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WO2015057012A1 - Anisotropic conductive film composition harmless to human body, anisotropic conductive film, and semiconductor device connected by film - Google Patents

Anisotropic conductive film composition harmless to human body, anisotropic conductive film, and semiconductor device connected by film Download PDF

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Publication number
WO2015057012A1
WO2015057012A1 PCT/KR2014/009783 KR2014009783W WO2015057012A1 WO 2015057012 A1 WO2015057012 A1 WO 2015057012A1 KR 2014009783 W KR2014009783 W KR 2014009783W WO 2015057012 A1 WO2015057012 A1 WO 2015057012A1
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WO
WIPO (PCT)
Prior art keywords
acrylate
meth
anisotropic conductive
conductive film
resin
Prior art date
Application number
PCT/KR2014/009783
Other languages
French (fr)
Korean (ko)
Inventor
고연조
강경구
김규봉
김이주
Original Assignee
삼성에스디아이 주식회사
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Application filed by 삼성에스디아이 주식회사 filed Critical 삼성에스디아이 주식회사
Priority to CN201480054014.XA priority Critical patent/CN105593945B/en
Publication of WO2015057012A1 publication Critical patent/WO2015057012A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
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    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
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    • H01L2224/294—Coating material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29438—Coating material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/29447—Copper [Cu] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
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    • H01L2224/294—Coating material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
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Definitions

  • the semiconductor device connected by the film formed from the said composition for anisotropic conductive films or the said anisotropic conductive film is provided.
  • Hansen solubility parameters of the representative solvents are shown in Table 1 below, and methyl ethyl ketone or toluene has been commonly used in the composition for the double anisotropic conductive film because of its high volatility and high solubility.
  • the anisotropic conductive film according to another embodiment of the present invention, the binder portion, the curing portion, the curing agent and the conductive particles, the trace amount of the solvent (s) harmless to the human body having a Hansen Solubility Parameter of 17 to 20 It may include.
  • the boiling point of the solvent may be 70 to 130 °C.
  • the solvent may include a first solvent having a Hansen solubility parameter of 17 to 20 and a boiling point of 70 to 100 ° C., and a second solvent having a Hansen solubility parameter of 17 to 20 and a boiling point of more than 100 to 130 ° C. or less. .
  • the hardened part may include an epoxy hardened part.
  • the epoxy cured part include a hydrogenated bisphenol resin, a phenol epoxy resin, a naphthalene epoxy resin, a novolac epoxy resin, and a bisphenol epoxy resin.
  • Example 3 In the same manner as in Example 1 except that 10% by weight of NBR resin (N-34, Nipon Xeon) was dissolved in toluene / methyl ethyl ketone (ratio 1: 1 (weight ratio)) in Example 1 It carried out to manufacture the composition of Comparative Example 3.
  • NBR resin N-34, Nipon Xeon
  • Example 1 Except for using 2.5% by weight of benzoyl peroxide instead of lauryl peroxide as a curing agent in Example 1 was prepared in the same manner as in Example 1 to prepare a composition for anisotropic conductive film of Comparative Example 4.

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Abstract

The present invention relates to: an anisotropic conductive film composition comprising a binder part, a hardening part, a hardening agent, conductive particles, and a solvent having Hansen solubility parameters of 17 to 20; an anisotropic conductive film; and a semiconductor device connected by the film.

Description

인체에 무해한 이방 도전성 필름용 조성물, 이방 도전성 필름, 및 상기 필름에 의해 접속된 반도체 장치 The semiconductor device connected by the composition for anisotropic conductive films, anisotropic conductive film, and the said film which are harmless to a human body
본 발명은 인체에 무해한 이방 도전성 필름용 조성물, 이방 도전성 필름, 및 상기 필름에 의해 접속된 반도체 장치에 관한 것이다. The present invention relates to a composition for an anisotropic conductive film that is harmless to a human body, an anisotropic conductive film, and a semiconductor device connected by the film.
이방 도전성 필름(Anisotropic Conductive Film, ACF)은 금속 코팅된 플라스틱 또는 금속 입자 등의 도전성 입자를 분산시킨 필름상의 접착제로서 평판 디스플레이 분야의 회로 접속, 반도체 분야의 부품 실장 등에 널리 사용되고 있다. 상기 이방 도전성 필름을 접속시키고자 하는 회로 사이에 위치시킨 후 일정 조건의 열 압착 공정을 거치면, 회로 단자들 사이는 도전성 입자에 의해 전기적으로 접속되고, 인접 회로 단자간 스페이스(space)에는 절연성 접착 수지가 충진되어 도전성 입자가 서로 독립하여 존재하기 때문에 절연성을 부여하게 된다.Anisotropic conductive film (ACF) is a film-like adhesive in which conductive particles such as metal-coated plastic or metal particles are dispersed, and is widely used for circuit connection in flat panel display field and component mounting in semiconductor field. When the anisotropic conductive film is placed between the circuits to be connected and subjected to a thermocompression process under a predetermined condition, the circuit terminals are electrically connected by conductive particles, and an insulating adhesive resin is formed in the space between adjacent circuit terminals. Is filled to impart insulation because the conductive particles are present independently of one another.
이러한 이방 도전성 접착 필름은 다양한 종류의 용매에 녹아 있는 고분자 바인더에 모노머, 첨가제, 경화제경화제, 도전성 입자 등을 섞고 이를 필름상으로 코팅 후 열로 용매를 휘발시켜 제조하는 것이 일반적이다. 경화제로 경화제 등을 사용하는 경화 시스템에서, 필름상 코팅 후 열에 의해 신속히 휘발되면서 고분자 바인더 등에 용해도가 높은 톨루엔과 메틸에틸케톤 등이 범용적으로 사용되고 있다(대한민국 특허 출원 공개번호 제10-2013-0068891호 및 대한민국 특허 출원 공개번호 제10-2012-0076185호). 그런데, 상기 톨루엔 및 메틸에틸케톤 등은 인체에 노출 시 생식독성을 야기하는 것으로 알려져 있다. 위와 같이 이방 도전성 필름의 제조에 유독성인 용매가 사용되고 있기 때문에 이방 도전성 필름 상에 인체에 유해한 휘발성 용매가 잔존할 수 밖에 없으며 이러한 휘발성 용매는 본딩 공정 중 필름이 열을 받게 됨에 따라 휘발되어 장기간 노출 시 작업자의 건강에 해를 끼칠 수 있다. 이를 최소화하기 위해서는 코팅 후 열로 용매를 휘발시키는 건조 공정에서 최대한 높은 열로 오랜 시간 동안 건조시키는 방법도 있으나 이 경우에도 필름의 표면이 먼저 건조되어 내부의 용매가 충분히 빠져 나오기 어렵고 온도를 올릴 경우 필름이 건조 공정 중 일부가 경화 반응이 진행되어 본래의 물성을 유지하지 못하는 경우가 발생한다. Such an anisotropic conductive adhesive film is generally prepared by mixing a monomer, an additive, a curing agent, conductive particles, and the like into a polymer binder dissolved in various kinds of solvents, and coating the film on a film to volatilize the solvent with heat. In a curing system using a curing agent or the like as a curing agent, toluene and methyl ethyl ketone having high solubility in polymer binders and the like are rapidly used by heat after coating on a film, and are commonly used. (Korean Patent Application Publication No. 10-2013-0068891 And Korean Patent Application Publication No. 10-2012-0076185. However, toluene and methyl ethyl ketone are known to cause reproductive toxicity upon exposure to humans. As toxic solvents are used in the manufacture of the anisotropic conductive film as described above, volatile solvents harmful to the human body remain on the anisotropic conductive film, and these volatile solvents are volatilized as the film receives heat during the bonding process, and thus, when exposed for a long time, It can harm worker's health. In order to minimize this, there is a method of drying for a long time with the highest heat in the drying process in which the solvent is volatilized by heat after coating, but even in this case, the surface of the film is dried first, so that the solvent inside it is hard to come out sufficiently, In some of the processes, the curing reaction proceeds to maintain the original properties.
