0.6 g,

ㅁ. 실란 커플링제(KBM-303, 제조원: 신에쯔주식회사) 3.0g,M. Silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 3.0 g,

ㅂ. 무정형 실리카(A200, 제조원: 대구사) 10 g.Iii. 10 g of amorphous silica (A200, manufactured by Daegu).

(2) 제 2 접착층(2) second adhesive layer

ㄱ. 전이금속 포착용 기능기(-CN, -COOH, -NCO, -SH 및 -NH 등) 함유 고분자 수지 (SG-P3계열(기능기 함량 25%), 제조원: 나가세) 210 g,A. 210 g of polymer resin containing a functional group (-CN, -COOH, -NCO, -SH and -NH, etc.) for transition metal capture (SG-P3 series (functional group content 25%), manufactured by Nagase)

ㄴ. 다관능 에폭시 수지(EP-5100R, 제조원: 국도화학) 또는 설퍼기를 가지는 에폭시 수지 (YSLV-120TE, 제조원 : 니폰스틸 케미칼) 75 g, N. 75 g of a polyfunctional epoxy resin (EP-5100R, manufactured by Kukdo Chemical) or an epoxy resin having a sulfur group (YSLV-120TE, manufactured by Nippon Steel Chemical),

ㄷ. 페놀 노블락 페놀형 경화수지(DL-92, 제조원:메이와 플라스틱산업주식회사) 65 g,C. 65 g of phenol noblock phenol type hardening resin (DL-92, a manufacturer: Meiwa Plastic Industry Co., Ltd.),

ㄹ. 포스핀계 경화촉매(TPP-K, TPP, 또는 TPP-MK 제조원: 메이화플라스틱산업주식회사) 4.0 g,D. Phosphine-based curing catalyst (TPP-K, TPP, or TPP-MK manufacturer: Meihwa Plastic Industry Co., Ltd.) 4.0 g,

ㅁ. 에폭시 실란 커플링제(KBM-303, 제조원: 신에쯔주식회사) 2.2g,M. Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 2.2 g,

ㅂ. 구형 실리카(SC-4500SQ, SC-2500SQ, 제조원: 아드마텍스(Admatechs)) 70 g,Iii. 70 g of spherical silica (SC-4500SQ, SC-2500SQ, Admatechs),

ㅅ. 전이금속 포착용 기능기 가지는 첨가제(아크릴로 니트릴, 제조원 : 알드리치, 또는 Ciba Irgamet계, 제조원 : 시바) 또는 멀켑토 또는 아미노 실란 커플링제 (KBM-573 또는 KBM-803, 제조원 : 신에쯔 주식회사) 1.0 g.G. Additives having functional groups for capturing transition metals (acrylonitrile, manufactured by Aldrich, or Ciba Irgamet, manufactured by Ciba) or mulletto or amino silane coupling agents (KBM-573 or KBM-803 manufactured by Shin-Etsu Co., Ltd.) 1.0 g.

<실시예 5>Example 5

(1) 제 1 접착층(1) first adhesive layer

ㄱ. 전이금속 포착용 기능기(-CN, -COOH, -NCO, -SH 및 -NH 등) 함유 고분자 수지 (SG-P3계열(기능기 함량 25%), 제조원: 나가세) 384 g,A. 384 g of polymer resin containing functional group (-CN, -COOH, -NCO, -SH and -NH, etc.) for capture transition metal (SG-P3 series (functional group content 25%), manufacturer: Nagase)

ㄴ. 다관능 에폭시 수지(EP-5100R, 제조원: 국도화학) 또는 설퍼기를 가지는 에폭시 수지 (YSLV-120TE, 제조원 : 니폰스틸 케미칼) 32 g, N. 32 g of a polyfunctional epoxy resin (EP-5100R, manufactured by Kukdo Chemical) or an epoxy resin having a sulfur group (YSLV-120TE, manufactured by Nippon Steel Chemical),

ㄷ. 아민계 경화수지(C-200S, 제조원:니폰 가야쿠) 11 g,C. 11 g of amine curing resins (C-200S, manufacturer: Nippon Kayaku),

ㄹ. 포스핀계 경화촉매(TPP-K, TPP, 또는 TPP-MK 제조원: 메이화플라스틱산업주식회사) 0.6 g,D. Phosphine curing catalyst (TPP-K, TPP, or TPP-MK manufacturer: Meihwa Plastic Industry Co., Ltd.) 0.6 g,

ㅁ. 실란 커플링제(KBM-303, 제조원: 신에쯔주식회사) 3.0g,M. Silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 3.0 g,

ㅂ. 무정형 실리카(A200, 제조원: 대구사) 10 g.Iii. 10 g of amorphous silica (A200, manufactured by Daegu).

(2) 제 2 접착층(2) second adhesive layer

ㄱ. 전이금속 포착용 기능기(-CN, -COOH, -NCO, -SH 및 -NH 등) 함유 고분자 수지 (SG-P3계열(기능기 함량 25%), 제조원: 나가세) 220 g,A. 220 g of polymer resin (SG-P3 series (functional group content 25%), containing a functional group for transition metal capture (-CN, -COOH, -NCO, -SH and -NH, etc.)

