KR20120109145A - Resin composition for adhesive film and the adhesive film using thereof - Google Patents

Resin composition for adhesive film and the adhesive film using thereof Download PDF

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Publication number
KR20120109145A
KR20120109145A KR1020110027378A KR20110027378A KR20120109145A KR 20120109145 A KR20120109145 A KR 20120109145A KR 1020110027378 A KR1020110027378 A KR 1020110027378A KR 20110027378 A KR20110027378 A KR 20110027378A KR 20120109145 A KR20120109145 A KR 20120109145A
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South Korea
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adhesive film
resin
curing agent
resin composition
latent curing
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KR1020110027378A
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Korean (ko)
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백경욱
김일
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한국과학기술원
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Priority to KR1020110027378A priority Critical patent/KR20120109145A/en
Priority to PCT/KR2011/009931 priority patent/WO2012134034A2/en
Publication of KR20120109145A publication Critical patent/KR20120109145A/en

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    • C—CHEMISTRY; METALLURGY
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
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    • C09J7/10—Adhesives in the form of films or foils without carriers
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    • C09J9/02—Electrically-conducting adhesives
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    • 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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    • C09J2301/304—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 the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
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    • C09J2301/314—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 the adhesive layer and/or the carrier being conductive
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    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Computer Hardware Design (AREA)
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  • Engineering & Computer Science (AREA)
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  • Adhesives Or Adhesive Processes (AREA)
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Abstract

PURPOSE: A resin composition for an adhesive film is provided to have by semi-permanent by having excellent storage performance, to not have limitations of drying process, and to be able to improve reliability and adhesion of a package. CONSTITUTION: A manufacturing method of a resin composition for an adhesive film comprises: a step of preparing 5-60 weight% of a thermoplastic resin, 25-94.9 weight% of a thermosetting resin, and 0.1-30 weight% of a light-latent hardener; a step of preparing 40-250 weight% of an organic solvent based on a total weight of the thermoplastic resin, thermosetting resin and light-latent hardener combined; and a step of manufacturing the resin composition for the adhesive film by mixing and dissolving the thermoplastic resin, thermosetting resin, light-latent hardener, and the organic solvent.

Description

접착필름용 수지 조성물 및 이를 이용한 접착필름{RESIN COMPOSITION FOR ADHESIVE FILM AND THE ADHESIVE FILM USING THEREOF}RESIN COMPOSITION FOR ADHESIVE FILM AND THE ADHESIVE FILM USING THEREOF

본 발명은 접착필름용 수지 조성물 및 이를 이용한 접착필름에 관한 것으로서, 더욱 상세하게는 상온 보관성이 뛰어난 유효기간이 반영구적이며, 광잠재성 경화제가 첨가되어 저온 속경화가 가능한 접착필름용 수지 조성물 및 이를 이용한 접착필름에 관한 것이다.
The present invention relates to a resin composition for an adhesive film and an adhesive film using the same, and more particularly, a shelf life excellent in room temperature storage properties is semipermanent, and a resin composition for an adhesive film capable of low temperature rapid curing by adding a photo latent curing agent. It relates to an adhesive film using the same.

전자 부품의 크기와 두께가 점점 작아지고 얇아짐에 따라 회로의 밀도와 정교함은 더욱 높아졌다. 이러한 전기적 접속이 요구되는 전자 부품의 상 회로와 하 회로를 물리적으로 접속, 고정시키기 위하여 접착제를 사용하게 되는데 그 사용형태에 따라 필름과 페이스트 형태로 나뉘게 된다.As the size and thickness of electronic components become smaller and thinner, the density and sophistication of the circuits become higher. Adhesives are used to physically connect and fix the upper circuit and the lower circuit of an electronic component requiring such electrical connection. The adhesive is divided into a film and a paste according to the use form.

또한, 도전 입자를 포함하는가 포함하지 않는가에 따라 전도성, 이방성전도성, 비전도성으로 나뉘게 된다. 따라서 전자 패키징에 사용되는 접착제는 이방성 전도 필름(ACF; Anisotropic Conductive Film, 이하 ACF), 이방성 전도 페이스트(ACP; Anisotropic Conductive paste, 이하 ACP), 비전도성 필름(NCF; Non-Conductive Film, 이하 NCF) 및 비전도성 페이스트(NCP; Non-Conductive Paste, 이하 NCP)로 나눌 수 있다.In addition, it is divided into conductive, anisotropic conductive, and non-conductive depending on whether or not it contains conductive particles. Therefore, adhesives used in electronic packaging include anisotropic conductive film (ACF), anisotropic conductive paste (ACP), and non-conductive film (NCF). And non-conductive pastes (NCPs).

필름 형태의 접착제(ACF, NCF)와 페이스트 형태의 접착제(ACP, NCP)는 그 형태와 조성에 따라 큰 차이점이 있다. 먼저 ACF 또는 NCF는 필름 형태로 코팅이 가능하도록 조성물 중에 코팅성을 돕는 유기용매가 포함되며, 필름 형태로 코팅된 후 유기용매를 건조시킨 후 제품화된다.Film adhesives (ACF, NCF) and paste adhesives (ACP, NCP) have a big difference depending on the form and composition. First, the ACF or NCF includes an organic solvent that helps coatability in the composition to enable coating in the form of a film, is coated in the form of a film, and then dried and commercialized.

ACP 또는 NCP는 필름과는 달리 기판위에 디스펜싱 등과 같은 방법으로 직접 도포하여 플립칩 공정을 수행하므로 내부의 기포 생성을 막기 위하여 유기용매가 포함되지 않는다. 또한 시린지(syringe)안에 페이스트 형태로 담겨져 제품화된다.Unlike the film, ACP or NCP is applied directly to the substrate by a method such as dispensing to perform a flip chip process, so that an organic solvent is not included to prevent the formation of bubbles inside. It is also marketed as a paste in a syringe.

이러한 접착필름 조성물의 절연성 접착성분으로는 열가소성수지와 열경화성수지 등이 사용되는데, 접속신뢰성 측면에서 주로 열경화성수지를 사용하고 있다. Thermoplastic resins and thermosetting resins are used as the insulating adhesive component of the adhesive film composition, and thermosetting resins are mainly used in terms of connection reliability.

그 중 가장 많이 사용되는 수지는 열경화성 수지로서, 이를 사용할 경우, 접착제를 피접착부재 사이에 개재시켜 열압착함으로써 접착이 이루어지는데, 충분한 접속신뢰성이나 접착강도를 위해 고온에서 상당한 경화반응 진행시간을 필요로 한다. 대표적으로 에폭시계 수지의 경우, 170 내지 180℃에서 20초 정도 또는 180 내지 210℃에서 10초 정도의 접착시간을 필요로 한다.Among them, the most commonly used resin is a thermosetting resin, and when it is used, adhesion is performed by thermally pressing an adhesive between the members to be bonded, and a considerable curing reaction time is required at a high temperature for sufficient connection reliability or adhesive strength. Shall be. Typically epoxy resins require an adhesion time of about 20 seconds at 170 to 180 ° C or about 10 seconds at 180 to 210 ° C.

하지만, 이러한 접착조건에서는 부품 간 접합 시 고온에 의해 생기는 열응력에 의한 불량 등 접합특성 저하와 신뢰성 저하 등의 문제들, 열 팽창에 의한 어긋남, 열에 의한 고분자 기판 등의 손상이 발생하는 등의 문제가 있다. 더욱이 최근 정밀 전자기기 분야에서는 회로의 고밀도화가 진행되고 있어 전극 폭, 전극 간격이 매우 좁아지며 기판의 재질 또한 유리전이온도가 낮은 PET등의 고분자 재질의 사용이 늘어나고 있어 이러한 문제는 심화되고 있다. 또한 장시간에 걸친 접속시간은 생산 효율을 저하시킨다.However, in such bonding conditions, problems such as deterioration of the bonding characteristics and reliability, such as defects due to high thermal stress caused by high temperature when joining parts, problems such as misalignment due to thermal expansion and damage of polymer substrate due to heat, etc. There is. Furthermore, in recent years in the field of precision electronic devices, circuit densities are increasing, so that electrode widths and electrode intervals become very narrow, and the use of polymer materials such as PET, which has a low glass transition temperature, increases the problem. In addition, the connection time over a long time reduces the production efficiency.