최근 환경 및 작업자의 건강에 대한 문제가 점점 사회문제로 이슈화되고 있으며 인체유해물질이 함유된 제품을 사용함으로 인해 작업자의 건강에 해가 되는 상황이 발생시 기업의 존폐와도 직결되는 심각한 상황이 발생할 수 있다. 따라서, 인체 유해물질이 함유되지 않는 제품에 대한 필요성은 날이 갈수록 커지고 있으나 기존의 이방 도전성 필름에서 이러한 유해물질을 제거하려는 노력은 없었으며 오히려 제품의 물성 향상을 위해 유해물질을 더욱 많이 첨가하는 경향이 있어 이를 해결하기 위한 방법이 시급하다.Recently, environmental and worker's health issues are becoming more and more social issues, and serious problems that can directly affect the company's existence can occur when a situation in which workers' health is harmed by using products containing harmful substances. have. Therefore, the necessity for products containing no human harmful substances is increasing day by day, but no efforts have been made to remove these harmful substances from existing anisotropic conductive films, but rather, more harmful substances are added to improve product properties. There is an urgent way to solve this problem.
본 발명은 인체에 무해한 이방 도전성 필름용 조성물 및 필름을 제공하고자 한다. 구체적으로, 인체에 노출되더라도 발암성, 간독성, 직업병, 생식독성 또는 건강을 손상시키지 않는 친환경적인 이방 도전성 필름용 조성물 및 필름을 제공하고자 한다. The present invention is to provide a composition and film for an anisotropic conductive film harmless to the human body. Specifically, to provide an environment-friendly composition for anisotropic conductive films and films that do not impair carcinogenicity, hepatotoxicity, occupational diseases, reproductive toxicity or health even when exposed to the human body.
본 발명은 또한 인체에 무해하면서도 접속 신뢰성 및 접착력이 양호하여 이방 도전성 접착제로서의 본연의 물성을 유지하는 이방 도전성 필름용 조성물 및 필름을 제공하는 것을 해결 과제로 한다.It is another object of the present invention to provide a composition and film for anisotropic conductive films that are harmless to human bodies and have good connection reliability and adhesion, and thus maintain their physical properties as an anisotropic conductive adhesive.
본 발명의 일 예에 따르면, 바인더부, 경화부, 경화제, 도전성 입자, 및 한센 용해도 파라미터(Hansen Solubility Parameter)가 17 내지 20인 용매를 포함하며, 단, 상기 용매가 톨루엔 혹은 메틸에틸케톤은 아닌, 이방 도전성 필름용 조성물이 제공된다.According to one embodiment of the present invention, a binder portion, a curing portion, a curing agent, conductive particles, and a Hansen Solubility Parameter (Hansen Solubility Parameter) of 17 to 20, wherein the solvent is not toluene or methyl ethyl ketone The composition for anisotropic conductive films is provided.
본 발명의 다른 일 예에 따르면, 바인더부, 경화부, 경화제 및 도전성 입자를 포함하고, 0 내지 1 ppm 이하의 메틸에틸케톤, 및 0 내지 10 ppm 이하의 톨루엔을 포함하는, 이방 도전성 필름이 제공된다. According to another embodiment of the present invention, there is provided an anisotropic conductive film comprising a binder portion, a curing portion, a curing agent and conductive particles, and containing 0 to 1 ppm or less methyl ethyl ketone, and 0 to 10 ppm or less toluene. do.
본 발명의 또 다른 일 예에 따르면, 상기 이방 도전성 필름용 조성물로부터 형성된 필름 혹은 상기 이방 도전성 필름에 의해 접속된 반도체 장치가 제공된다. According to another example of this invention, the semiconductor device connected by the film formed from the said composition for anisotropic conductive films or the said anisotropic conductive film is provided.
본 발명의 예들에 따른 이방 도전성 필름용 조성물 및 필름은 무해 용매를 사용함으로써 인체에 독성을 야기하지 않으며, 구체적으로 발암성, 간독성, 직업병, 생식독성 또는 건강 손상 등을 야기하지 않는다.Compositions and films for anisotropic conductive films according to examples of the present invention do not cause toxicity to the human body by using a harmless solvent, and specifically does not cause carcinogenicity, hepatotoxicity, occupational disease, reproductive toxicity or health damage.
또한, 인체에 무해하면서도 바인더부 및 경화제와의 조액 안정성 혹은 용해도가 양호한 용매를 사용함으로써 접착력 및 접속저항 등의 물성이 우수하다. In addition, by using a solvent that is harmless to the human body and has a good solution stability or solubility with the binder portion and the curing agent, it is excellent in physical properties such as adhesion and connection resistance.
도 1은 본 발명의 일 예에 따른 이방성 도전 필름으로 서로 접속된 제1 전극(70) 및 제2 전극(80)을 각각 포함하는 제1 피접속부재(50)와 제2 피접속부재(60)를 포함하는 반도체 장치(30)를 도시한다.1 is an anisotropic conductive film according to an embodiment of the present invention, the first to-be-connected member 50 and the second to-be-connected member 60 each including a first electrode 70 and a second electrode 80 connected to each other. 3 illustrates a semiconductor device 30 including a semiconductor device 30.
도 2는 이방 도전성 필름용 조성물이 시간 경과시 상 분리로 인해 도전입자의 뭉침 현상이 나타남을 보여주는 비교예 1의 이방 도전성 필름의 현미경 사진이다. FIG. 2 is a micrograph of the anisotropic conductive film of Comparative Example 1 showing that the composition for the anisotropic conductive film exhibits agglomeration of conductive particles due to phase separation over time.
도 3은 이방 도전성 필름용 조성물이 시간 경과시 상 분리되지 않아 도전입자가 균일하게 분산된 형태임을 보여주는 실시예 1의 이방 도전성 필름의 현미경 사진이다.Figure 3 is a micrograph of the anisotropic conductive film of Example 1 showing that the composition for the anisotropic conductive film is not phase separated over time, the conductive particles are uniformly dispersed.
본 발명의 일 예에 따른 이방 도전성 필름용 조성물은, 바인더부, 경화부, 경화제, 도전성 입자, 및 한센 용해도 파라미터(Hansen Solubility Parameter)가 17 내지 20인 용매를 포함하며, 단, 상기 용매가 톨루엔 혹은 메틸에틸케톤은 아닐 수 있다. 상기 이방 도전성 필름용 조성물에서 사용될 수 있는 용매로 메틸에틸케톤 혹은 톨루엔과 같이 인체에 유해한 성분은 제외된다. 따라서, 본 발명에서 사용될 수 있는 용매는 한센 용해도 파라미터(Hansen Solubility Parameter)가 17 내지 20이면서 인체에 무해한 용매이다. 상기 용매는 비점이 70 내지 130℃일 수 있다. 상기 용매는 예를 들어, 한센 용해도 파라미터 및/또는 비점이 상이한 용매를 2종 이상 사용할 수 있다. 이 경우, 용매는 한센 용해도 파라미터가 17 내지 20이면서 비점이 70℃ 내지 100℃인 제1 용매와 한센 용해도 파라미터가 17 내지 20이면서 비점이 100℃ 초과 내지 130℃인 제2 용매를 포함할 수 있다. 본원에서 한센 용해도 파라미터는 다음 식 1로 정의될 수 있다:The composition for an anisotropic conductive film according to an embodiment of the present invention includes a binder portion, a curing portion, a curing agent, conductive particles, and a solvent having a Hansen Solubility Parameter of 17 to 20, provided that the solvent is toluene Or methylethyl ketone. As a solvent that may be used in the composition for anisotropic conductive films, components harmful to human body such as methyl ethyl ketone or toluene are excluded. Therefore, the solvent that can be used in the present invention is a solvent that is harmless to the human body with a Hansen Solubility Parameter of 17 to 20. The solvent may have a boiling point of 70 to 130 ℃. The solvent may be, for example, two or more solvents having different Hansen solubility parameters and / or boiling points. In this case, the solvent may include a first solvent having a Hansen solubility parameter of 17 to 20 and a boiling point of 70 ° C. to 100 ° C., and a second solvent having a Hansen solubility parameter of 17 to 20 and a boiling point of more than 100 ° C. to 130 ° C. . The Hansen solubility parameter can be defined herein as Equation 1:
[식 1][Equation 1]
δ t 2=δ d 2+δ p 2+δ h 2 δ t 2 = δ d 2 + δ p 2 + δ h 2
상기 식 1에서, In Formula 1,
δ t가 한센 용해도 파라미터이고, δ d는 분자간의 분산 에너지이고, δ p는 분자간의 분자내 쌍극자 힘의 에너지이고, δ h는 분자간의 수소 결합 에너지를 나타낸다. δ t is the Hansen solubility parameter, δ d is the intermolecular dispersion energy, δ p is the energy of the intermolecular dipole force, and δ h is the hydrogen bonding energy between the molecules.