ㄴ. 다관능 에폭시 수지(EP-5100R, 제조원: 국도화학) 또는 설퍼기를 가지는 에폭시 수지 (YSLV-120TE, 제조원 : 니폰스틸 케미칼) 80 g, N. 80 g of a polyfunctional epoxy resin (EP-5100R, manufactured by Kukdo Chemical) or an epoxy resin having a sulfur group (YSLV-120TE, manufactured by Nippon Steel Chemical),

ㄷ. 페놀 노블락 페놀형 경화수지(DL-92, 제조원:메이와 플라스틱산업주식회사) 60 g,C. 60 g of phenol noblock phenol type hardening resin (DL-92, a manufacturer: Meiwa Plastic Industry Co., Ltd.),

ㄹ. 포스핀계 경화촉매(TPP-K, TPP, 또는 TPP-MK 제조원: 메이화플라스틱산업주식회사) 3.8 g,D. Phosphine-based curing catalyst (TPP-K, TPP, or TPP-MK manufacturer: Meihwa Plastic Industry Co., Ltd.) 3.8 g,

ㅁ. 에폭시 실란 커플링제(KBM-303, 제조원: 신에쯔주식회사) 2.2g,M. Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 2.2 g,

ㅂ. 구형 실리카(SC-4500SQ, SC-2500SQ, 제조원: 아드마텍스(Admatechs)) 70 g,Iii. 70 g of spherical silica (SC-4500SQ, SC-2500SQ, Admatechs),

ㅅ. 전이금속 포착용 기능기 가지는 첨가제(아크릴로 니트릴, 제조원 : 알드리치, 또는 Ciba Irgamet계, 제조원 : 시바) 또는 멀켑토 또는 아미노 실란 커플링제 (KBM-573 또는 KBM-803, 제조원 : 신에쯔 주식회사) 1.0 g.G. Additives having functional groups for capturing transition metals (acrylonitrile, manufactured by Aldrich, or Ciba Irgamet, manufactured by Ciba) or mulletto or amino silane coupling agents (KBM-573 or KBM-803 manufactured by Shin-Etsu Co., Ltd.) 1.0 g.

<실시예 6><Example 6>

(1) 제 1 접착층(1) first adhesive layer

ㄱ. 전이금속 포착용 기능기(-CN, -COOH, -NCO, -SH 및 -NH 등) 함유 고분자 수지 (SG-P3계열(기능기 함량 25%), 제조원: 나가세) 275 g,A. 275 g of polymer resin containing functional group (-CN, -COOH, -NCO, -SH and -NH, etc.) for transition metal capture (SG-P3 series (functional group content 25%), manufactured by Nagase)

ㄴ. 다관능 에폭시 수지(EP-5100R, 제조원: 국도화학) 또는 설퍼기를 가지는 에폭시 수지 (YSLV-120TE, 제조원 : 니폰스틸 케미칼) 70 g, N. 70 g of a polyfunctional epoxy resin (EP-5100R, manufactured by Kukdo Chemical) or an epoxy resin having a sulfur group (YSLV-120TE, manufactured by Nippon Steel Chemical),

ㄷ. 페놀 노블락 페놀형 경화수지(DL-92, 제조원:메이와 플라스틱산업주식회사) 19 g,C. 19 g of phenol noblock phenol type hardening resin (DL-92, a manufacturer: Meiwa Plastic Industry Co., Ltd.),

ㄹ. 포스핀계 경화촉매(TPP-K, TPP, 또는 TPP-MK 제조원: 메이화플라스틱산업주식회사) 0.5 g,D. Phosphine curing catalyst (TPP-K, TPP, or TPP-MK manufacturer: Meihwa Plastic Industry Co., Ltd.) 0.5 g,

ㅁ. 실란 커플링제(KBM-303, 제조원: 신에쯔주식회사) 3.0g,M. Silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 3.0 g,

ㅂ. 무정형 실리카(A200, 제조원: 대구사) 10 g.Iii. 10 g of amorphous silica (A200, manufactured by Daegu).

(2) 제 2 접착층(2) second adhesive layer

ㄱ. 전이금속 포착용 기능기(-CN, -COOH, -NCO, -SH 및 -NH 등) 함유 고분자 수지 (SG-P3계열(기능기 함량 25%), 제조원: 나가세) 220 g,A. 220 g of polymer resin (SG-P3 series (functional group content 25%), containing a functional group for transition metal capture (-CN, -COOH, -NCO, -SH and -NH, etc.)

ㄴ. 다관능 에폭시 수지(EP-5100R, 제조원: 국도화학) 또는 설퍼기를 가지는 에폭시 수지 (YSLV-120TE, 제조원 : 니폰스틸 케미칼) 80 g, N. 80 g of a polyfunctional epoxy resin (EP-5100R, manufactured by Kukdo Chemical) or an epoxy resin having a sulfur group (YSLV-120TE, manufactured by Nippon Steel Chemical),

ㄷ. 페놀 노블락 페놀형 경화수지 (DL-92, 제조원:메이와 플라스틱산업주식회사) 60 g,C. Phenolic Noble Phenolic Curing Resin (DL-92, Manufacturer: Meiwa Plastic Industry Co., Ltd.) 60 g,

ㄹ. 포스핀계 경화촉매(TPP-K, TPP, 또는 TPP-MK 제조원: 메이화플라스틱산 업주식회사) 3.8 g,D. 3.8 g of phosphine-based curing catalyst (TPP-K, TPP, or TPP-MK manufacturer: Meihwa Plastic Industry Co., Ltd.),

ㅁ. 에폭시 실란 커플링제(KBM-303, 제조원: 신에쯔주식회사) 2.2g,M. Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 2.2 g,

ㅂ. 구형 실리카(SC-4500SQ, SC-2500SQ, 제조원: 아드마텍스(Admatechs)) 70 g,Iii. 70 g of spherical silica (SC-4500SQ, SC-2500SQ, Admatechs),

ㅅ. 전이금속 포착용 기능기 가지는 첨가제(아크릴로 니트릴, 제조원 : 알드리치, 또는 Ciba Irgamet계, 제조원 : 시바) 또는 멀켑토 또는 아미노 실란 커플링제 (KBM-573 또는 KBM-803, 제조원 : 신에쯔 주식회사) 1.0 g.G. Additives having functional groups for capturing transition metals (acrylonitrile, manufactured by Aldrich, or Ciba Irgamet, manufactured by Ciba) or mulletto or amino silane coupling agents (KBM-573 or KBM-803 manufactured by Shin-Etsu Co., Ltd.) 1.0 g.