또한, 상기의 문제점을 극복하기 위해 저온에서 가열 의해 라디칼 중합이 일어나고, 가교에 의해 경화되는 라디칼 중합성 수지인 아크릴 수지를 사용하는 접착재료의 사용이 늘어나고 있으며, 더욱 낮은 온도에서 접합이 가능한 핫멜트(hotmelt) 타입과 같은 열가소성수지 기반의 접착재료의 사용도 늘어나고 있다.In addition, in order to overcome the above problems, the use of an adhesive material using an acrylic resin, which is a radical polymerizable resin that is heated by heating at a low temperature and is cured by crosslinking, is increasing, and hot melts that can be bonded at a lower temperature ( The use of thermoplastic resin-based adhesive materials such as hotmelt) is also increasing.

하지만 이러한 경우에도 기존 에폭시계 수지에 비해 물성이 좋지 않아 접합 특성, 열주기(Thermal cycling), 프레셔 쿠커 테스트(Pressure cooker test), 고온고습, 고온저장 등의 신뢰성이 매우 떨어지는 문제점이 발생한다.However, even in this case, the physical properties are poor compared to the existing epoxy resin, so the reliability of bonding properties, thermal cycling, pressure cooker test, high temperature, high humidity, and high temperature storage occurs.

따라서, 더욱 낮은 저온에서 단시간에 경화가 가는 에폭시계 수지의 접합재료의 개발이 활발하지만 접착필름 제조시 경화시작온도가 유기용매의 건조 공정의 온도보다 더 높게 나타나야 유기용매 건조 단계에서 경화가 일어나지 않는다는 제약 사항 때문에 한계에 도달해 있다.Therefore, the development of the bonding material of the epoxy-based resin that is cured in a short time at a lower temperature is active, but the curing start temperature should be higher than the temperature of the drying process of the organic solvent in the adhesive film production does not occur in the organic solvent drying step Limits have been reached due to constraints.

또한, 사용제품에 비해 경화시작온도를 10 ℃ 낮춘 접합재료의 상온 저장시 저온 경화를 위해 경화시작온도를 낮추게 되면 상온저장성이 매우 떨어져 유효기간(shelf life)이 빠르게 감소하게 된다.
In addition, when the curing start temperature is lowered for low temperature curing at room temperature storage of the bonding material lowering the curing start temperature by 10 ° C. compared to the used product, shelf life is very low and shelf life decreases rapidly.

본 발명의 목적은 광잠재성 경화제를 포함하여 상온에서 보관성이 뛰어나 유효기간이 반영구적이며 건조공정에 제약이 없고 저온에서 단시간에 경화가 이루어져 전자 부품간 접합 시 고온에 의해 생기는 열응력, 열 팽창에 의한 어긋남, 열에 의한 고분자 기판 등의 손상이 발생하는 등의 문제를 해결해 주며 동시에 패키지 자체의 높은 신뢰성 및 접착력도 우수한 접착필름용 수지 조성물 및 이를 이용한 접착필름을 제공하는데 있다.The purpose of the present invention is to include a light latent curing agent, excellent storage properties at room temperature, semi-permanent shelf life, and there is no restriction in the drying process, the curing is performed in a short time at low temperature, thermal stress caused by high temperature when bonding between electronic components, thermal expansion The present invention provides a resin composition for an adhesive film and an adhesive film using the same, which solves problems such as misalignment due to heat and damage to a polymer substrate due to heat.

본 발명이 이루고자 하는 기술적 과제들은 이상에서 언급한 기술적 과제들로 제한되지 않으며, 언급되지 않은 다른 기술적 과제들은 아래의 기재로부터 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 명확하게 이해될 수 있을 것이다.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not intended to limit the invention to the particular embodiments that are described. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not restrictive of the invention, There will be.

상기와 같은 목적을 달성하기 위한, 본 발명의 접착필름용 수지 조성물은 열가소성 수지, 열경화성 수지, 광잠재성 경화제와 유기용매를 포함한다.In order to achieve the above object, the resin composition for an adhesive film of the present invention includes a thermoplastic resin, a thermosetting resin, a photo latent curing agent and an organic solvent.

특히, 상기 열가소성 수지는 5~60 중량%, 상기 열경화성 수지는 25~94.9 중량%, 및 상기 광잠재성 경화제는 0.1~30 중량%로 조성되며, 상기 유기용매는 상기 열가소성 수지, 상기 열경화성 수지 및 상기 광잠재성 경화제, 전체 중량의 40~250 중량%로 혼합된다.In particular, the thermoplastic resin is 5 to 60% by weight, the thermosetting resin is 25 to 99.4% by weight, and the optical latent curing agent is composed of 0.1 to 30% by weight, the organic solvent is the thermoplastic resin, the thermosetting resin and The light latent curing agent, 40 to 250% by weight of the total weight is mixed.

상기 접착필름용 수지 조성물은 전기적 특성 향상을 위해 금속 분말 또는 금속이 코팅된 폴리머볼의 도전성 입자를 더 포함하며, 또한, 상기 접착필름용 수지 조성물은 물리적 특성 향상을 위해 실리카 필러의 첨가제를 더 포함하기도 한다.The adhesive composition for the adhesive film further includes conductive particles of a metal powder or a metal coated polymer ball for improving electrical properties, and the adhesive composition for the adhesive film further includes an additive of a silica filler to improve physical properties. Sometimes.

본 발명의 접착필름은 상기 접착필름용 수지 조성물을 이용한 것으로써, 구체적으로 열가소성 수지, 열경화성 수지 및 광잠재성 경화제를 포함하는며, 특히 상기 열가소성 수지 5~60 중량%, 상기 열경화성 수지 25~94.9 중량% 및 상기 광잠재성 경화제 0.1~30 중량%로 이루어진다.The adhesive film of the present invention uses the resin composition for the adhesive film, and specifically includes a thermoplastic resin, a thermosetting resin and a photo latent curing agent, in particular the thermoplastic resin 5 to 60% by weight, the thermosetting resin 25 to 99.4 Wt% and 0.1-30 wt% of the optical latent curing agent.

상기 접착필름은 120 ℃이하에서 20초 이하에 경화반응이 완료되는 것이 특징이다.The adhesive film is characterized in that the curing reaction is completed in 20 seconds or less at 120 ℃ or less.

상기 광잠재성 경화제는 광산발생제(PAG; photo acid generator), 광염발생제(PBG, photo base generator) 중 어느 하나 이상인 것이 특징이다.The photo latent curing agent is any one or more of a photo acid generator (PAG), a photo base generator (PBG).

상기 접착필름은 전기적 특성 향상을 위해 금속 분말 또는 금속이 코팅된 폴리머볼의 도전성 입자를 더 포함하며, 또한, 상기 접착필름은 물리적 특성 향상을 위해 실리카 필러의 첨가제를 더 포함하기도 한다.The adhesive film further includes conductive particles of a metal powder or a metal-coated polymer ball to improve electrical properties, and the adhesive film may further include an additive of a silica filler to improve physical properties.

본 발명의 접착필름의 제조방법은 열가소성 수지 5~60 중량%, 열경화성 수지 25~94.9 중량%, 및 광잠재성 경화제 0.1~30 중량% 조성을 준비하는 제1단계와, 상기 열가소성 수지, 상기 열경화성 수지와 상기 광잠재성 경화제, 전체 중량의 40~250 중량%의 유기용매를 준비하는 제2단계와, 상기 제1단계에서 준비한 상기 열가소성 수지, 열경화성 수지 및 광잠재성 경화제와 상기 제2단계에서 준비한 상기 유기용매를 혼합 및 용해시켜 접착필름용 수지 조성물을 제조하는 제3단계 및 상기 접착필름용 수지 조성물을 이형지 또는 웨이퍼 위에 도포 및 건조하여 접착필름을 제조하는 제4단계를 포함한다.The method for preparing an adhesive film of the present invention includes preparing a composition of 5 to 60 wt% of a thermoplastic resin, 25 to 99.4 wt% of a thermosetting resin, and 0.1 to 30 wt% of a photo latent curing agent, and the thermoplastic resin and the thermosetting resin. And a second step of preparing the optical latent curing agent and an organic solvent having a total weight of 40 to 250% by weight, and the thermoplastic resin, the thermosetting resin and the optical latent curing agent prepared in the first step, and the second step. And a fourth step of preparing the adhesive film by mixing and dissolving the organic solvent and applying and drying the adhesive film resin composition on a release paper or a wafer.