상기한 한센 용해도 파라미터 범위에서 바인더부, 혹은 라우릴 퍼옥시드 및 큐멘 히드로퍼옥시드와 같은 경화제와 조액안정성이 양호하고, 용해도가 높아 이방 도전성 필름의 접착성 및 접속 신뢰성이 유지될 수 있다. 한센 용해도 파라미터(Hansen Solubility Parameter)가 17 내지 20이면서 인체에 무해한 용매의 예로는 메틸 아세테이트, 에틸 아세테이트, 부틸 아세테이트와 같은 알킬아세테이트류, 이소프로필알코올, 이소부틸알코올과 같은 알코올류 등을 들 수 있다. 따라서, 메틸 아세테이트, 에틸 아세테이트, 부틸 아세테이트, 이소프로필알코올, 및 이소부틸알코올 중에서 선택된 1종 이상의 용매가 사용될 수 있다. 한센 용해도 파라미터가 17 내지 20인 용매를 2종 이상 사용하는 경우, 비점이 70℃ 내지 100℃인 제1 용매와 비점이 100℃ 초과 내지 130℃인 제2 용매를 함께 사용할 수 있다. 상기 제1 용매는 한센 용해도 파라미터가 17 내지 20이면서 비점이 70℃ 내지 100℃이고 인체에 무해한 용매라면 제한없이 사용할 수 있으나, 예를 들어, 에틸 아세테이트, 이소프로필아세테이트 등을 들 수 있다. 상기 제2 용매는 한센 용해도 파라미터(Hansen Solubility Parameter)가 17 내지 20이면서 비점이 100℃ 초과 내지 130℃이고 인체에 무해한 용매라면 제한없이 사용할 수 있으나, 예를 들어, 부틸 아세테이트, 이소프로알코올, 이소부틸알코올 등을 들 수 있다. 보다 구체적으로, 에틸 아세테이트 및 부틸 아세테이트 중 1종 이상을 사용할 수 있다. 경화제로 라디칼 반응 개시제를 사용하는 라디칼 반응 시스템 혹은 이온성 경화 시스템에서 범용적으로 사용되는 용매인 메틸에틸케톤 혹은 톨루엔 등은 각각 인체에 흡수되어 생식독성을 야기하므로 본 발명에서 사용될 수 있는 용매에서 제외된다.In the Hansen solubility parameter range, the binder portion, or a curing agent such as lauryl peroxide and cumene hydroperoxide and coarse liquid stability are good, and the solubility is high so that the adhesion and connection reliability of the anisotropic conductive film can be maintained. Examples of solvents that are harmless to the human body having a Hansen Solubility Parameter of 17 to 20 include alkyl acetates such as methyl acetate, ethyl acetate, and butyl acetate, alcohols such as isopropyl alcohol, and isobutyl alcohol, and the like. . Thus, one or more solvents selected from methyl acetate, ethyl acetate, butyl acetate, isopropyl alcohol, and isobutyl alcohol can be used. When two or more solvents having a Hansen solubility parameter of 17 to 20 are used, a first solvent having a boiling point of 70 ° C to 100 ° C and a second solvent having a boiling point of more than 100 ° C to 130 ° C can be used together. The first solvent may be used without limitation as long as the Hansen solubility parameter is 17 to 20 and the boiling point is 70 ° C. to 100 ° C. and is harmless to the human body. For example, ethyl acetate, isopropyl acetate, and the like may be used. The second solvent may be used without limitation as long as the Hansen Solubility Parameter is 17 to 20, a boiling point of more than 100 ° C to 130 ° C, and harmless to the human body. For example, butyl acetate, isoproalcohol, iso Butyl alcohol etc. are mentioned. More specifically, one or more of ethyl acetate and butyl acetate can be used. Methylethylketone or toluene, which are solvents commonly used in radical reaction systems or ionic curing systems that use radical reaction initiators as curing agents, are absorbed by the human body and cause reproductive toxicity, so they are excluded from solvents that can be used in the present invention. do.
대표적인 용매들의 한센 용해도 파라미터는 아래 표 1과 같으며, 이중 이방 도전성 필름용 조성물에는 통상 빠른 휘발성 및 높은 용해성으로 메틸에틸케톤 혹은 톨루엔 등이 통상 사용되어 오고 있다.Hansen solubility parameters of the representative solvents are shown in Table 1 below, and methyl ethyl ketone or toluene has been commonly used in the composition for the double anisotropic conductive film because of its high volatility and high solubility.
표 1
용매 δ/MPa1/2 용매 δ/MPa1/2
δ t δ d δ p δ h δ t δ d δ p δ h
n-부탄 14.1 14.1 0 0 아세톤 20 15.5 10.4 7
n-펜탄 14.5 14.5 0 0 메틸에틸케톤 19 16 9 5.1
n-헥산 14.9 14.9 0 0 메탄올 29.6 15.1 12.3 22.3
n-헵탄 15.3 15.3 0 0 에탄올 26.5 15.8 8.8 19.4
n-옥탄 15.5 15.5 0 0 알릴알코올 25.7 16.2 10.8 16.8
벤젠 18.6 18.4 0 2 1-프로판올 24.5 16 6.8 17.4
톨루엔 18.2 18 1.4 2 2-프로판올 23.5 15.8 6.1 16.4
나프탈렌 20.3 19.2 2 5.9 1-부탄올 23.1 16 5.7 15.8
스티렌 19 18.6 1 4.1 2-부탄올 22.2 15.8 5.7 14.5
o-자일렌 18 17.8 1 3.1 에틸 포름에이트 18.7 15.5 7.2 7.6
에틸벤젠 17.8 17.8 0.6 1.4 프로필렌1,2카보네이트 27.3 20 18 4.1
클로로메탄 17 15.3 6.1 3.9 디에틸카보네이트 17.9 16.6 3.1 6.1
메틸렌클로라이드 20.3 18.2 6.3 6.1 이소부틸아세테이트 16.8 15.1 3.7 6.3
1,1-디클로로에틸렌 18.8 17 6.8 4.5 클로로포름 19 17.8 3.1 5.7
에틸렌디클로라이드 20.9 19 7.4 4.1
Table 1
menstruum δ / MPa 1/2 menstruum δ / MPa 1/2
δ t δ d δ p δ h δ t δ d δ p δ h
n-butane 14.1 14.1 0 0 Acetone 20 15.5 10.4 7
n-pentane 14.5 14.5 0 0 Methyl ethyl ketone 19 16 9 5.1
n-hexane 14.9 14.9 0 0 Methanol 29.6 15.1 12.3 22.3
n-heptane 15.3 15.3 0 0 ethanol 26.5 15.8 8.8 19.4
n-octane 15.5 15.5 0 0 Allyl alcohol 25.7 16.2 10.8 16.8
benzene 18.6 18.4 0 2 1-propanol 24.5 16 6.8 17.4
toluene 18.2 18 1.4 2 2-propanol 23.5 15.8 6.1 16.4
naphthalene 20.3 19.2 2 5.9 1-butanol 23.1 16 5.7 15.8
Styrene 19 18.6 One 4.1 2-butanol 22.2 15.8 5.7 14.5
o-xylene 18 17.8 One 3.1 Ethyl formate 18.7 15.5 7.2 7.6
Ethylbenzene 17.8 17.8 0.6 1.4 Propylene 1,2 Carbonate 27.3 20 18 4.1
Chloromethane 17 15.3 6.1 3.9 Diethyl carbonate 17.9 16.6 3.1 6.1
Methylene chloride 20.3 18.2 6.3 6.1 Isobutyl Acetate 16.8 15.1 3.7 6.3
1,1-dichloroethylene 18.8 17 6.8 4.5 chloroform 19 17.8 3.1 5.7
Ethylenedichloride 20.9 19 7.4 4.1