<비교예 1>Comparative Example 1

ㄱ. 전이금속 포착용 기능기(-CN, -COOH, -NCO, -SH 및 -NH 등) 함유 고분자 수지 (SG-P3계열(기능기 함량 25%), 제조원: 나가세) 384 g,A. 384 g of polymer resin containing functional group (-CN, -COOH, -NCO, -SH and -NH, etc.) for capture transition metal (SG-P3 series (functional group content 25%), manufacturer: Nagase)

ㄴ. 다관능 에폭시 수지 (EP-5100R, 제조원: 국도화학) 또는 설퍼기를 가지는 에폭시 수지 (YSLV-120TE, 제조원 : 니폰스틸 케미칼) 32 g, N. 32 g of a polyfunctional epoxy resin (EP-5100R, manufactured by Kukdo Chemical) or an epoxy resin having a sulfur group (YSLV-120TE, manufactured by Nippon Steel Chemical),

ㄷ. 페놀 노블락 페놀형 경화수지 (DL-92, 제조원:메이와 플라스틱산업주식회사) 11 g,C. Phenolic Noble Phenolic Curing Resin (DL-92, Manufacturer: Meiwa Plastic Industry Co., Ltd.) 11 g,

ㄹ. 포스핀계 경화촉매(TPP-K, TPP, 또는 TPP-MK 제조원: 메이화플라스틱산업주식회사) 0.6 g,D. Phosphine curing catalyst (TPP-K, TPP, or TPP-MK manufacturer: Meihwa Plastic Industry Co., Ltd.) 0.6 g,

ㅁ. 실란 커플링제 (KBM-303, 제조원: 신에쯔주식회사) 3.0g,M. Silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 3.0 g,

ㅂ. 무정형 실리카 (A200, 제조원: 대구사) 10 g.Iii. 10 g of amorphous silica (A200, manufactured by Daegu).

<비교예 2>Comparative Example 2

ㄱ. 전이금속 포착용 기능기(-CN, -COOH, -NCO, -SH 및 -NH 등) 함유 고분자 수지 (SG-P3계열(기능기 함량 25%), 제조원: 나가세) 220 g,A. 220 g of polymer resin (SG-P3 series (functional group content 25%), containing a functional group for transition metal capture (-CN, -COOH, -NCO, -SH and -NH, etc.)

ㄴ. 다관능 에폭시 수지 (EP-5100R, 제조원: 국도화학) 또는 설퍼기를 가지는 에폭시 수지 (YSLV-120TE, 제조원 : 니폰스틸 케미칼) 80 g, N. 80 g of a polyfunctional epoxy resin (EP-5100R, manufactured by Kukdo Chemical) or an epoxy resin having a sulfur group (YSLV-120TE, manufactured by Nippon Steel Chemical),

ㄷ. 페놀 노블락 페놀형 경화수지 (DL-92, 제조원:메이와 플라스틱산업주식회사) 60 g,C. Phenolic Noble Phenolic Curing Resin (DL-92, Manufacturer: Meiwa Plastic Industry Co., Ltd.) 60 g,

ㄹ. 포스핀계 경화촉매(TPP-K, TPP, 또는 TPP-MK 제조원: 메이화플라스틱산업주식회사) 3.8 g,D. Phosphine-based curing catalyst (TPP-K, TPP, or TPP-MK manufacturer: Meihwa Plastic Industry Co., Ltd.) 3.8 g,

ㅁ. 에폭시 실란 커플링제 (KBM-303, 제조원: 신에쯔주식회사) 2.2g,M. Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 2.2 g,

ㅂ. 구형 실리카 (SC-4500SQ, SC-2500SQ, 제조원: 아드마텍스(Admatechs)) 70 g,Iii. 70 g spherical silica (SC-4500SQ, SC-2500SQ, Admatechs),

ㅅ. 전이금속 포착용 기능기 가지는 첨가제(아크릴로 니트릴, 제조원 : 알드리치, 또는 Ciba Irgamet계, 제조원 : 시바) 또는 멀켑토 또는 아미노 실란 커플링제 (KBM-573 또는 KBM-803, 제조원 : 신에쯔 주식회사) 1.0 g.G. Additives having functional groups for capturing transition metals (acrylonitrile, manufactured by Aldrich, or Ciba Irgamet, manufactured by Ciba) or mulletto or amino silane coupling agents (KBM-573 or KBM-803 manufactured by Shin-Etsu Co., Ltd.) 1.0 g.