상기 제4단계에서 건조처리시 상기 접착필름용 내의 유기용매가 휘발되어 상기 접착필름은 상기 열가소성 수지, 열경화성 수지 및 광잠재성 경화제로 이루어지며, 상기 제4단계에서 도포 및 건조처리는 옐로우 룸(yellow room)에서 이루어지는 것이 특징이다.
In the fourth step, the organic solvent in the adhesive film is volatilized, and the adhesive film is composed of the thermoplastic resin, the thermosetting resin, and the optical latent curing agent. yellow room).

이상에서 설명한 바와 같이 본 발명에 의해, 광잠재성 경화제를 포함하여 상온에서 보관성이 뛰어나 유효기간이 반영구적이며 건조공정에 제약이 없으며 120 ℃이하의 저온 조건에서 단시간인, 20초 이내에 경화가능한 접착필름용 수지 조성물을 제공할 수 있다.As described above, the present invention includes an optical latent curing agent, has excellent storage properties at room temperature, has a shelf life semipermanent, and is not limited to a drying process, and can be cured within 20 seconds at a low temperature of 120 ° C. or less for a short time. The resin composition for films can be provided.

이와 같이 상기 수지 조성물을 이용하여 제조된 접착필름은 전자 부품간 접합시 고온에 의해 생기는 열응력, 열 팽창에 의한 어긋남, 열에 의한 고분자 기판 등의 손상을 해결해주며 동시에 패키지 자체의 높은 신뢰성 및 접착력도 우수하다.
As described above, the adhesive film manufactured by using the resin composition solves thermal stress caused by high temperature when bonding electronic components, misalignment caused by thermal expansion, and damage to the polymer substrate due to heat, and at the same time, high reliability and adhesive strength of the package itself. great.

도 1은 comma roll coating의 모식도.
도 2는 본 발명의 접착필름을 사용하여 칩을 접합하는 공정도를 나타낸 도면.
도 3은 헥사플루오르안티모닉산을 형성하는 광산발생제(PAG)의 화학구조를 나타낸 도면.
도 4a는 본 발명의 접착필름에 대해 DSC 동적 스캔(DSC dynamic scan)을 나타낸 도면.
도 4b는 본 발명의 접착필름에 대해 100℃의 일정온도에서 DSC 등온선 스캔(DSC isothermal scan)을 나타낸 도면.
도 5a는 본 발명의 접착필름에 대해 형광등 노출(1hr) 또는 형광등 노출 후 추가로 UV를 조사(1hr-exp 0.5 J/cm2)후 반응성을 나타낸 도면.
도 5b는 UV 조사 후 실온에서 보관가능한 저장성을 나타낸 도면.
도 6은 열가소성 수지(T.P.: thermoplastic)의 함량에 따른 접합된 구조체의 박리 접착강도(peel strength, gf/cm)를 나타낸 도면.
도 7a는 수지(resin)와 PAG 함량(10 wt%, 20 wt%)에 따른 UV 투과율을 나타낸 도면.
도 7b는 상기 도 7a에서 A부분의 확대도.
도 8은 상기 도 7a 및 도 7b의 결과를 기반으로 UV투과율에 따른 PAG 최대함량을 나타낸 도면.
도 9는 경화 발열 반응에 따른 PAG 최소함량을 나타낸 도면.1 is a schematic diagram of a comma roll coating.
2 is a view showing a process for bonding the chip using the adhesive film of the present invention.
FIG. 3 shows the chemical structure of a photoacid generator (PAG) forming hexafluoroantimonic acid. FIG.
Figure 4a is a diagram showing a DSC dynamic scan (DSC dynamic scan) for the adhesive film of the present invention.
Figure 4b is a DSC isothermal scan (DSC isothermal scan) at a constant temperature of 100 ℃ for the adhesive film of the present invention.
Figure 5a is a view showing the reactivity after the irradiation (1hr-exp 0.5 J / cm 2 ) further UV irradiation (1hr) or after the fluorescent lamp exposure to the adhesive film of the present invention.
Figure 5b is a view showing the storage properties that can be stored at room temperature after UV irradiation.
Figure 6 is a view showing the peel strength (peel strength, gf / cm) of the bonded structure according to the content of the thermoplastic resin (TP: thermoplastic).
Figure 7a is a view showing the UV transmittance according to the resin (resin) and PAG content (10 wt%, 20 wt%).
7B is an enlarged view of a portion A in FIG. 7A.
8 is a view showing the maximum PAG content according to the UV transmittance based on the results of FIGS. 7a and 7b.
9 is a view showing the minimum PAG content according to the curing exothermic reaction.

이하, 첨부된 도면을 참조하여 본 발명의 바람직한 실시예를 상세하게 설명한다. 도면들 중 동일한 구성요소들은 가능한 어느 곳에서든지 동일한 부호로 표시한다. 또한 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 상세한 설명은 생략한다.Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Like elements in the figures are denoted by the same reference numerals wherever possible. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.

본 발명의 접착필름용 수지 조성물은 열가소성 수지, 광잠재성 경화제, 열경화성 수지 및 유기용매를 포함하여 조성된다.The resin composition for an adhesive film of the present invention comprises a thermoplastic resin, a photo latent curing agent, a thermosetting resin, and an organic solvent.

상기 열가소성 수지는 경화 및 접착 작용을 발휘하는 것으로서 스티렌 부타디엔 수지, 에틸렌 비닐 수지, 에스테르계 수지, 실리콘 수지, 페녹시 수지, 아미드계 수지, 아크릴 수지, 아크릴레이트계 수지 또는 폴리비닐부티랄 수지 또는 이들의 혼합물 등이 사용가능하다.The thermoplastic resins exhibit hardening and adhesive action, and include styrene butadiene resin, ethylene vinyl resin, ester resin, silicone resin, phenoxy resin, amide resin, acrylic resin, acrylate resin, or polyvinyl butyral resin or these. Mixtures thereof and the like can be used.

상기 열가소성 수지는 조성물 중 5~60중량%를 차지하며, 이때 함량이 5 중량% 미만일 경우에 도막의 형태를 유지하고자 하는 힘 응집력이 떨어져 필름 형성능이 떨어질 수 있으며, 60 중량%를 초과할 경우에는 경화 및 접착능이 떨어지는 문제가 있다.The thermoplastic resin occupies 5 to 60% by weight of the composition, and when the content is less than 5% by weight, the force cohesion to maintain the form of the coating may be reduced, and thus the film forming ability may be lowered. There is a problem of poor curing and adhesion.

상기 열경화성 수지 또한 경화 및 접착 작용을 발휘하는 것으로서 에폭시계 수지 또는 폴리이미드 수지, 또는 이들의 혼합물 등이 사용되며, 바람직하게는 에폭시계 수지를 사용함이 좋다.As the thermosetting resin also exhibits a curing and adhesive action, an epoxy resin, a polyimide resin, a mixture thereof, or the like is used, and preferably an epoxy resin is used.

상기 에폭시계 수지는 특별히 한정되지 않으나, 필름의 형상을 고려하면 고상 또는 고상에 근접한 에폭시로서, 하나 이상의 관능기를 가지고 있는 에폭시 수지가 바람직하다.The epoxy resin is not particularly limited, but in consideration of the shape of the film, an epoxy resin having one or more functional groups is preferable as the solid phase or the epoxy near the solid phase.

상기 고상 에폭시계 수지로는 특별히 제한되지는 않으나 예를 들면, 비스페놀계 에폭시, 페놀 노볼락(Phenol novolac)계 에폭시, o-크레졸 노볼락(Cresol novolac)계 에폭시, 다관능 에폭시, 아민계 에폭시, 복소환 함유 에폭시, 치환형 에폭시, 나프톨계 에폭시 및 이들의 유도체를 들 수 있다.The solid epoxy resin is not particularly limited, but for example, bisphenol epoxy, phenol novolac epoxy, o-cresol novolac epoxy, polyfunctional epoxy, amine epoxy, Heterocyclic containing epoxy, substituted epoxy, naphthol epoxy and derivatives thereof.