상기 표 1의 용매 중 대다수가 인체에 흡수시 발암성, 간독성, 직업병, 생식독성 혹은 건강상 해를 끼치는 것으로 알려져 있다. 예를 들어, 벤젠, 포름알데히드, 클로로포름, 트리클로로에틸렌, 1,3-부타디엔, 카본테트라클로라이드 또는 에틸렌 옥사이드는 발암성 물질로 알려져 있다. 예를 들어, N,N-다이메틸포름알데히드(N,N-Dimethylformaldehyde)는 간독성 물질로 알려져 있다. 또한, N,N-다이메틸아세틸아세타마이드(N,N-Dimethylacethylacetamide), 노말헥산(n-Hexane) 등은 직업병 유발 독성 물질로, 2-메톡시에탄올(2-Methoxyethanol), 2-에톡시에탄올(2-Ethoxyethanol), 2-메톡시에틸 아세테이트(2-Methoxyethyl Acetate), 2-에톡시에틸 아세테이트(2-Ethoxyethyl Acetate), 비스(2-메톡시에틸)에테르 (Bis(2-methoxyethyl)Ether), 톨루엔(Toluene), o,m,p-자일렌(o,m,p-Xylene), 메틸에틸케톤(Methyl Ethyl Ketone) 등은 생식독성 물질로 알려져 있다(표 2 참조).Many of the solvents in Table 1 are known to cause carcinogenicity, hepatotoxicity, occupational diseases, reproductive toxicity or health hazards when absorbed into the human body. For example, benzene, formaldehyde, chloroform, trichloroethylene, 1,3-butadiene, carbon tetrachloride or ethylene oxide are known as carcinogenic substances. For example, N, N-dimethylformaldehyde is known as a hepatotoxic substance. In addition, N, N-dimethylacetylacetamide (N, N-Dimethylacethylacetamide) and normal hexane (n-Hexane) are toxic substances causing occupational diseases, and 2-methoxyethanol and 2-ethoxy 2-Ethoxyethanol, 2-Methoxyethyl Acetate, 2-Ethoxyethyl Acetate, Bis (2-methoxyethyl) Ether ), Toluene, toluene, o, m, p-xylene and methyl ethyl ketone are known as reproductive toxic substances (see Table 2).
표 2
유해물질 리스트
구분 물질명 영문명 CAS 번호 기준
1 벤젠 Benzene 71-43-2 발암성
2 포름알데히드 Formaldehyde 50-00-0 발암성
3 트리클로로에틸렌 Trichloroethylene(TCE) 79-01-6 발암성
4 1,3-부타디엔 1,3-Butadiene 106-99-0 발암성
5 카본 테트라클로라이드 Carbon tetrachloride 56-23-5 발암성
6 클로로포름 Chloroform 67-66-3 발암성
7 에틸렌 옥사이드 Ethylene Oxide 75-21-8 발암성
8 N,N-디메틸포름알데히드 N,N-Dimethylformaldehyde 68-12-2 간독성
9 N,N-디메틸아세트아마이드 N,N-Dimethylacetamide 127-19-5 직업병 유발
10 노말헥산 n-Hexane 110-54-3 직업병 유발
11 2-메톡시에탄올 2-Methoxyethanol 109-86-4 생식독성
12 2-에톡시에탄올 2-Ethoxyethanol 110-80-5 생식독성
13 2-메톡시아세테이트 2-methoxyacetate 110-49-6 생식독성
14 2-에톡시에틸 아세테이트 2-Ethoxyethyl Acetate 111-15-9 생식독성
15 비스(2-메톡시에틸)에테르 Bis(2-methoxyethyl)Ether 111-96-6 생식독성
16 톨루엔 Toluene 108-88-3 생식독성
17 o,m,p-자일렌 o,m,p-Xylene 1330-20-7 생식독성
18 메틸에틸케톤 MethylEthyl Ketone 78-93-3 생식독성
TABLE 2
Hazardous Substances List
division Substance English name CAS number standard
One benzene Benzene 71-43-2 Carcinogenic
2 Formaldehyde Formaldehyde 50-00-0 Carcinogenic
3 Trichloroethylene Trichloroethylene (TCE) 79-01-6 Carcinogenic
4 1,3-butadiene 1,3-Butadiene 106-99-0 Carcinogenic
5 Carbon tetrachloride Carbon tetrachloride 56-23-5 Carcinogenic
6 chloroform Chlororoform 67-66-3 Carcinogenic
7 Ethylene oxide Ethylene Oxide 75-21-8 Carcinogenic
8 N, N-dimethylformaldehyde N, N-Dimethylformaldehyde 68-12-2 Hepatotoxicity
9 N, N-dimethylacetamide N, N-Dimethylacetamide 127-19-5 Occupational disease
10 Normal hexane n-Hexane 110-54-3 Occupational disease
11 2-methoxyethanol 2-Methoxyethanol 109-86-4 Reproductive toxicity
12 2-ethoxyethanol 2-Ethoxyethanol 110-80-5 Reproductive toxicity
13 2-methoxyacetate 2-methoxyacetate 110-49-6 Reproductive toxicity
14 2-ethoxyethyl acetate 2-Ethoxyethyl Acetate 111-15-9 Reproductive toxicity
15 Bis (2-methoxyethyl) ether Bis (2-methoxyethyl) Ether 111-96-6 Reproductive toxicity
16 toluene Toluene 108-88-3 Reproductive toxicity
17 o, m, p-xylene o, m, p-Xylene 1330-20-7 Reproductive toxicity
18 Methyl ethyl ketone MethylEthyl Ketone 78-93-3 Reproductive toxicity
위와 같이 접착제에 사용되는 대부분의 용매들이 작업자의 건강에 해를 끼칠 수 있는 인체 유해물질이라는 것을 인식하고 있음에도 불구하고 이를 대체할만한 용매가 없어 계속 사용하고 있는 실정이다. Although it is recognized that most of the solvents used in the adhesive are harmful to the human body, which may harm the health of the worker, there is no solvent to replace them.
본 발명에서 이방 도전성 필름용 조성물에 사용될 수 있는 용매는 인체에 무해한 성분이어야 할 뿐 아니라, 바인더부 및 경화제 등과의 용해도 혹은 조액 안정성이 좋아야 한다. 본 발명에서 한센 용해도 파라미터(Hansen Solubility Parameter)가 17 내지 20인 용매를 사용하는 것은 바인더부 및 경화제 등과의 용해도 혹은 조액안정성 측면에서 유리하다. 또한, 한센 용해도 파라미터(Hansen Solubility Parameter)가 17 내지 20인 용매를 사용하는 것은 이방 도전성 필름의 접착성 및 접속 신뢰성 측면에서 유리하다.The solvent that can be used in the composition for anisotropic conductive films in the present invention should not only be a component harmless to the human body, but also have good solubility or solution stability with a binder portion and a curing agent. In the present invention, the use of a solvent having a Hansen Solubility Parameter of 17 to 20 is advantageous in terms of solubility or crude liquid stability with a binder part, a curing agent, and the like. In addition, it is advantageous to use a solvent having a Hansen Solubility Parameter of 17 to 20 in view of adhesion and connection reliability of the anisotropic conductive film.
구체적으로 본 발명의 일 양태는, 한센 용해도 파라미터(Hansen Solubility Parameter)가 17 내지 20이면서 비점이 70 내지 130℃인 용매를 사용할 수 있다. 용매의 비점이 70 내지 130℃이면 건조 공정에서 용매가 신속히 건조되어 제거되어 잔류 용매로 인한 필름 물성의 저하를 방지할 수 있다. Specifically, in one embodiment of the present invention, a solvent having a Hansen Solubility Parameter of 17 to 20 and a boiling point of 70 to 130 ° C may be used. When the boiling point of the solvent is 70 to 130 ° C., the solvent is quickly dried and removed in the drying process, thereby preventing deterioration of film properties due to the residual solvent.