<비교예 3 ~ 4><Comparative Examples 3 to 4>

(1) 제 1 접착층(1) first adhesive layer

ㄱ. 전이금속 포착용 기능기(-CN, -COOH, -NCO, -SH 및 -NH 등) 함유 고분자 수지 (SG-P3계열(기능기 함량 25%), 제조원: 나가세) 384 g,A. 384 g of polymer resin containing functional group (-CN, -COOH, -NCO, -SH and -NH, etc.) for capture transition metal (SG-P3 series (functional group content 25%), manufacturer: Nagase)

ㄴ. 다관능 에폭시 수지 (EP-5100R, 제조원: 국도화학) 또는 설퍼기를 가지는 에폭시 수지 (YSLV-120TE, 제조원 : 니폰스틸 케미칼) 32 g, N. 32 g of a polyfunctional epoxy resin (EP-5100R, manufactured by Kukdo Chemical) or an epoxy resin having a sulfur group (YSLV-120TE, manufactured by Nippon Steel Chemical),

ㄷ. 페놀 노블락 페놀형 경화수지 (DL-92, 제조원:메이와 플라스틱산업주식회사) 11 g,C. Phenolic Noble Phenolic Curing Resin (DL-92, Manufacturer: Meiwa Plastic Industry Co., Ltd.) 11 g,

ㄹ. 포스핀계 경화촉매(TPP-K, TPP, 또는 TPP-MK 제조원: 메이화플라스틱산업주식회사) 0.6 g,D. Phosphine curing catalyst (TPP-K, TPP, or TPP-MK manufacturer: Meihwa Plastic Industry Co., Ltd.) 0.6 g,

ㅁ. 실란 커플링제 (KBM-303, 제조원: 신에쯔주식회사) 3.0g,M. Silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 3.0 g,

ㅂ. 무정형 실리카 (A200, 제조원: 대구사) 10 g.Iii. 10 g of amorphous silica (A200, manufactured by Daegu).

(2) 제 2 접착층(2) second adhesive layer

ㄱ. 전이금속 포착용 기능기(-CN, -COOH, -NCO, -SH 및 -NH 등) 함유 고분자 수지 (SG-P3계열(기능기 함량 25%), 제조원: 나가세) 220 g,A. 220 g of polymer resin (SG-P3 series (functional group content 25%), containing a functional group for transition metal capture (-CN, -COOH, -NCO, -SH and -NH, etc.)

ㄴ. 다관능 에폭시 수지 (EP-5100R, 제조원: 국도화학) 또는 설퍼기를 가지는 에폭시 수지 (YSLV-120TE, 제조원 : 니폰스틸 케미칼) 80 g, N. 80 g of a polyfunctional epoxy resin (EP-5100R, manufactured by Kukdo Chemical) or an epoxy resin having a sulfur group (YSLV-120TE, manufactured by Nippon Steel Chemical),

ㄷ. 페놀 노블락 페놀형 경화수지 (DL-92, 제조원:메이와 플라스틱산업주식회사) 60 g,C. Phenolic Noble Phenolic Curing Resin (DL-92, Manufacturer: Meiwa Plastic Industry Co., Ltd.) 60 g,

ㄹ. 포스핀계 경화촉매(TPP-K, TPP, 또는 TPP-MK 제조원: 메이화플라스틱산업주식회사) 3.8 g,D. Phosphine-based curing catalyst (TPP-K, TPP, or TPP-MK manufacturer: Meihwa Plastic Industry Co., Ltd.) 3.8 g,

ㅁ. 에폭시 실란 커플링제 (KBM-303, 제조원: 신에쯔주식회사) 2.2g,M. Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 2.2 g,

ㅂ. 구형 실리카 (SC-4500SQ, SC-2500SQ, 제조원: 아드마텍스(Admatechs)) 70 g,Iii. 70 g spherical silica (SC-4500SQ, SC-2500SQ, Admatechs),

ㅅ. 전이금속 포착용 기능기 가지는 첨가제(아크릴로 니트릴, 제조원 : 알드리치, 또는 Ciba Irgamet계, 제조원 : 시바) 또는 멀켑토 또는 아미노 실란 커플링제 (KBM-573 또는 KBM-803, 제조원 : 신에쯔 주식회사) 1.0 g.G. Additives having functional groups for capturing transition metals (acrylonitrile, manufactured by Aldrich, or Ciba Irgamet, manufactured by Ciba) or mulletto or amino silane coupling agents (KBM-573 or KBM-803 manufactured by Shin-Etsu Co., Ltd.) 1.0 g.

<비교예 5>Comparative Example 5

(1) 제 1 접착층(1) first adhesive layer

ㄱ. 전이금속 포착용 기능기(-CN, -COOH, -NCO, -SH 및 -NH 등) 함유 고분자 수지 (SG-P3계열(기능기 함량 25%), 제조원: 나가세) 210 g,A. 210 g of polymer resin containing a functional group (-CN, -COOH, -NCO, -SH and -NH, etc.) for transition metal capture (SG-P3 series (functional group content 25%), manufactured by Nagase)

ㄴ. 다관능 에폭시 수지 (EP-5100R, 제조원: 국도화학) 또는 설퍼기를 가지는 에폭시 수지 (YSLV-120TE, 제조원 : 니폰스틸 케미칼) 90 g, N. 90 g of a polyfunctional epoxy resin (EP-5100R, manufactured by Kukdo Chemical) or an epoxy resin having a sulfur group (YSLV-120TE, manufactured by Nippon Steel Chemical),

ㄷ. 페놀 노블락 페놀형 경화수지 (DL-92, 제조원:메이와 플라스틱산업주식회사) 20 g,C. Phenolic Noble Phenolic Curing Resin (DL-92, Manufacturer: Meiwa Plastic Industry Co., Ltd.) 20 g,

ㄹ. 포스핀계 경화촉매(TPP-K, TPP, 또는 TPP-MK 제조원: 메이화플라스틱산업주식회사) 0.6 g,D. Phosphine curing catalyst (TPP-K, TPP, or TPP-MK manufacturer: Meihwa Plastic Industry Co., Ltd.) 0.6 g,

ㅁ. 실란 커플링제 (KBM-303, 제조원: 신에쯔주식회사) 3.0g,M. Silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 3.0 g,

ㅂ. 무정형 실리카 (A200, 제조원: 대구사) 10 g.Iii. 10 g of amorphous silica (A200, manufactured by Daegu).