상기 열경화성 수지는 조성물 중 25~94.9 중량%를 차지하며, 이때 함량이 25 중량% 미만일 경우에 반응성이 느려서 속경화되지 않을 수 있게 되며, 94.9 중량%를 초과할 경우에는 필름형성능이 떨어지는 문제가 있다.The thermosetting resin occupies 25 to 99.4% by weight of the composition, and when the content is less than 25% by weight, the reactivity is slow so that it may not be cured quickly, and when it exceeds 94.9% by weight, there is a problem that the film forming ability is lowered. .

상기와 같은 열경화성 수지는 상온에서는 불활성 상태지만, 가열 용융 후에 활성화되기 때문에 충분한 접속신뢰성이나 접착강도를 얻기 위해서는 고온에서 상당한 경화반응 진행시간이 필요하다. Although the above-mentioned thermosetting resin is inert at room temperature, since it is activated after hot melting, a considerable curing reaction progress time is required at high temperature to obtain sufficient connection reliability and adhesive strength.

따라서, 본 발명은 120℃ 이하의 저온에서도 속경화가 가능하여 고온에서 장시간에 걸친 접착시간에 의한 제품특성 및 생산 효율성을 저하시키는 기존의 문제를 해소한다.Therefore, the present invention solves the existing problem of lowering the product characteristics and production efficiency due to the rapid curing at a low temperature of less than 120 ℃ by long time adhesion time at high temperature.

즉, 상기 열경화성 수지를 경화시키는 경화제로 광잠재성 경화제를 사용하여 UV가 조사되기 전에는 잠재성이 매우 뛰어나 유효기간이 반영구적이며 건조공정에 제약이 없으면서도 UV 조사 이후에는 잠재성이 사라지고 120℃ 이하의 저온 속경화를 가능하게 한다.In other words, the latent curing period is very excellent before the UV irradiation using a photo latent curing agent as a curing agent to cure the thermosetting resin, the shelf life is semi-permanent, and there is no restriction in the drying process, the potential disappears after UV irradiation and 120 ℃ or less Enables low temperature rapid curing.

상기 광잠재성 경화제는 광산발생제(PAG; photo acid generator), 광염발생제(PBG, photo base generator) 중 어느 하나 이상을 사용하는 것으로서 상기 광산발생제(PAG; photo acid generator)는 구체적인 예로, 오니움염계인 요드니움염(iodonium salts) 술포늄염(sulfonium salts), 포스포늄염, 디아조니움염, 피리디니움염, 이미드류가 있으며, 이들은 1종 또는 2종 이상의 혼합물 형태로 사용될 수 있다.The photo latent curing agent is any one or more of a photo acid generator (PAG), a photo base generator (PBG), the photo acid generator (PAG) is a specific example, Onium salts include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and imides, and these may be used in the form of one kind or a mixture of two or more kinds.

상기 광잠재성 경화제는 조성물 중 0.1~30 중량%를 차지하며, 이때 함량이 0.1 중량% 미만일 경우에 발열량이 감소하게 되며, 함량이 30 중량%를 초과할 경우에는 투과도가 매우 낮아져 25 ㎛ 두께의 필름 경우 바닥에 50% 정도의 UV만 도달하게 된다. 이에 조성물에서 바람직하게는 0.25~25 중량%를 차지하는 것이 좋다.The photo latent curing agent occupies 0.1 to 30% by weight of the composition, in which the calorific value is reduced when the content is less than 0.1% by weight, and when the content is more than 30% by weight, the transmittance is very low to have a thickness of 25 μm. In the case of film, only 50% of the UV reaches the bottom. In the composition it is preferable to occupy 0.25 to 25% by weight.

상기 유기용매는 코팅을 위해 점도를 낮추기 위한 용도로 첨가된 것으로서, 상기 열가소성 수지, 상기 열경화성 수지와 상기 광잠재성 경화제, 전체 중량의 40~250 중량%로 포함되는 것이 좋다.The organic solvent is added for the purpose of lowering the viscosity for coating, and the thermoplastic resin, the thermosetting resin and the photo latent curing agent, may be included in 40 to 250% by weight of the total weight.

상기 유기용매는 상기 열가소성 수지, 상기 열경화성 수지와 상기 광잠재성 경화제를 용해시킬 수 있는 용매이면 모두 사용가능하므로 특별히 종류 및 용매의 비중에 제한되지는 않으나, 예를 들면 톨루엔, 자일렌, 프로필렌 글리콜 모노메틸 에테르 아세테이트, 벤젠, 아세톤, 메틸에틸케톤, 테트라히드로 퓨란, 디메틸포름알데히드, 시클로헥사논 등을 사용할 수 있다.The organic solvent may be used as long as it is a solvent capable of dissolving the thermoplastic resin, the thermosetting resin and the photo latent curing agent, but is not particularly limited to the type and specific gravity of the solvent. For example, toluene, xylene, and propylene glycol Monomethyl ether acetate, benzene, acetone, methyl ethyl ketone, tetrahydrofuran, dimethylformaldehyde, cyclohexanone and the like can be used.

한편, 본 발명의 접착필름은 하기 제조과정을 통해 제조된다.On the other hand, the adhesive film of the present invention is manufactured through the following manufacturing process.

1. 제1단계1. The first step

열가소성 수지는 5~60 중량%로, 열경화성 수지는 25~94.9 중량%로, 광잠재성 경화제는 0.1~30 중량%로 준비한다.
The thermoplastic resin is 5 to 60% by weight, the thermosetting resin is 25 to 99.4% by weight, and the optical latent curing agent is prepared at 0.1 to 30% by weight.

2. 제2단계2. Second Step

상기 열가소성 수지, 상기 열경화성 수지 및 상기 광잠재성 경화제 전체 중량의 40~250 중량%의 유기용매를 준비하다.
An organic solvent of 40 to 250% by weight of the thermoplastic resin, the thermosetting resin, and the total weight of the photo latent curing agent is prepared.

3. 제3단계3. The third step

상기 제1단계에서 준비한 상기 열가소성 수지, 열경화성 수지 및 광잠재성 경화제와 상기 제2단계에서 준비한 상기 유기용매를 혼합 및 용해시켜 접착필름용 수지 조성물을 제조한다.The thermoplastic resin, the thermosetting resin and the photo latent curing agent prepared in the first step and the organic solvent prepared in the second step are mixed and dissolved to prepare a resin composition for an adhesive film.

여기서 추가로 상기 수지 조성물의 용도에 따라, 전기적 특성 향상을 위해 니켈 등의 금속 분말 또는 금과 니켈 등의 금속이 코팅된 폴리머볼 등의 도전성 입자를 포함하며, 이때, 상기 금속분말 또는 폴리머볼은 조성물 전체중량대비 25 중량%까지 더 첨가된다.Here, according to the use of the resin composition, in order to improve the electrical properties include metal particles such as nickel or conductive particles such as polymer balls coated with metals such as gold and nickel, wherein the metal powder or polymer balls Further up to 25% by weight of the total weight of the composition is added.

또한, 추가로 물리적 특성 향상을 위해 실리카 필러 등의 첨가제를 더 포함할 수도 있으며, 이로 인해 열팽창계수의 감소 및 모듈러스의 상승효과를 갖게 된다.
In addition, in order to further improve physical properties, an additive such as a silica filler may be further included, thereby reducing the coefficient of thermal expansion and synergistic effect of modulus.

4. 제4단계4. Fourth Step

상기 접착필름용 수지 조성물을 이형지 또는 웨이퍼 위에 도포 및 건조하여 접착필름을 제조한다.The adhesive composition for the adhesive film is coated and dried on a release paper or a wafer to prepare an adhesive film.

상기 도포 및 건조처리는 옐로우 룸(yellow room)에서 이루어지며, 이때, 접착필름용 수지조성물 내의 유기용매가 휘발되어 상기 접착필름은 상기 열가소성 수지, 열경화성 수지 및 광잠재성 경화제만으로 이루어진다.The coating and drying process is performed in a yellow room. At this time, the organic solvent in the resin composition for the adhesive film is volatilized, and the adhesive film is composed of only the thermoplastic resin, the thermosetting resin, and the light latent curing agent.