본 발명의 또 다른 양태에서, 상기 용매는 1종 단독을 사용하거나 2종 이상의 용매를 시차를 두고 별개로 적용하여 사용하거나 이를 혼합하여 사용할 수 있다. 구체적으로 본 발명의 일 양태는, 한센 용해도 파라미터(Hansen Solubility Parameter)가 17 내지 20이면서 비점이 70 내지 100℃인 제1 용매와 한센 용해도 파라미터(Hansen Solubility Parameter)가 17 내지 20이면서 비점이 100 초과 내지 130℃이하인 제2 용매를 함께 사용할 수 있다. 비점이 상이한 2종 이상의 용매를 혼용하면 한 종류의 용매만을 사용한 경우에 비해 용매가 쉽게 휘발되는 것으로 인한 필름의 비평탄성이 개선될 수 있다. 한센 용해도 파라미터가 17 내지 20이면서 비점이 70 내지 100℃인 용매의 예로는 에틸 아세테이트, 이소프로필아세테이트 등을 들 수 있고, 한센 용해도 파라미터가 17 내지 20이면서 비점이 100 초과 내지 130℃이하인 용매의 예로는 부틸 아세테이트, 이소프로알코올, 이소부틸알코올 등을 들 수 있다. In another embodiment of the present invention, the solvent may be used alone, or two or more solvents may be used separately at staggered time or may be used in combination. Specifically, an aspect of the present invention provides a first solvent having a Hansen Solubility Parameter of 17 to 20 and a boiling point of 70 to 100 ° C., and a Hansen Solubility Parameter of 17 to 20 and having a boiling point of more than 100. It may be used together with a second solvent that is up to 130 ℃. The use of two or more solvents having different boiling points may improve the non-flatness of the film due to the volatilization of the solvent as compared to the case where only one type of solvent is used. Examples of the solvent having a Hansen solubility parameter of 17 to 20 and a boiling point of 70 to 100 ° C include ethyl acetate, isopropyl acetate, and the like. Examples of a solvent having a Hansen solubility parameter of 17 to 20 and a boiling point of more than 100 to 130 ° C or less. Butyl acetate, isoproalcohol, isobutyl alcohol, etc. are mentioned.
본 발명의 또 다른 일 예에 따르면, 바인더부, 경화부, 경화제 및 도전성 입자를 포함하는 인체에 무해한 이방 도전성 필름이 제공된다. 본원에서 '무해한'이란 용어가 사용되는 경우, 이는 장기간 인체에 노출시에, 발암성, 간독성, 직업병, 생식독성 또는 건강 상의 문제를 일으킴 없이 안전하게 사용될 수 있음을 의미한다. 구체적으로 '인체에 무해한'이란 용어가 사용된 경우, 이는 인체 유해물질이 필름 내 실질적으로 존재하지 않는 것을 의미할 수 있다. 보다 구체적으로 인체 유해물질의 함량이 0ppm이거나 10ppm 이하인 것을 의미한다. 보다 더 구체적으로 0ppm이거나 5ppm 이하, 또는 0 ppm이거나 1 ppm 이하인 것을 의미한다. 인체 유해 물질로는 예를 들어, 벤젠, 포름알데히드, 트리클로로에틸렌, 1,3-부타디엔, 카본 테트라크롤라이드, 클로로포름, 에틸렌 옥사이드, N,N-다이메틸포름알데히드, N,N-디메틸아세트아미드, 노말헥산, 2-메톡시에탄올, 2-에톡시에탄올, 2-메톡시아세테이트, 2-에톡시에틸 아세테이트, 비스(2-메톡시에틸)아테르, 톨루엔, ortho, meta, para-자일렌, 또는 메틸에틸케톤 등을 들 수 있다. According to another example of the present invention, an anisotropic conductive film harmless to a human body including a binder portion, a curing portion, a curing agent, and conductive particles is provided. When the term 'harmless' is used herein, it means that upon prolonged exposure to the human body it can be safely used without causing carcinogenicity, hepatotoxicity, occupational disease, reproductive toxicity or health problems. Specifically, when the term 'harmless to human body' is used, it may mean that the human harmful substance is substantially not present in the film. More specifically, it means that the content of human harmful substances is 0ppm or less than 10ppm. More specifically, it means 0 ppm or 5 ppm or less, or 0 ppm or 1 ppm or less. Human harmful substances include, for example, benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachromide, chloroform, ethylene oxide, N, N-dimethylformaldehyde, N, N-dimethylacetamide , Normal hexane, 2-methoxyethanol, 2-ethoxyethanol, 2-methoxyacetate, 2-ethoxyethyl acetate, bis (2-methoxyethyl) ether, toluene, ortho, meta, para-xylene, Or methyl ethyl ketone.
본 발명의 또 다른 일 예에 따른 이방 도전성 필름은, 바인더부, 경화부, 경화제 및 도전성 입자를 포함하고, 0 내지 1 ppm 이하의 메틸에틸케톤, 및 0 내지 10 ppm 이하의 톨루엔을 포함할 수 있다. 이방 도전성 필름의 제조에 메틸에틸케톤이나 톨루엔이 사용되는 경우, 상기 용매의 건조 공정을 거쳐 상당수의 용매를 휘발 제거하더라도 필름에 용매가 잔류하는 것을 피할 수 없다. 본 발명에서는 이방 도전성 필름의 제조 중 메틸에틸케톤이나 톨루엔을 용매로 전혀 사용하지 않기 때문에 필름 중 메틸에틸케톤이나 톨루엔이 실질적으로 존재하지 않는다. 따라서, 메틸에틸케톤이 0 내지 1 ppm 이하이고 톨루엔이 0 내지 10 ppm 이하인 것은 상기 성분들이 필름에서 실질적으로 검출되지 않음을 나타낸다. 구체적으로 상기 메틸에틸케톤은 0 내지 0.5 ppm 이하일 수 있고, 톨루엔은 0 내지 5ppm 이하일 수 있다. 보다 구체적으로 상기 메틸에틸케톤 및 톨루엔은 각각 0 ppm 혹은 검출기의 검출 한도 이하로 존재할 수 있으며, 이 경우 Not Detected, 또는 N.D.로 표시되어질 수 있다. 본원에서 톨루엔, 메틸에틸케톤, 벤젠 등과 같은 용매의 함량은 공지된 방법으로 측정할 수 있으나, 예를 들어, GC/MC를 사용해 EPA 5021, 8260에 기재된 방법으로 성분 분석을 하여 측정할 수 있다. 예를 들어, 이방 도전성 필름 조성물을 제조하고 이를 1시간 동안 25℃에서 교반하고, 상기 교반된 조성물을 이형 필름 위에 16㎛의 두께로 도포한 다음 70℃에서 15분 동안 건조시킨 후 용매의 함량을 측정할 수 있다.An anisotropic conductive film according to another embodiment of the present invention, including a binder portion, a curing portion, a curing agent and conductive particles, may include 0 to 1 ppm or less methyl ethyl ketone, and 0 to 10 ppm or less toluene. have. When methyl ethyl ketone or toluene is used in the production of the anisotropic conductive film, even if a large number of solvents are volatilized off through the drying step of the solvent, the solvent remains in the film. In the present invention, since methyl ethyl ketone or toluene is not used as a solvent during the production of the anisotropic conductive film, methyl ethyl ketone and toluene are substantially not present in the film. Thus, a methyl ethyl ketone of 0 to 1 ppm or less and toluene of 0 to 10 ppm or less indicates that the components are not substantially detected in the film. Specifically, the methyl ethyl ketone may be 0 to 0.5 ppm or less, and toluene may be 0 to 5 ppm or less. More specifically, the methyl ethyl ketone and toluene may be respectively present at 0 ppm or below the detection limit of the detector, in which case it may be expressed as Not Detected or N.D. The content of the solvent such as toluene, methyl ethyl ketone, benzene and the like can be measured by a known method, but can be measured, for example, by component analysis by the method described in EPA 5021, 8260 using GC / MC. For example, an anisotropic conductive film composition is prepared and stirred at 25 ° C. for 1 hour, the stirred composition is applied on a release film to a thickness of 16 μm, and then dried at 70 ° C. for 15 minutes to increase the solvent content. It can be measured.