(2) 제 2 접착층(2) second adhesive layer

ㄱ. 전이금속 포착용 기능기(-CN, -COOH, -NCO, -SH 및 -NH 등) 함유 고분자 수지 (SG-P3계열(기능기 함량 25%), 제조원: 나가세) 220 g,A. 220 g of polymer resin (SG-P3 series (functional group content 25%), containing a functional group for transition metal capture (-CN, -COOH, -NCO, -SH and -NH, etc.)

ㄴ. 다관능 에폭시 수지 (EP-5100R, 제조원: 국도화학) 또는 설퍼기를 가지는 에폭시 수지 (YSLV-120TE, 제조원 : 니폰스틸 케미칼) 80 g, N. 80 g of a polyfunctional epoxy resin (EP-5100R, manufactured by Kukdo Chemical) or an epoxy resin having a sulfur group (YSLV-120TE, manufactured by Nippon Steel Chemical),

ㄷ. 페놀 노블락 페놀형 경화수지 (DL-92, 제조원:메이와 플라스틱산업주식회사) 60 g,C. Phenolic Noble Phenolic Curing Resin (DL-92, Manufacturer: Meiwa Plastic Industry Co., Ltd.) 60 g,

ㄹ. 포스핀계 경화촉매(TPP-K, TPP, 또는 TPP-MK 제조원: 메이화플라스틱산업주식회사) 3.8 g,D. Phosphine-based curing catalyst (TPP-K, TPP, or TPP-MK manufacturer: Meihwa Plastic Industry Co., Ltd.) 3.8 g,

ㅁ. 에폭시 실란 커플링제 (KBM-303, 제조원: 신에쯔주식회사) 2.2g,M. Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 2.2 g,

ㅂ. 구형 실리카 (SC-4500SQ, SC-2500SQ, 제조원: 아드마텍스(Admatechs)) 70 g,Iii. 70 g spherical silica (SC-4500SQ, SC-2500SQ, Admatechs),

ㅅ. 전이금속 포착용 기능기 가지는 첨가제(아크릴로 니트릴, 제조원 : 알드리치, 또는 Ciba Irgamet계, 제조원 : 시바) 또는 멀켑토 또는 아미노 실란 커플링제 (KBM-573 또는 KBM-803, 제조원 : 신에쯔 주식회사) 1.0 g.G. Additives having functional groups for capturing transition metals (acrylonitrile, manufactured by Aldrich, or Ciba Irgamet, manufactured by Ciba) or mulletto or amino silane coupling agents (KBM-573 or KBM-803 manufactured by Shin-Etsu Co., Ltd.) 1.0 g.

<비교예 6>Comparative Example 6

(1) 제 1 접착층(1) first adhesive layer

ㄱ. 전이금속 포착용 기능기(-CN, -COOH, -NCO, -SH 및 -NH 등) 함유 고분자 수지 (SG-P3계열(기능기 함량 25%), 제조원: 나가세) 210 g,A. 210 g of polymer resin containing a functional group (-CN, -COOH, -NCO, -SH and -NH, etc.) for transition metal capture (SG-P3 series (functional group content 25%), manufactured by Nagase)

ㄴ. 다관능 에폭시 수지 (EP-5100R, 제조원: 국도화학) 또는 설퍼기를 가지는 에폭시 수지 (YSLV-120TE, 제조원 : 니폰스틸 케미칼) 90 g, N. 90 g of a polyfunctional epoxy resin (EP-5100R, manufactured by Kukdo Chemical) or an epoxy resin having a sulfur group (YSLV-120TE, manufactured by Nippon Steel Chemical),

ㄷ. 아민계 경화수지 (C-200S, 제조원:니폰 가야쿠) 20 g,C. Amine cured resin (C-200S, manufacturer: Nippon Kayaku) 20 g,

ㄹ. 포스핀계 경화촉매(TPP-K, TPP, 또는 TPP-MK 제조원: 메이화플라스틱산업주식회사) 0.6 g,D. Phosphine curing catalyst (TPP-K, TPP, or TPP-MK manufacturer: Meihwa Plastic Industry Co., Ltd.) 0.6 g,

ㅁ. 실란 커플링제 (KBM-303, 제조원: 신에쯔주식회사) 3.0g,M. Silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 3.0 g,

ㅂ. 무정형 실리카 (A200, 제조원: 대구사) 10 g.Iii. 10 g of amorphous silica (A200, manufactured by Daegu).

(2) 제 2 접착층(2) second adhesive layer

ㄱ. 전이금속 포착용 기능기(-CN, -COOH, -NCO, -SH 및 -NH 등) 함유 고분자 수지 (SG-P3계열(기능기 함량 25%), 제조원: 나가세) 220 g,A. 220 g of polymer resin (SG-P3 series (functional group content 25%), containing a functional group for transition metal capture (-CN, -COOH, -NCO, -SH and -NH, etc.)