상기 옐로우 룸(yellow room)은 파장이 가장 짧은 노란색 가시광선으로 방 전체가 노란빛을 띄는 방을 의미하는 것으로서 상기 접착필름용 수지 조성물이 특정 빛에 의해 반응하지 않게 하기 위한 목적으로 상기 도포 및 건조처리는 옐로우 룸(yellow room)에 이루어지는 것이 바람직하다.The yellow room refers to a room in which the whole room is yellow with yellow visible light having a shortest wavelength. The coating and drying treatments are performed for the purpose of preventing the adhesive composition from reacting with a specific light. Is preferably made in a yellow room.

상기 접착필름을 코팅하는 방법으로는 본 발명이 속하는 기술분야에서 알려져 있는 통상의 제조방법을 제한없이 사용하여 제조할 수 있다. As the method for coating the adhesive film can be prepared using a conventional manufacturing method known in the art to which the present invention belongs.

예를 들어, 도 1(간략한 comma roll coating의 모식도)에 도시되어 있듯이 이형지 위에 슬러리(slurry; 본 발명의 접착필름용 수지 조성물)이 코팅되어 나가고 이후 특정온도로 셋팅되어 있는 옐로우 룸(yellow room)의 건조 영역(Drying zone)을 지나면서 유기용매(solvent)가 휘발되는 콤마롤 코팅(comma roll coating)방법, 그 외에 스프레이, 닥터 블레이드(doctorblade), 메니스커스(meniscus), 스핀코팅, 스크린 프린팅, 스텐실 프린팅, 그라비아코팅 등 다양한 코팅방법 등 을 통해서 형성될 수 있다.For example, as shown in FIG. 1 (schematic diagram of a simple comma roll coating), a slurry (slurry; a resin composition for an adhesive film of the present invention) is coated on a release paper and then set to a specific temperature. A comma roll coating method in which an organic solvent is volatilized through the drying zone of the spray, in addition to spraying, doctorblade, meniscus, spin coating, and screen printing. It can be formed through a variety of coating methods, such as stencil printing, gravure coating.

이와 같이 제조된 접착필름은 실온에서 무한정 보관이 가능하다.The adhesive film thus prepared can be stored indefinitely at room temperature.

상기 접착필름의 두께는 10 내지 100㎛인 것이 바람직하다. 이는 건조 공정에 적합한 두께임과 동시에 상기 두께가 접착제를 이용한 전자 패키지 구조에서 물리적인 접착력 및 전기적 절연, 또는 전기적 접속 등의 패키지용 접착제의 역할이 원활이 이루어지기 때문이다.It is preferable that the thickness of the said adhesive film is 10-100 micrometers. This is because a thickness suitable for a drying process and the thickness of the package adhesive such as physical adhesive force, electrical insulation, or electrical connection in the electronic package structure using the adhesive are performed smoothly.

도 2에 나타나 있듯이, 상기와 같이 광잠재성 경화제가 함유된 접착필름이 경화되지 않은 상태에서 기판위에 가압착 등의 방법으로 접착되고(일반 형광등 아래에서 작업시 shelf life < 1 day)되고 이형지 또는 커버 필름을 제거한 다음 UV를 비추면(이때 shelf life < few hours) 광잠재성 경화제가 열에 의해 경화반응을 일으킬 수 있는 경화제로 활성화된다. UV 조사 이후 기판 또는 칩을 하부 기판 또는 칩과 정렬, 열압착 공정을 통하여 접합 공정이 수행된다.As shown in Figure 2, as described above, the adhesive film containing the optical latent curing agent is adhered to the substrate by pressing or the like in the uncured state (shelf life <1 day when working under a normal fluorescent lamp) and the release paper or Removing the cover film and then irradiating with UV (shelf life <few hours) activates the latent curing agent as a curing agent that can cause a curing reaction by heat. After UV irradiation, the bonding process is performed by aligning the substrate or chip with the lower substrate or chip, and thermocompression bonding.

이때, UV를 비추기 전에는 광잠재성 경화제의 활성이 일어나지 않으나, UV를 비춘 후에 광잠재성 경화제가 열에 의해 경화 반응을 일으킬 수 있는 경화제로 활성화되므로 100 ℃이하의 저온에서 15 초이하의 짧은 시간에 경화반응이 완료되어 접착되게 된다.
At this time, the activity of the light latent curing agent does not occur before the UV light is irradiated, but since the light latent curing agent is activated as a curing agent that can cause a curing reaction by heat after UV light, at a short time of 15 seconds or less at a low temperature below 100 ℃ The curing reaction is completed and bonded.

이하에서는 실시예 및 실험예를 들어 본 발명에 관하여 더욱 상세하게 설명할 것이나. 이들 실시예는 단지 설명의 목적을 위한 것으로 본 발명의 보호 범위를 제한하고자 하는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. These examples are for illustrative purposes only and are not intended to limit the protection scope of the present invention.

<실시예 1> 본 발명의 접착필름 제조Example 1 Preparation of Adhesive Film of the Present Invention

반고상 상태의 비스페놀 A타입의 에폭시 수지 (Epoxy Equivalent Weight(EEW) 230~270) 38 wt%, 고상 상태의 비스페놀 A타입의 에폭시 수지(EEW 450~500) 38 wt%, 비스페놀 A타입의 페녹시 수지 (중량평균분자량 60,000~80,000의 열가소성수지) 19 wt% 및 도 3에 명시된 헥사플루오로안티모닉산을 형성하는 광산 발생제(PAG) 5 wt%를 유기용매인 테트라하이드로퓨란(에폭시 수지, 페녹시수지, 광산발생제 전체의 중량을 기준으로 150 중량%)에 용해시켜 접착필름용 수지 조성물을 제조하였다. 38 wt% of bisphenol A type epoxy resin (Epoxy Equivalent Weight (EEW) 230 ~ 270), 38 wt% of bisphenol A type epoxy resin (EEW 450 ~ 500), phenoxy of bisphenol A type 19 wt% of the resin (the thermoplastic resin having a weight average molecular weight of 60,000 to 80,000) and 5 wt% of the photoacid generator (PAG) forming the hexafluoroantimonic acid shown in FIG. 3 were added to the organic solvent tetrahydrofuran (epoxy resin, phenoxy The resin composition for the adhesive film was prepared by dissolving in 150 wt%) of the resin and the photoacid generator.

상기 수지 조성물을 옐로우 룸에서 comma roll coating 방법을 통해 이형지 위에 150 ㎛ 두께의 갭과 5cm 폭으로 분당 50 cm의 속도로 도포하였고 도포 직후 90 ℃ 의 온도에서 5분간 유지하는 건조 공정을 통해 유기용매만 휘발되도록 건조시켜 이형지 위에 에폭시 수지 76 wt% (반고상 38 wt%, 고상 38 wt%), 열가소성 수지 19 wt%, PAG 5 wt%로 구성된 약 50 ㎛ 두께의 접착필름을 제조하였다.The resin composition was applied on a release paper at a rate of 50 cm per minute with a gap of 150 μm in thickness and 5 cm on a release paper by a comma roll coating method in a yellow room, and then organic solvent only through a drying process maintained at a temperature of 90 ° C. for 5 minutes immediately after application. After drying to volatilize, an adhesive film having a thickness of about 50 μm consisting of 76 wt% epoxy resin (38 wt% semisolid, 38 wt% solid), 19 wt% thermoplastic resin, and 5 wt% PAG was prepared on the release paper.

<실험예 1> 극저온 접합의 가능성 측정Experimental Example 1 Possibility Measurement of Cryogenic Bonding

도 4a 및 도 4b에 나타나 있듯이, 본 발명의 실시예 1에서 제조된 접착필름의 UV 노광 전 후의, 기존 공정에 비하여 극저온인 100 ℃에서의 경화속도를 열분석기(DSC; Differential Scanning Calorimeter)의 동적 스캔(Dynamic scan)을 통해 확인하였다. 그 결과 UV 조사전의 접착 필름(non-exposure)은 200 ℃에서도 경화 반응을 일으키지 않아 높은 잠재성을 가진 것을 확인하였고, i-line의 UV에 0.5 J/cm2 의 양으로 조사된 접착 필름은 100 ℃(도 4a)에서 15초(도 4b) 안에 경화가 완료됨을 확인하였다.
As shown in Figure 4a and Figure 4b, before and after the UV exposure of the adhesive film prepared in Example 1 of the present invention, the curing rate of the thermal analyzer (DSC; Differential Scanning Calorimeter) at a curing temperature of 100 ℃ It was confirmed through a scan (Dynamic scan). As a result, it was confirmed that the adhesive film (non-exposure) before the UV irradiation did not cause a curing reaction even at 200 ℃ has a high potential, the adhesive film irradiated in the amount of 0.5 J / cm 2 to the UV of the i-line 100 It was confirmed that the curing was completed in 15 seconds (Fig. 4b) at ℃ (Fig. 4a).