상기 예의 이방 도전성 필름은 추가로 벤젠 함량이 0 내지 1 ppm 이하일 수 있다. 벤젠은 일반적으로 바인더부의 유기 용매로 사용되거나 상기 유기 용매의 구성 중 일부 포함되거나, 경화제인 벤조일 퍼옥사이드와 같은 벤젠 고리를 함유하는 라디칼 개시제의 분해로 생성되어 이방 도전성 필름 내 잔류하여 인체에 발암을 일으킬 수 있다. 이방 도전성 필름용 조성물에서 인체에 유해한 벤조일 퍼옥사이드와 같은 벤젠 고리를 함유하는 경화제 대신, 인체에 해가 없는 라우릴 퍼옥시드 또는 큐멘 히드로퍼옥시드와 같은 탄소수 7 내지 16의 포화 알킬기 함유 퍼옥시드 또는 사이클로헥산기 함유 퍼옥시드와 같은 경화제를 사용할 수 있다. 상기 라우릴 퍼옥시드 또는 큐멘 히드로퍼옥시드와 같은 경화제는 한센 용해도 파라미터(Hansen Solubility Parameter)가 17 내지 20인 용매와 조액안정성 혹은 용해도가 양호하여 이방 도전성 필름의 물성을 저하시키지 않을 수 있다. 구체적으로 본 발명의 일 예에 따른 이방 도전성 필름 중 벤젠은 N.D. 혹은 0 ppm일 수 있다.The anisotropic conductive film of the above example may further have a benzene content of 0 to 1 ppm or less. Benzene is generally used as an organic solvent in the binder portion or included in part of the composition of the organic solvent, or is produced by decomposition of a radical initiator containing a benzene ring such as benzoyl peroxide as a curing agent and remains in the anisotropic conductive film to cause carcinogenesis to the human body. Can cause. Instead of a curing agent containing a benzene ring, such as benzoyl peroxide, which is harmful to humans in the composition for anisotropic conductive films, peroxides or cyclones containing 7 to 16 carbon atoms, such as lauryl peroxide or cumene hydroperoxide, which are harmless to the human body. A curing agent such as hexane group-containing peroxide can be used. The curing agent such as lauryl peroxide or cumene hydroperoxide may have a solvent having a Hansen Solubility Parameter of 17 to 20 and a crude liquid stability or solubility, thereby not deteriorating physical properties of the anisotropic conductive film. Specifically, benzene in the anisotropic conductive film according to an embodiment of the present invention is N.D. Or 0 ppm.
본 발명의 또 다른 일 예에 따른 이방 도전성 필름은, 바인더부, 경화부, 경화제 및 도전성 입자를 포함하고, 한센 용해도 파라미터(Hansen Solubility Parameter)가 17 내지 20인 인체에 무해한 용매(들)을 미량 포함할 수 있다. 상기 용매의 비점은 70 내지 130℃일 수 있다. 상기 용매는 일 양태에서, 한센 용해도 파라미터가 17 내지 20이고 비점이 70 내지 100℃인 제1 용매와 한센 용해도 파라미터가 17 내지 20이면서 비점이 100 초과 내지 130℃이하인 제2 용매를 포함할 수 있다. 상기 용매(들)는 이방 도전성 필름에 10 ppm 초과의 양으로, 구체적으로 100 ppm 초과 내지 900 ppm의 양으로 잔류할 수 있다. 인체에 무해한 용매의 예로는 메틸 아세테이트, 에틸 아세테이트, 부틸 아세테이트와 같은 알킬아세테이트류, 이소프로필알코올, 이소부틸알코올과 같은 알코올류 등을 들 수 있다. 따라서, 메틸 아세테이트, 에틸 아세테이트, 부틸 아세테이트, 이소프로필알코올, 및 이소부틸알코올 중에서 선택된 1종 이상의 용매가 사용될 수 있다. 구체적으로, 에틸 아세테이트 및 부틸 아세테이트 중 1종 이상을 사용할 수 있다. 상기 경화제는 라우릴 퍼옥시드 및 큐멘 히드로퍼옥시드 중 1종 이상이 선택될 수 있다.The anisotropic conductive film according to another embodiment of the present invention, the binder portion, the curing portion, the curing agent and the conductive particles, the trace amount of the solvent (s) harmless to the human body having a Hansen Solubility Parameter of 17 to 20 It may include. The boiling point of the solvent may be 70 to 130 ℃. In one aspect, the solvent may include a first solvent having a Hansen solubility parameter of 17 to 20 and a boiling point of 70 to 100 ° C., and a second solvent having a Hansen solubility parameter of 17 to 20 and a boiling point of more than 100 to 130 ° C. or less. . The solvent (s) may remain in the anisotropic conductive film in an amount greater than 10 ppm, specifically in an amount greater than 100 ppm to 900 ppm. Examples of solvents harmless to the human body include methyl acetate, ethyl acetate, alkyl acetates such as butyl acetate, alcohols such as isopropyl alcohol and isobutyl alcohol, and the like. Thus, one or more solvents selected from methyl acetate, ethyl acetate, butyl acetate, isopropyl alcohol, and isobutyl alcohol can be used. Specifically, one or more of ethyl acetate and butyl acetate can be used. The curing agent may be selected from one or more of lauryl peroxide and cumene hydroperoxide.
본 발명의 또 다른 일 예에 따른 이방 도전성 필름은, 이를 제1 피접속부재와 제2 피접속부재 사이에 위치시키고, 70℃, 1초간, 1.0MPa의 조건에서 가압착 및 150℃, 4초간, 4.0MPa 조건에서 본압착시의 접착력이 700 gf/cm 이상, 구체적으로 800 gf/cm 이상일 수 있다. 또한, 발명의 또 다른 일 예에 따른 이방 도전성 필름은, 이를 상기 접착력 측정 방법에 기재된 가압착 및 본압착 조건으로 제1 피접속부재와 제2 피접속부재 사이에 접속시키고, 상기 접속된 필름을 85℃ 및 85상대습도%의 고온 고습 챔버에서 500 시간 보관시 신뢰성 평가 후 접착력이 500gf/cm 이상, 구체적으로 600gf/cm 이상일 수 있다.In the anisotropic conductive film according to another embodiment of the present invention, it is placed between the first to be connected and the second to-be-connected member, and press-bonded at 150 ° C. for 4 seconds at 70 ° C. for 1 second and 1.0 MPa. , The adhesive force at the time of the main compression under 4.0 MPa conditions may be 700 gf / cm or more, specifically 800 gf / cm or more. In addition, in the anisotropic conductive film according to another embodiment of the invention, it is connected between the first to-be-connected member and the second to-be-connected member under the pressure bonding and the main crimping conditions described in the method for measuring the adhesive force, and the connected film After storage for 500 hours in a high temperature and high humidity chamber at 85 ° C. and 85% relative humidity%, the adhesive strength may be 500 gf / cm or more, specifically 600 gf / cm or more.
본 발명의 또 다른 일 예에 따른 이방 도전성 필름은, 이를 제1 피접속부재와 제2 피접속부재 사이에 위치시키고, 70℃, 1초간, 1.0MPa의 조건에서 가압착 및 150℃, 4초간, 4.0MPa 조건에서 본압착한 후의 접속 저항이 0.6 Ω 이하이고, 상기 접속된 필름을 85℃ 및 85상대습도%의 고온 고습 챔버에서 500 시간 보관후 신뢰성 평가 후 접속저항이 3 Ω 이하일 수 있다.In the anisotropic conductive film according to another embodiment of the present invention, it is placed between the first to be connected and the second to-be-connected member, and press-bonded at 150 ° C. for 4 seconds at 70 ° C. for 1 second and 1.0 MPa. , The connection resistance after the main compression under the conditions of 4.0MPa is 0.6 kPa or less, the connected film may be 3 kPa or less after reliability evaluation after storing the connected film in a high temperature and high humidity chamber of 85 ℃ and 85% relative humidity%.