ㄴ. 다관능 에폭시 수지 (EP-5100R, 제조원: 국도화학) 또는 설퍼기를 가지는 에폭시 수지 (YSLV-120TE, 제조원 : 니폰스틸 케미칼) 80 g, N. 80 g of a polyfunctional epoxy resin (EP-5100R, manufactured by Kukdo Chemical) or an epoxy resin having a sulfur group (YSLV-120TE, manufactured by Nippon Steel Chemical),

ㄷ. 페놀 노블락 페놀형 경화수지 (DL-92, 제조원:메이와 플라스틱산업주식회사) 60 g,C. Phenolic Noble Phenolic Curing Resin (DL-92, Manufacturer: Meiwa Plastic Industry Co., Ltd.) 60 g,

ㄹ. 포스핀계 경화촉매(TPP-K, TPP, 또는 TPP-MK 제조원: 메이화플라스틱산업주식회사) 3.8 g,D. Phosphine-based curing catalyst (TPP-K, TPP, or TPP-MK manufacturer: Meihwa Plastic Industry Co., Ltd.) 3.8 g,

ㅁ. 에폭시 실란 커플링제 (KBM-303, 제조원: 신에쯔주식회사) 2.2g,M. Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 2.2 g,

ㅂ. 구형 실리카 (SC-4500SQ, SC-2500SQ, 제조원: 아드마텍스(Admatechs)) 70 g,Iii. 70 g spherical silica (SC-4500SQ, SC-2500SQ, Admatechs),

ㅅ. 전이금속 포착용 기능기 가지는 첨가제(아크릴로 니트릴, 제조원 : 알드리치, 또는 Ciba Irgamet계, 제조원 : 시바) 또는 멀켑토 또는 아미노 실란 커플링 제 (KBM-573 또는 KBM-803, 제조원 : 신에쯔 주식회사) 1.0 g.G. Additives having functional groups for capturing transition metals (acrylonitrile, manufactured by Aldrich or Ciba Irgamet, manufactured by Ciba) or merceto or amino silane coupling agents (KBM-573 or KBM-803, manufactured by Shin-Etsu Co., Ltd.) ) 1.0 g.

[두께 측정][Thickness measurement]

필름의 두께를 측정하기 위하여 필름을 20×80mm 크기로 자른 시료를 준비한다. In order to measure the thickness of the film, a sample obtained by cutting the film into a size of 20 × 80 mm is prepared.

그 다음에는, 두께 측정기의 영점을 맞춘 후 필름의 두께를 3회 측정하여 평균치를 기록하였다.Then, after zeroing the thickness meter, the thickness of the film was measured three times and the average value was recorded.

[표면 에너지 측정][Surface energy measurement]

필름의 표면 에너지를 측정하기 위하여 필름을 20×80mm 크기로 자른 시료를 준비한다. 표면 에너지 측정기기의 샘플 스테이지(Sample Stage)에 적당한 크기의 테이프를 시료의 양쪽부분에 붙여 고정시킨다. 물방울이 떨어지는 높이를 10 cm를 맞춘 후 준비된 시료를 물방울이 떨어지는 위치에 둔다. 한방울 떨어진 물방울의 접촉각을 기계로 자동 측정하고 이 값을 이용하여 표면 에너지를 계산한 후 그 값을 하기 [표 1]에 정리하였다.In order to measure the surface energy of the film, a sample obtained by cutting the film into a size of 20 × 80 mm is prepared. A suitable size tape is attached to both sides of the sample and fixed to the sample stage of the surface energy measuring instrument. Set the height of the drop of water to 10 cm, and then place the prepared sample in the position of dropping water. The contact angle of a drop of water droplets was automatically measured by a machine and the surface energy was calculated using this value, and the values are summarized in the following [Table 1].

[색도측정][Color Measurement]

필름의 전이금속 이온에 대한 반응성을 색도측정을 통하여 구분하고자 반응 후 필름의 색도를 측정하였다. 이를 측정하기 위하여 전이금속으로 오염된 5미크론 막을 필름과 합지한 후 16mm×16mm 커버글라스에 60℃ 조건에서 라미네이 션(Lamination)하고, 125℃에서 1시간 및 175℃에서 3시간을 반복한 후, 색의 변색 정도를 색도계를 이용하여 측정한다. 이때 그 값은 밝기를 나타내는 L과 붉은색과 노락색 경향을 나타내는 a와 b로 각각의 값을 얻을 수 있으며 이를 하기 [표 1]에 L과 (a,b)로 정리하였다. The chromaticity of the film was measured after the reaction to distinguish the reactivity of the film with the transition metal ion through chromaticity measurement. To measure this, a 5 micron film contaminated with transition metal was laminated with a film, and then laminated on a 16 mm × 16 mm cover glass at 60 ° C., and repeated 1 hour at 125 ° C. and 3 hours at 175 ° C. The degree of discoloration of the color is measured using a colorimeter. At this time, the values can be obtained as L and the a and b indicating the red and yellow trends of brightness, and summarized as L and (a, b) in the following [Table 1].

[소자 작동성] [Device operation]

소자 작동성을 알아보기 위하여 접착필름을 이용하여 반도체 칩 조립과정을 거친 후 소자의 작동성을 확인한 후 작동성 여부를 pass, non-pass, partial fail, fail로 구분하여 [표 1]에 정리하였다.After the semiconductor chip assembly process using the adhesive film to check the device operability, the operability of the device is confirmed and the operability is classified into pass, non-pass, partial fail, and fail in [Table 1]. .