<실험예 2> 형광등 아래에서의 작업성 측정Experimental Example 2 Measurement of Workability under Fluorescent Lamps

도 5a에 나타나 있듯이, 상기 실시예 1에서 제조된 접착필름을 소비전력 40 W 일반 형광등 아래에서 1시간 동안 노출 시킨 뒤의 온도에 따른 발열 반응거동을 DSC의 Dynamic scan을 통해 확인하였다(도 5a-1hr).As shown in Figure 5a, the exothermic reaction behavior according to the temperature after exposing the adhesive film prepared in Example 1 under a power consumption of 40 W general fluorescent lamp for 1 hour was confirmed by the dynamic scan of the DSC (Fig. 5a- 1hr).

형광등에 1시간 노출 후 i-line 의 UV에 0.5 J/cm2 의 양으로 조사 후의 온도에 따른 발열 반응거동 또한 DSC의 Dynamic scan을 통해 확인하였다(도 5a 1hr+exp 0.5 J/cm2 ). 도 5a 상에서 "exp'란 노광(exposure)을 지칭하는 약자이다.Exothermic reaction behavior according to the temperature after irradiation in the amount of 0.5 J / cm 2 to the UV of the i-line after 1 hour exposure to the fluorescent lamp was also confirmed by the dynamic scan of the DSC (Fig. 5a 1hr + exp 0.5 J / cm 2 ). "Exp 'on FIG. 5A is an abbreviation for exposure.

그 결과, 형광등에만 노출된 접착필름은 발열반응을 보이지 않았으나, 이후 UV에 추가 노출된 접착필름만 발열반응을 보여주었다. 이를 통하여 접착필름 내에 광잠재성 경화제로 첨가되어 있는 PAG가 형광등 아래에서는 반응하지 않으며 UV에서만 반응하여 경화제를 생성하는 것을 알 수 있다.As a result, the adhesive film exposed only to the fluorescent lamp did not show an exothermic reaction, but only the adhesive film further exposed to UV showed an exothermic reaction. Through this, it can be seen that PAG added as an optical latent curing agent in the adhesive film does not react under a fluorescent lamp but reacts only with UV to generate a curing agent.

즉, 형광등 아래에서 단기간에 이루어지는 가접합 공정에서 잠재성이 유지되며 가접합 공정 및 이후 작업에 문제가 없음을 알 수 있다.
In other words, it can be seen that the potential is maintained in the temporary bonding process performed under a fluorescent lamp in a short period of time and there is no problem in the temporary bonding process and subsequent operations.

<실험예 3> 가접합 및 UV 조사 이후 작업성 측정Experimental Example 3 Measurement of Workability after Temporary Bonding and UV Irradiation

도 5b에 나타나 있듯이, 상기 실시예 1에서 제조된 접착 필름을 i-line의 UV에 0.5 J/cm2 의 양으로 조사 후 보관 시간에 따른 발열량의 감소를 DSC의 Dynamic scan을 통해 확인하였다. 도 5b 상에서 "exp'란 노광(exposure)을 지칭하는 약자이다.As shown in Figure 5b, after irradiating the adhesive film prepared in Example 1 in an amount of 0.5 J / cm 2 to the UV of the i-line it was confirmed through the dynamic scan of the DSC calorific value according to the storage time. In FIG. 5B, "exp 'is an abbreviation for exposure.

발열량
(Exothermic heat)Calorific value
(Exothermic heat) 0 min0 min 101.4 mj/g101.4 mj / g 30 min30 min 101.6 mj/g101.6 mj / g 1 hr1 hr 94.2 mj/g94.2 mj / g 2 hr2 hr 84.0 mg/g84.0 mg / g

상기 표 1에 나타나 있듯이 UV조사 후 1시간이후 부터 발열량의 감소가 관측 되었으며 이는 UV조사 이후 상온에서의 경화 속도가 매우 느림을 말해준다. 가접합 이후 본 접합(main bonding)까지 주로 1분 이내에 이루어짐을 고려하면 UV조사 이후 본 접합 전까지 경화는 일어나지 않으며 본 접합의 작업성에 문제가 없음을 알 수 있다.
As shown in Table 1, a decrease in calorific value was observed after 1 hour after UV irradiation, which indicates that the curing rate at room temperature after UV irradiation is very slow. Considering that the main bonding after the temporary bonding is mainly made within 1 minute, curing does not occur until the main bonding after UV irradiation, and there is no problem in the workability of the main bonding.

<실험예 4> 접합특성 (접합력) 평가 <Experiment 4> Evaluation of bonding characteristics (bonding force)

상기 실시예 1에서 제조된 접착필름의 전자 패키지용 접합제로서의 특성 평가를 위하여 유기 경성기판과 연성기판간의 접합제로 사용하여 접합력을 측정하였다. 유기 경성기판으로서는 경화된 에폭시 수지와 유리섬유로 이루어진 FR4(Flame Retardant type 4) 재질의 기판을 사용하였으며, 유기 연성기판으로는 폴리이미드 재질의 기판을 사용하였다. 유기 경성기판의 접합부에 상기 실시예 1에서 제조된 접착필름을 2.5 mm × 25 mm 크기로 잘라 80 ℃에서 가접합한 뒤 i-line의 UV에 0.5 J/cm2 의 양으로 조사되었으며 그 후 유기 연성기판과 110 ℃의 온도에서 15 초간 3 MPa의 압력으로 열 압착 공정을 통하여 접합되었다.In order to evaluate the properties of the adhesive film prepared in Example 1 as a bonding agent for an electronic package, bonding strength was measured using the bonding agent between the organic hard substrate and the flexible substrate. As the organic hard substrate, a FR4 (Flame Retardant type 4) substrate made of a cured epoxy resin and glass fiber was used, and a polyimide substrate was used as the organic flexible substrate. The adhesive film prepared in Example 1 was cut to a size of 2.5 mm × 25 mm at the junction of the organic hard substrate, and temporarily bonded at 80 ° C., and irradiated in an amount of 0.5 J / cm 2 to the UV of the i-line. The flexible substrate was bonded through a thermocompression process at a pressure of 3 MPa for 15 seconds at a temperature of 110 ° C.

접합된 구조체를 90 ℃ 박리(Peel) 접합 테스트를 통하여 접착 강도를 측정한 결과, 도 6에 나타나 있듯이 열가소성 수지(T.P)의 중량이 19 wt%일 때 박리 접착강도가 700 gf/cm 로 매우 우수함을 확인하였다.
As a result of measuring the adhesive strength of the bonded structure through a 90 ° C. Peel bonding test, as shown in FIG. 6, when the weight of the thermoplastic resin (TP) was 19 wt%, the peeling adhesive strength was very excellent as 700 gf / cm. It was confirmed.

<실험예 5> UV 투과도에 따른 최대 PAG 함량 조사Experimental Example 5 Investigation of Maximum PAG Content According to UV Transmittance

도 7a에 나타나 있듯이, 수지(Resin)와, PAG 10 wt%와, PAG 20 wt%에 대한 UV 흡광도(absorbance, log10 IO/I(IO; 조사된 UV강도, I; 투과되어 측정된 UV강도))를 측정하였고, 상기 도 7a에서 사용되는 i-line(365 nm) UV에서의 좀 더 명확한 흡광도의 수치를 확인하기 위해 도 7a의 A 부분을 확대해 본 결과, 도 7b와 같이 나타났다.As shown in Figure 7a, the UV absorbance (resin), 10 wt% PAG and 20 wt% PAG, log 10 I O / I (I O ; irradiated UV intensity, I; transmitted and measured UV intensity)) was measured, and the enlarged portion A of FIG. 7A was confirmed as shown in FIG. 7B to confirm the value of the absorbance at i-line (365 nm) UV used in FIG. 7A. .