본 발명의 또 다른 일 예는 본원에 개시된 이방 도전성 필름용 조성물로부터 형성된 이방 도전성 필름 혹은 본원에 개시된 이방 도전성 필름에 의해 접속된 반도체 장치를 제공한다. 상기 반도체 장치는, 제1 전극을 함유하는 제1 피접속부재; 제2 전극을 함유하는 제2 피접속부재; 상기 제1 피접속부재와 상기 제2 피접속부재 사이에 위치하여 상기 제1 전극 및 상기 제2 전극을 접속시키는 본 발명에 따른 이방 도전성 필름을 포함한다. 도 1을 참조하면, 상기 반도체 장치는 이방성 도전 필름으로 서로 접속된 제1 전극(70) 및 제2 전극(80)을 각각 포함하는 제1 피접속부재(50)와 제2 피접속부재(60)를 포함한다. 제1 전극(70)이 형성된 제1 피접속부재(50)와 제2 전극(80)이 형성된 제2 피접속부재(60) 사이에 이방 도전성 필름을 위치시키고 압착시키면 제1 전극(70)와 제2 전극(80)이 도전 입자(3)를 통해 서로 접속된다. Another example of the present invention provides a semiconductor device connected by an anisotropic conductive film formed from the composition for an anisotropic conductive film disclosed herein or an anisotropic conductive film disclosed herein. The semiconductor device includes a first to-be-connected member containing a first electrode; A second to-be-connected member containing a second electrode; An anisotropic conductive film according to the present invention positioned between the first to-be-connected member and the second to-be-connected member to connect the first electrode and the second electrode. Referring to FIG. 1, the semiconductor device includes a first connected member 50 and a second connected member 60 each including a first electrode 70 and a second electrode 80 connected to each other by an anisotropic conductive film. ). When the anisotropic conductive film is positioned between the first to-be-connected member 50 on which the first electrode 70 is formed and the second to-be-connected member 60 on which the second electrode 80 is formed and pressed, the first electrode 70 and The second electrode 80 is connected to each other via the conductive particles 3.
이하 본 발명에 제시된 용매와 함께 사용될 수 있는 이방 도전성 필름의 조성물의 각 성분의 예에 대해 상술하나, 이는 단지 예시로써 제공되는 것이며, 발명이 이에 제한되는 것은 아니다.Hereinafter, examples of the respective components of the composition of the anisotropic conductive film that can be used with the solvents presented in the present invention are described above, but these are provided by way of example only, and the invention is not limited thereto.
바인더부Binder section
본 발명의 이방 도전성 필름용 조성물은 필름의 매트릭스 역할을 하는 바인더부를 포함할 수 있다. 상기 바인더부의 예로는 아크릴계, 우레탄 아크릴레이트계, 아크릴로니트릴계, 스티렌-아크릴로니트릴계, 부타디엔계, 폴리아미드계, 올레핀계, 페녹시 수지, 우레탄계 및 실리콘계 수지로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있다. 예를 들어, 바인더부는 아크릴계 수지 및 우레탄 아크릴레이트계 수지로 이루어진 군으로부터 선택될 수 있다. 예를 들어, 바인더부는 아크릴계 수지; 및 NBR(nitrile butadiene rubber)계 수지 및 우레탄계 수지로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있다.The composition for anisotropic conductive films of the present invention may include a binder portion that serves as a matrix of the film. Examples of the binder portion include one selected from the group consisting of acrylic, urethane acrylate, acrylonitrile, styrene-acrylonitrile, butadiene, polyamide, olefin, phenoxy resins, urethane and silicone resins. It may contain the above. For example, the binder portion may be selected from the group consisting of acrylic resins and urethane acrylate resins. For example, the binder portion may be acrylic resin; And NBR (nitrile butadiene rubber) resin and urethane resin.
바인더부는 이방 도전성 필름용 조성물 중 고형분 기준으로 40- 80 중량%로 포함될 수 있다. 상기 범위 내에서, 필름 형성이 잘 이루어질 수 있다. The binder part may be included in an amount of 40 to 80 wt% based on solids in the composition for an anisotropic conductive film. Within this range, film formation can be achieved well.
경화부Curing Part
본 발명의 이방 도전성 필름용 조성물은 경화부를 포함할 수 있다. 상기 경화부의 예로 라디칼 반응성 아크릴계 경화부를 포함할 수 있다. 상기 아크릴계 경화부의 예로 우레탄 (메타)아크릴레이트 및 (메타)아크릴레이트 단량체를 들 수 있다. 우레탄 (메타)아크릴레이트는 우레탄 결합 및 양 말단에 이중 결합을 포함한다. 우레탄 (메타)아크릴레이트 제조를 위한 중합 반응은 특별히 제한되지 않는다. (메타)아크릴레이트 단량체는 특별히 제한되지는 않지만, 1,6-헥산디올 모노(메타)아크릴레이트, 2-히드록시에틸 (메타)아크릴레이트, 2-히드록시프로필 (메타)아크릴레이트, 2-히드록시부틸 (메타)아크릴레이트, 2-히드록시-3-페닐옥시프로필 (메타)아크릴레이트, 1,4-부탄디올 (메타)아크릴레이트, 2-히드록시에틸 (메타)아크릴로일 포스페이트, 4-히드록시부틸(메타)아크릴레이트, 4-히드록시사이클로헥실 (메타)아크릴레이트, 네오펜틸글리콜 모노(메타)아크릴레이트, 트리메틸올에탄 디(메타)아크릴레이트, 트리메틸올프로판 디(메타)아크릴레이트, 펜타에리스리톨 트리(메타)아크릴레이트, 디펜타에리스리톨 펜타(메타)아크릴레이트, 펜타에리스리톨 헥사(메타)아크릴레이트, 디펜타에리스리톨 헥사(메타)아크릴레이트, 글리세린 디(메타)아크릴레이트, 히드로퍼퓨릴 (메타)아크릴레이트, 이소데실 (메타)아크릴레이트, 2-(2-에톡시에톡시)에틸 (메타)아크릴레이트, 스테아릴 (메타)아크릴레이트, 라우릴 (메타)아크릴레이트, 2-페녹시에틸 (메타)아크릴레이트, 이소보닐 (메타)아크릴레이트, 트리데실 (메타)아크릴레이트, 에톡시 부가형 노닐페놀 (메타)아크릴레이트, 에틸렌글리콜 디(메타)아크릴레이트, 트리에틸렌글리콜 디(메타)아크릴레이트, 테트라에틸렌글리콜 디(메타)아크릴레이트, 폴리에틸렌글리콜 디(메타)아크릴레이트, 1,3-부틸렌글리콜 디(메타)아크릴레이트, 트리프로필렌글리콜 디(메타)아크릴레이트, 에톡시 부가형 비스페놀-A 디(메타)아크릴레이트, 시클로헥산디메탄올 디(메타)아크릴레이트, 페녹시-t-글리콜 (메타)아크릴레이트, 2-메타아크릴로일록시메틸 포스페이트, 2-메타아크릴로일록시에틸 포스페이트, 디메틸올 트리시클로데케인 디(메타)아크릴레이트, 트리메틸올 프로판 벤조에이트 아크릴레이트 및 이들의 혼합물로 이루어진 군으로부터 선택되는 1종 이상이 될 수 있지만, 이들에 제한되는 것은 아니다.The composition for anisotropic conductive films of this invention can contain a hardening part. Examples of the hardening part may include a radical reactive acrylic hardening part. As an example of the said acryl-type hardening part, a urethane (meth) acrylate and a (meth) acrylate monomer are mentioned. Urethane (meth) acrylates include urethane bonds and double bonds at both ends. The polymerization reaction for producing urethane (meth) acrylate is not particularly limited. The (meth) acrylate monomer is not particularly limited, but is 1,6-hexanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol (meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, 4 -Hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentylglycol mono (meth) acrylate, trimethylolethane di (meth) acrylate, trimethylolpropane di (meth) acrylic Pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin di (meth) acrylate, Hydroperfuryl (meth) acrylate, isodecyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tridecyl (meth) acrylate, ethoxy addition nonylphenol (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, Ethoxy addition type bisphenol-A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, phenoxy-t-glycol (meth) acrylate, 2-methacryloyloxymethyl phosphate, 2-methacryl Loyle It may be, but is not limited to, one or more selected from the group consisting of oxyethyl phosphate, dimethylol tricyclodecane di (meth) acrylate, trimethylol propane benzoate acrylate and mixtures thereof.