[용융점도측정] Melt Viscosity Measurement

필름의 점도를 측정하기 위하여 각각의 필름을 4겹으로 60℃에서 합지하고 지름이 25mm로 원형 컷팅 하였다. 이때 두께는 400 ~ 440㎛정도이다. 점도측정범위는 30℃에서 130℃까지 측정하였고 승온조건은 5℃/분이다. 경화전 25℃와 다이 어태치 온도에서 흐름성을 가늠하는 100℃와 와이어의 요철을 충전할 때 충전성을 가늠하는 130℃에서의 에타(Eta) 값을 제시하였다.In order to measure the viscosity of the film, each film was laminated in four layers at 60 ° C. and circular cut to a diameter of 25 mm. At this time, the thickness is about 400 ~ 440㎛. Viscosity measurement range was measured from 30 ℃ to 130 ℃ and the temperature rising condition is 5 ℃ / min. Eta values at 100 ° C. for flowability at 25 ° C. and die attach temperature before curing and 130 ° C. for fillability when filling unevenness of wires are presented.

[접착력] [Adhesiveness]

이산화 막으로 코팅되어있는 두께 725㎛ 웨이퍼를 5mm×5mm 크기로 자른 뒤 접착 필름과 함께 60℃ 조건에서 라미네이션(Lamination)하고 접착부분만 남기고 절단하였다. 온도가 100℃인 열판 위에 감광성 폴리이미드로 코팅되어 있는 두께 725㎛와 10mm×10mm 크기 웨이퍼를 놓고 그 위에 접착제가 라미네이션된 웨이퍼 조각을 1.0초 동안 1.0 kgf의 힘으로 압착한 뒤, 125℃에서 1시간 및 175℃에서 3시간을 반복한 후, 85℃／85％RH, 48h 흡습 후 270℃에서의 파괴 강도를 측정했다.A 725 μm thick wafer coated with a dioxide film was cut to a size of 5 mm × 5 mm, and then laminated at 60 ° C. with an adhesive film, and cut, leaving only the adhesive part. Place a 725 μm thick and 10 mm × 10 mm wafer coated with a photosensitive polyimide on a hotplate having a temperature of 100 ° C., and then press the adhesive-laminated wafer piece with 1.0 kgf for 1.0 sec. After repeating 3 hours at time and 175 degreeC, the breaking strength in 270 degreeC was measured after 85 degreeC / 85% RH and 48h moisture absorption.

[표 1][Table 1]

Figure 112008089001404-pat00001
Figure 112008089001404-pat00001

※ "고분자함량(1)"에서 고분자의 전체 기능기 중 전이금속 포착용 기능기를 20 ~ 40% 포함※ "Polymer content (1)" contains 20-40% of functional groups for transition metal capture among all functional groups of polymer

※ "가혹(3)"의 이온 노출 양이 "일반(2)"의 이온 노출 양의 50배※ The amount of ion exposure of "Severe (3)" is 50 times the amount of ion exposure of "General (2)"

상기 [표 1]을 통해서 나타난 바와 같이, 실시예 1 ~ 3의 경우 제 1 접착층의 두께 조절을 통하여 전이금속의 환원능력은 최대화 하면서 복층구조 접착 필름의 유동성을 유지할 수 있음을 확인할 수 있다. As shown in Table 1, it can be seen that in Examples 1 to 3, the fluidity of the multilayer structure adhesive film can be maintained while maximizing the reducing ability of the transition metal by controlling the thickness of the first adhesive layer.

제 1 접착층의 두께가 증가할수록 전이금속의 환원능력은 증가하나, 그 두께가 전체 접착층의 두께의 30% 이상이 되면 와이어의 충진성 불량에 의한 보이드 발생 또는 접착제에 의한 와이어의 눌림 현상에 의한 신뢰도 불량이 발생할 수 있다. 이는 비교예 1, 비교에 3 및 비교예 4의 결과를 통하여 확인할 수 있다. As the thickness of the first adhesive layer increases, the reducing capacity of the transition metal increases, but when the thickness is 30% or more of the thickness of the entire adhesive layer, reliability due to void generation due to poor fillability of the wire or pressing of the wire by the adhesive Defects may occur. This can be confirmed through the results of Comparative Example 1, Comparative 3 and Comparative Example 4.

또한 비교예 4와 같이 제 1 접착층의 두께가 제 2 접착층과 유사해질 경우 두 필름간의 팽창계수의 차이에 의한 계면 분리성(단차 filling성)의 문제가 발생할 수 있다. 반대로 비교예 2의 경우와 같이 제 2 접착층으로만 이루어질 경우 제 1 접착층의 전이금속 환원력을 가지지 못하기 때문에 칩의 작동 효율성을 극대화 시키는 능력이 저하됨을 알 수 있다. In addition, when the thickness of the first adhesive layer is similar to that of the second adhesive layer as in Comparative Example 4, a problem of interfacial separation (step filling property) may occur due to a difference in expansion coefficient between the two films. On the contrary, as in the case of Comparative Example 2, since only the second adhesive layer does not have the transition metal reducing power of the first adhesive layer, the ability to maximize the operational efficiency of the chip may be deteriorated.

실시예 4의 경우 제 2 접착층의 유동성 증가를 목적으로 전이금속이온을 환원시키는 고분자의 함량이 감소한다 할지라도 제 1 접착층의 전이금속 환원능력에 의하여 칩의 작동 효율성을 극대화 시키는 역할 수행에 문제가 없음을 알 수 있다. In the case of Example 4, even if the content of the polymer for reducing the transition metal ions is reduced for the purpose of increasing the fluidity of the second adhesive layer, there is a problem in maximizing the operational efficiency of the chip by the transition metal reducing ability of the first adhesive layer. It can be seen that there is no.

실시예 5의 경우 접착제 1층의 경화 시스템에 의한 전이금속 환원능력에 의하여 칩의 작동 효율성을 극대화시키는 역할 수행에 차이가 없음을 알 수 있다. In the case of Example 5 it can be seen that there is no difference in the performance of the role of maximizing the operating efficiency of the chip by the ability to reduce the transition metal by the curing system of the adhesive 1 layer.