즉, 흡광도(absorbance)가 360 nm 파장에서 PAG 10 wt%에서 0.12, PAG 20 wt%에서 0.24로 PAG의 wt% 함량에 0.012배 정확히 비례하는 것을 확인하였다.That is, the absorbance (absorbance) was found to be exactly proportional to the wt% content of PAG by 0.12 at 10 wt% PAG, 0.24 at 20 wt% PAG at 360 nm wavelength.

이에, 실시예 1에 사용된 i-line (365 nm 파장)에서 수지(Resin)는 100%, PAG 10 wt%는 75.9%, PAG 20 wt%는 57.5%의 투과율을 나타냄을 확인하였다. Thus, in the i-line (365 nm wavelength) used in Example 1 it was confirmed that the resin (Resin) 100%, PAG 10 wt% was 75.9%, PAG 20 wt% showed a transmittance of 57.5%.

도 8에 나타나 있듯이, 상기 도 7a 및 도 7b의 실험결과에서 얻어진 PAG의 wt% 함량별 흡광도의 비례상수 0.012를 기반으로 PAG 함량별 투과율(Transmittance, I/IO)로 환산하였으며 이에, PAG 최대함량으로 25 wt%(투과율 50%)를 사용하는 것이 가장 바람직함을 알 수 있었다.
As shown in Figure 8, based on the proportional constant 0.012 of the absorbance for each wt% content of PAG obtained in the experimental results of Figures 7a and 7b converted into transmittance (Transmittance, I / I O ) for each PAG content, the maximum PAG It was found that it is most preferable to use 25 wt% (transmittance 50%) as the content.

<실험예 6> 경화 발열 반응에 따른 PAG 최소 함량 조사Experimental Example 6 Investigation of Minimum PAG Content by Curing Exothermic Reaction

도 9에 나타나 있듯이, 경화가 일어나게 되면 발열이 일어나 heat flow를 표현하는 그래프가 아래로 꺼지게 되며, 이 아래로 꺼진 면적이 발열량이 된다. 이 발열량이 모든 중량%에서 0.5 wt%까지는 실험적 오차 수준 내에서 거의 같은 반면에 0.25 wt%에서는 확연히 감소된 면적을 확인할 수 있다.As shown in FIG. 9, when hardening occurs, heat is generated, and a graph representing the heat flow is turned off, and the area turned off becomes a calorific value. This calorific value is almost the same at the experimental error level up to 0.5 wt% at all weight%, while at 0.25 wt%, a markedly reduced area can be seen.

즉, PAG 의 함량이 0.5 wt%에서도 충분한 발열량이 검출되는 것을 알 수 있으며 0.5 wt% 미만이 되면 발열량이 감소되는 것을 알 수 있다.That is, even when the content of PAG is 0.5 wt%, it can be seen that sufficient calorific value is detected, and when it is less than 0.5 wt%, the calorific value is reduced.

이를 통해 PAG의 최소함량으로는 0.5 wt%를 사용하는 것이 가장 바람직함을 알 수 있었다.
This shows that it is most preferable to use 0.5 wt% as the minimum content of PAG.

상기 실험결과, 본 발명에 의해, 광잠재성 경화제를 포함하여 상온에서 보관성이 뛰어나 유효기간이 반영구적이며 건조공정에 제약이 없으며 120 ℃이하의 저온 조건에서 단시간인, 20초 이내에 경화가능한 접착필름을 사용하여 전자 부품간 접합시 고온에 의해 생기는 열응력, 열 팽창에 의한 어긋남, 열에 의한 고분자 기판 등의 손상을 해결해주며 동시에 패키지 자체의 높은 신뢰성 및 우수한 접착력을 얻을 수 있다.
As a result of the above experiment, the present invention, including the latent curing agent, excellent storage properties at room temperature, the shelf life is semi-permanent, there is no restriction in the drying process, the adhesive film curable within 20 seconds short time at low temperature conditions below 120 ℃ This solves the problem of thermal stress caused by high temperature during thermal bonding, misalignment caused by thermal expansion, and damage to the polymer substrate due to heat, and at the same time, high reliability and excellent adhesion of the package itself can be obtained.

상기의 본 발명은 바람직한 실시예를 중심으로 살펴보았으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 본질적 기술 범위 내에서 상기 본 발명의 상세한 설명과 다른 형태의 실시예들을 구현할 수 있을 것이다. 여기서 본 발명의 본질적 기술범위는 특허청구범위에 나타나 있으며, 그와 동등한 범위 내에 있는 모든 차이점은 본 발명에 포함된 것으로 해석되어야 할 것이다. The present invention has been described with reference to the preferred embodiments, and those skilled in the art to which the present invention pertains to the detailed description of the present invention and other forms of embodiments within the essential technical scope of the present invention. Could be. The scope of the present invention is defined by the appended claims, and all differences within the scope of the claims are to be construed as being included in the present invention.

Claims (22)