이에 반하여 제 1 접착층에 포함되는 고분자의 전이금속 포착용 기능기가 감소하면 전이금속 환원능력의 저하로 칩의 작동 효율성을 극대화 시키는 역할 수행 에 문제가 발생할 수 있으며 그 함량 또한 중요한 인자임을 실시예 6, 비교예 5 및 비교예 6에서 알 수 있다.On the other hand, if the transition metal capture functional group of the polymer included in the first adhesive layer is reduced, a problem may occur in maximizing the operational efficiency of the chip due to a decrease in the transition metal reduction ability. It can be seen in Comparative Example 5 and Comparative Example 6.

이상에서는 본 발명의 일 실시예를 중심으로 설명하였지만, 당업자의 수준에서 다양한 변경이나 변형을 가할 수 있다. 이러한 변경과 변형이 본 발명의 범위를 벗어나지 않는 한 본 발명에 속한다고 할 수 있다. 따라서, 본 발명의 권리범위는 이하에 기재되는 청구범위에 의해 판단되어야 할 것이다.Although the above has been described with reference to one embodiment of the present invention, various changes and modifications can be made at the level of those skilled in the art. Such changes and modifications may belong to the present invention without departing from the scope of the present invention. Therefore, the scope of the present invention should be judged by the claims described below.

도 1은 본 발명에 따른 복층구조의 접착 필름을 나타낸 단면도.1 is a cross-sectional view showing an adhesive film of a multilayer structure according to the present invention.

Claims (7)

기재 필름 상부에 형성되며, 전이금속 포착용 기능기를 갖는 고분자 바인더50 ~ 90중량%를 포함하는 접착제 조성물로 구비된 제 1 접착층; 및A first adhesive layer formed on the base film and provided with an adhesive composition including 50 to 90% by weight of a polymeric binder having a functional group for capturing transition metal; And 상기 제 1 접착층 상부에 구비되며, 전이금속 포착용 기능기를 갖는 고분자 바인더 15 ~ 30중량%를 포함하는 접착제 조성물로 구비된 제 2 접착층을 포함하는 반도체용 복층구조 접착 필름.The multilayer structure adhesive film for a semiconductor provided on the said 1st contact bonding layer and including the 2nd contact bonding layer provided with the adhesive composition containing 15-30 weight% of polymeric binders with a function for capturing a transition metal. 제 1 항에 있어서,The method of claim 1, 상기 전이금속 포착용 기능기는 -CN, -COOH, -NCO, -SH 또는 -NH 중 선택된 하나 이상을 포함하는 것을 특징으로 하는 반도체용 복층구조 접착 필름.The transition metal capture functional group is a multilayer structure adhesive film for a semiconductor, characterized in that it comprises at least one selected from -CN, -COOH, -NCO, -SH or -NH. 제 1 항에 있어서,The method of claim 1, 상기 전이금속 포착용 기능기를 갖는 고분자 바인더에 포함되는 전이금속 포착용 기능기를 갖는 모노머는 상기 각 접착층의 고분자 바인더의 중량을 기준으로 20 ~ 40%로 포함되는 것을 특징으로 하는 반도체용 복층구조 접착 필름.Monomer having a transition metal trapping functional group included in the polymer binder having a functional group for trapping the metal is characterized in that it comprises 20 to 40% based on the weight of the polymer binder of each adhesive layer . 제 1 항에 있어서,The method of claim 1, 상기 제 1 접착층의 두께는 전체 접착 필름 두께의 8 ~ 25%이고, 제 2 접착층의 두께는 전체 접착 필름 두께의 75 ~ 98%가 되도록 형성되는 것을 특징으로 하는 반도체용 복층구조 접착 필름.The thickness of the first adhesive layer is 8 to 25% of the total adhesive film thickness, the thickness of the second adhesive layer is formed to be 75 to 98% of the total adhesive film thickness, the multilayer structure adhesive film for a semiconductor. 제 1 항의 상기 복층구조 접착 필름을 구성하는 반도체용 접착제 조성물로서, 전이금속 포착용 기능기를 갖는 바인더 수지 2 ~ 50중량%, 에폭시 수지 4 ~ 50 중량%, 페놀 경화형 수지 3 ~ 50 중량%, 경화 촉매 0.1 ~ 10 중량%, 실란 커플링제 0.1 ~ 10 중량%, 충진제 0.1 ~ 50중량% 및 잔부의 첨가제를 포함하는 것을 특징으로 하는 반도체용 접착제 조성물.The adhesive composition for semiconductors which comprises the said multilayer structure adhesive film of Claim 1 which is 2-50 weight% of binder resins which have a functional group for transition metal capture, 4-50 weight% of epoxy resins, 3-50 weight% of phenol curable resins, and hardening Adhesive composition for a semiconductor comprising 0.1 to 10% by weight of a catalyst, 0.1 to 10% by weight of a silane coupling agent, 0.1 to 50% by weight of a filler and the balance of additives. 제 5 항에 있어서, The method of claim 5, 상기 접착제 조성물은 전이금속 포착용 첨가제를 더 포함하는 것을 특징으로 하는 반도체용 접착제 조성물.The adhesive composition is an adhesive composition for a semiconductor, further comprising an additive for capturing transition metals. 제 1 항의 복층구조 접착 필름을 포함하는 것을 특징으로 하는 다이싱 다이본딩 필름.Dicing die-bonding film comprising the multilayer structure adhesive film of claim 1.
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