열가소성 수지, 열경화성 수지, 광잠재성 경화제와 유기용매를 포함하는,
접착필름용 수지 조성물.
Comprising a thermoplastic resin, a thermosetting resin, a latent curing agent and an organic solvent,
Resin composition for an adhesive film.
제1항에 있어서,
상기 열가소성 수지는 5~60 중량%, 상기 열경화성 수지는 25~94.9 중량%, 및 상기 광잠재성 경화제는 0.1~30 중량%로 조성되는,
접착필름용 수지 조성물.
The method of claim 1,
5 to 60 wt% of the thermoplastic resin, 25 to 99.4 wt% of the thermosetting resin, and 0.1 to 30 wt% of the latent curing agent,
Resin composition for an adhesive film.
제2항에 있어서,
상기 유기용매는 상기 열가소성 수지, 상기 열경화성 수지 및 상기 광잠재성 경화제, 전체 중량의 40~250 중량%로 혼합되는,
접착필름용 수지 조성물.
The method of claim 2,
The organic solvent is mixed with the thermoplastic resin, the thermosetting resin and the photo latent curing agent, 40 to 250% by weight of the total weight,
Resin composition for an adhesive film.
제1항 내지 제3항 중 어느 한항에 있어서,
상기 광잠재성 경화제는 광산발생제(PAG), 광염발생제(PBG) 중 어느 하나 이상인,
접착필름용 수지 조성물.
The method according to any one of claims 1 to 3,
The photo latent curing agent is any one or more of a photo-acid generator (PAG), photo-acid generator (PBG),
Resin composition for an adhesive film.
제1항 내지 제3항 중 어느 한항에 있어서,
상기 접착필름용 수지 조성물은 전기적 특성 향상을 위해 금속 분말 또는 금속이 코팅된 폴리머볼의 도전성 입자를 더 포함하는,
접착필름용 수지 조성물.
The method according to any one of claims 1 to 3,
The resin composition for an adhesive film further comprises conductive particles of a metal powder or a metal coated polymer ball to improve electrical properties,
Resin composition for an adhesive film.
제1항 내지 제3항 중 어느 한항에 있어서,
상기 접착필름용 수지 조성물은 물리적 특성 향상을 위해 실리카 필러의 첨가제를 더 포함하는,
접착필름용 수지 조성물.
The method according to any one of claims 1 to 3,
The resin composition for an adhesive film further comprises an additive of a silica filler to improve physical properties,
Resin composition for an adhesive film.
열가소성 수지 5~60 중량%, 열경화성 수지 25~94.9 중량%, 및 광잠재성 경화제 0.1~30 중량% 조성을 준비하는 제1단계;
상기 열가소성 수지, 상기 열경화성 수지와 상기 광잠재성 경화제, 전체 중량의 40~250 중량%의 유기용매를 준비하는 제2단계; 및,
상기 제1단계에서 준비한 상기 열가소성 수지, 열경화성 수지 및 광잠재성 경화제와 상기 제2단계에서 준비한 상기 유기용매를 혼합 및 용해시켜 접착필름용 수지 조성물을 제조하는 제3단계;를 포함하는,
접착필름용 수지 조성물의 제조방법.
A first step of preparing a composition of 5 to 60 wt% of a thermoplastic resin, 25 to 99.4 wt% of a thermosetting resin, and 0.1 to 30 wt% of a latent curing agent;
A second step of preparing the thermoplastic resin, the thermosetting resin, the optical latent curing agent, and an organic solvent having a total weight of 40 to 250 wt%; And,
And a third step of preparing a resin composition for an adhesive film by mixing and dissolving the thermoplastic resin, the thermosetting resin, and the optical latent curing agent prepared in the first step, and the organic solvent prepared in the second step.
Method for producing a resin composition for an adhesive film.
제7항에 있어서,
상기 광잠재성 경화제는 광산발생제(PAG), 광염발생제(PBG) 중 어느 하나 이상인,
접착필름용 수지 조성물의 제조방법.
The method of claim 7, wherein
The photo latent curing agent is any one or more of a photo-acid generator (PAG), photo-acid generator (PBG),
Method for producing a resin composition for an adhesive film.
제7항 또는 제8항 중 어느 한항에 있어서,
상기 제3단계에서 제조된 접착필름용 수지 조성물은 전기적 특성 향상을 위해 금속 분말 또는 금속이 코팅된 폴리머볼의 도전성 입자를 더 포함하는,
접착필름용 수지 조성물의 제조방법.
The method according to any one of claims 7 to 8,
The resin composition for an adhesive film prepared in the third step further comprises conductive particles of a metal powder or a metal coated polymer ball to improve electrical properties,
Method for producing a resin composition for an adhesive film.
제7항 또는 제8항 중 어느 한항에 있어서,
상기 제3단계에서 제조된 접착필름용 수지 조성물은 물리적 특성 향상을 위해 실리카 필러의 첨가제를 더 포함하는,
접착필름용 수지 조성물의 제조방법.
The method according to any one of claims 7 to 8,
The resin composition for the adhesive film prepared in the third step further comprises an additive of the silica filler to improve physical properties,
Method for producing a resin composition for an adhesive film.
열가소성 수지, 열경화성 수지 및 광잠재성 경화제를 포함하는,
접착필름.
Comprising a thermoplastic resin, a thermosetting resin and a latent curing agent,
Adhesive film.
제11항에 있어서,
상기 열가소성 수지 5~60 중량%, 상기 열경화성 수지 25~94.9 중량% 및 상기 광잠재성 경화제 0.1~30 중량로 이루어지는,
접착필름.
The method of claim 11,
5 to 60% by weight of the thermoplastic resin, 25 to 99.4% by weight of the thermosetting resin, and 0.1 to 30% by weight of the latent curing agent,
Adhesive film.
제11항 또는 제12항 중 어느 한항에 있어서,
상기 광잠재성 경화제는 광산발생제(PAG; photo acid generator), 광염발생제(PBG, photo base generator) 중 어느 하나 이상인,
접착필름.
The method according to any one of claims 11 to 12,
The photo latent curing agent is any one or more of a photo acid generator (PAG), a photo base generator (PBG),
Adhesive film.
제11항 또는 제12항 중 어느 한항에 있어서,
상기 접착필름은 전기적 특성 향상을 위해 금속 분말 또는 금속이 코팅된 폴리머볼의 도전성 입자를 더 포함하는,
접착필름.
The method according to any one of claims 11 to 12,
The adhesive film further comprises conductive particles of a metal powder or a metal-coated polymer ball to improve electrical properties,
Adhesive film.
제11항 또는 제12항 중 어느 한항에 있어서,
상기 접착필름은 물리적 특성 향상을 위해 실리카 필러의 첨가제를 더 포함하는,
접착필름.
The method according to any one of claims 11 to 12,
The adhesive film further comprises an additive of a silica filler to improve physical properties,
Adhesive film.
제11항 또는 제12항 중 어느 한항에 있어서,
상기 접착필름은 120 ℃이하에서 20초 이하에 경화반응이 완료되는,
접착필름.
The method according to any one of claims 11 to 12,
The adhesive film is the curing reaction is completed in 20 seconds or less at 120 ℃ or less,
Adhesive film.
열가소성 수지 5~60 중량%, 열경화성 수지 25~94.9 중량%, 및 광잠재성 경화제 0.1~30 중량% 조성을 준비하는 제1단계;
상기 열가소성 수지, 상기 열경화성 수지와 상기 광잠재성 경화제, 전체 중량의 40~250 중량%의 유기용매를 준비하는 제2단계;
상기 제1단계에서 준비한 상기 열가소성 수지, 열경화성 수지 및 광잠재성 경화제와 상기 제2단계에서 준비한 상기 유기용매를 혼합 및 용해시켜 접착필름용 수지 조성물을 제조하는 제3단계; 및
상기 접착필름용 수지 조성물을 이형지 또는 웨이퍼 위에 도포 및 건조하여 접착필름을 제조하는 제4단계;를 포함하는,
접착필름의 제조방법.
A first step of preparing a composition of 5 to 60 wt% of a thermoplastic resin, 25 to 99.4 wt% of a thermosetting resin, and 0.1 to 30 wt% of a latent curing agent;
A second step of preparing the thermoplastic resin, the thermosetting resin, the optical latent curing agent, and an organic solvent having a total weight of 40 to 250 wt%;
A third step of preparing a resin composition for an adhesive film by mixing and dissolving the thermoplastic resin, the thermosetting resin and the photo latent curing agent prepared in the first step, and the organic solvent prepared in the second step; And
A fourth step of manufacturing an adhesive film by applying and drying the resin composition for the adhesive film on a release paper or a wafer; comprising,
Method of producing an adhesive film.
제17항에 있어서,
상기 제4단계에서 건조처리시 상기 접착필름용 내의 유기용매가 휘발되어 상기 접착필름은 상기 열가소성 수지, 열경화성 수지 및 광잠재성 경화제로 이루어지는,
접착필름의 제조방법.
18. The method of claim 17,
In the fourth step, the organic solvent in the adhesive film is volatilized during the drying process, and the adhesive film is made of the thermoplastic resin, the thermosetting resin, and the optical latent curing agent.
Method of producing an adhesive film.
제17항에 있어서,
상기 제4단계에서 도포 및 건조처리는 옐로우 룸(yellow room)에서 이루어지는,
접착필름의 제조방법.
18. The method of claim 17,
In the fourth step, the coating and drying process is performed in a yellow room,
Method of producing an adhesive film.
제17항 내지 제19항 중 어느 한항에 있어서,
상기 광잠재성 경화제는 광산발생제(PAG), 광염발생제(PBG) 중 어느 하나 이상인,
접착필름의 제조방법.
The method according to any one of claims 17 to 19,
The photo latent curing agent is any one or more of a photo-acid generator (PAG), photo-acid generator (PBG),
Method of producing an adhesive film.
제17항 내지 제19항 중 어느 한항에 있어서,
상기 제4단계에서 제조된 접착필름은 전기적 특성 향상을 위해 금속 분말 또는 금속이 코팅된 폴리머볼의 도전성 입자를 더 포함하는,
접착필름의 제조방법
The method according to any one of claims 17 to 19,
The adhesive film prepared in the fourth step further includes conductive particles of a metal powder or a metal coated polymer ball to improve electrical properties,
Manufacturing method of adhesive film
제17항 내지 제19항 중 어느 한항에 있어서,
상기 제4단계에서 제조된 접착필름은 물리적 특성 향상을 위해 실리카 필러의 첨가제를 더 포함하는,
접착필름의 제조방법The method according to any one of claims 17 to 19,
The adhesive film prepared in the fourth step further comprises an additive of the silica filler to improve physical properties,
Manufacturing method of adhesive film
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JP3651624B2 (en) * 1995-11-21 2005-05-25 日立化成工業株式会社 Circuit connection member
KR100934553B1 (en) * 2007-11-16 2009-12-29 제일모직주식회사 Method for producing an anisotropic conductive film and an anisotropic conductive film produced thereby
KR100891414B1 (en) * 2007-11-20 2009-04-02 제일모직주식회사 Anisotropic conductive film composition for high storage stability
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KR20210108769A (en) * 2020-02-26 2021-09-03 한국과학기술원 Anisotropic conductive adhesives with solder conductive particles and flux additives for a thermo-compression bonding and electrical interconnection method of electrical component using the same
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US11791302B2 (en) 2020-10-26 2023-10-17 Nitto Denko Corporation Thermosetting sheet, dicing die bonding film, and semiconductor apparatus

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