또 다른 경화부의 예로는 에폭시계 경화부를 포함할 수 있다. 상기 에폭시계 경화부의 예로 수첨 비스페놀 수지, 페놀계 에폭시 수지, 나프탈렌계 에폭시 수지, 노볼락계 에폭시 수지, 비스페놀계 에폭시 수지 등을 들 수 있다. Another example of the hardened part may include an epoxy hardened part. Examples of the epoxy cured part include a hydrogenated bisphenol resin, a phenol epoxy resin, a naphthalene epoxy resin, a novolac epoxy resin, and a bisphenol epoxy resin.
경화부는 이방 도전성 필름용 조성물 중 고형분 기준으로 10-40 중량%로 포함될 수 있다. 상기 범위 내에서, 접착력, 외관 등의 물성이 우수하며 신뢰성 후 안정적일 수 있다.The hardened part may be included in an amount of 10-40 wt% based on solids in the composition for an anisotropic conductive film. Within this range, the physical properties such as adhesion, appearance, etc. may be excellent and stable after reliability.
경화제Hardener
본 발명의 이방 도전성 필름용 조성물은 경화제를 포함할 수 있다. 경화제는 경화부의 경화를 개시하거나 촉매하는 역할을 하며, 따라서, 경화부의 종류에 따라 적절히 선택될 수 있다. 상기 라디칼 반응성 아크릴계 경화부를 포함할 경우에는 경화제로 광중합형 개시제 또는 열경화형 개시제 중 1종 이상을 조합하여 사용할 수 있다. 구체적으로, 열경화형 개시제를 사용할 수 있다. 구체예에서, 경화제로 라우릴 퍼옥시드, 큐멘 히드로퍼옥시드와 같은 인체에 무해한 반응 개시제 1종 혹은 2종 이상을 조합하여 사용할 수 있다. The composition for anisotropic conductive films of this invention can contain a hardening | curing agent. The curing agent plays a role of initiating or catalyzing the curing of the curing portion, and thus may be appropriately selected according to the type of the curing portion. When including the said radical reactive acryl-type hardening part, it can use combining a 1 or more types of photoinitiator or a thermosetting initiator as a hardening | curing agent. Specifically, a thermosetting initiator can be used. In an embodiment, one or two or more kinds of reaction initiators that are harmless to the human body, such as lauryl peroxide and cumene hydroperoxide, may be used as the curing agent.
또한 상기 에폭시계 경화부를 포함할 경우에는 이미다졸계, 히드라지드계, 3불화 붕소 아미노염, 설포늄염, 디아조늄염, 아민이미드염, 아민염, 암모늄염, 디시안디아미드염 등의 이온중합성 촉매형 경화제를 사용할 수 있다.In addition, in the case of including the epoxy cured portion, ion polymerization such as imidazole, hydrazide, boron trifluoride amino salt, sulfonium salt, diazonium salt, amineimide salt, amine salt, ammonium salt and dicyandiamide salt Catalytic curing agents can be used.
상기 경화제는 이방 도전성 필름용 조성물 중 고형분 기준으로 0.5-10중량%로 포함될 수 있다. 상기 범위 내에서, 경화에 필요한 충분한 반응이 일어나며 적당한 분자량 형성을 통해 본딩 후 접착력, 신뢰성 등에서 우수한 물성을 기대할 수 있다. The curing agent may be included in 0.5-10% by weight based on solids in the composition for an anisotropic conductive film. Within this range, sufficient reaction occurs for curing and excellent physical properties can be expected in bonding strength, reliability and the like after bonding through the formation of a suitable molecular weight.
벤조일 퍼옥시드는 필름 내 발암성 물질인 벤젠 고리를 포함하므로 본원에서 사용되지 않는다. Benzoyl peroxide is not used herein because it contains a benzene ring, which is a carcinogenic substance in the film.
도전성 입자Conductive particles
본 발명의 이방 도전성 필름용 조성물은 도전 성능을 부여해주는 도전성 입자를 포함한다. The composition for anisotropic conductive films of this invention contains electroconductive particle which gives electroconductive performance.
도전성 입자는 이방 도전성 필름용 조성물 중 고형분 기준으로 1-20중량%로 포함될 수 있다. 상기 범위 내에서, 전기적 도통이 적절하게 이루어질 수 있고 쇼트 등이 발생하지 않을 수 있다. 적당한 도전성 입자의 양은 상기 이방 도전성 필름의 용도에 따라 결정되며 그 함량이 달라질 수 있다. Electroconductive particle may be included in 1-20 weight% based on solid content in the composition for anisotropic conductive films. Within this range, electrical conduction can be made properly and no short or the like can occur. The amount of suitable conductive particles is determined according to the use of the anisotropic conductive film and the content thereof may vary.
도전성 입자로는 금(Au), 은(Ag), 니켈(Ni), 구리(Cu), 땜납 등을 포함하는 금속 입자; 탄소; 폴리에틸렌, 폴리프로필렌, 폴리에스테르, 폴리스티렌, 폴리비닐알코올 등을 포함하는 수지 및 그 변성 수지를 입자로 하여 금(Au), 은(Ag), 니켈(Ni), 구리(Cu), 땜납 등을 포함하는 금속을 코팅한 것; 그 위에 절연 입자를 추가하여 코팅한 절연화 처리된 도전성 입자 등을 1종 이상 사용할 수 있다.As electroconductive particle, Metal particle containing gold (Au), silver (Ag), nickel (Ni), copper (Cu), solder, etc .; carbon; Resin including polyethylene, polypropylene, polyester, polystyrene, polyvinyl alcohol, and the like, and modified resin thereof include gold (Au), silver (Ag), nickel (Ni), copper (Cu), solder, and the like. Coated with metal; Insulated electroconductive particle etc. which coated and added the insulating particle on it can be used 1 or more types.
도전성 입자의 크기는 특별히 제한되지는 않지만, 접착력과 접속 신뢰성을 위해 직경은 1㎛ 내지 20㎛가 바람직할 수 있다.The size of the conductive particles is not particularly limited, but the diameter may be 1 μm to 20 μm for adhesion and connection reliability.
또한, 본 발명의 이방 도전성 필름용 조성물은 기본 물성을 저해하지 않으면서 부가적인 물성을 제공하기 위해 실란커플링제 및/또는 산화티타늄 등을 추가로 포함할 수 있다. 첨가제는 특별히 제한되지 않지만, 고형분 기준으로 이방 도전성 필름용 조성물 중 0.01-10중량%로 포함될 수 있다.In addition, the composition for anisotropic conductive film of the present invention may further include a silane coupling agent and / or titanium oxide in order to provide additional physical properties without inhibiting the basic physical properties. The additive is not particularly limited, but may be included in an amount of 0.01-10% by weight in the composition for anisotropic conductive films on a solids basis.
본 발명은 본 발명의 이방 도전성 필름용 조성물로 형성된 이방 도전성 필름을 제공한다. 이방 도전성 필름을 형성하는 데에는 특별한 장치나 설비가 필요하지 않는다. 예를 들면, 본 발명의 이방 도전성 필름용 조성물을 인체에 무해한 유기 용매에 용해시켜 액상화한 후 도전성 입자가 분쇄되지 않는 속도 범위 내에서 일정 시간 동안 교반하고, 이를 이형 필름 위에 일정한 두께, 예를 들면 10-50㎛의 두께로 도포한 다음 일정시간 건조시켜 유기 용매를 휘발시키거나 또는 추가로 자외선 경화시킴으로써 4-40㎛ 두께의 이방 도전성 필름을 얻을 수 있다.The present invention provides an anisotropic conductive film formed of the composition for an anisotropic conductive film of the present invention. No special device or equipment is necessary to form the anisotropic conductive film. For example, after dissolving the composition for anisotropic conductive film of the present invention in an organic solvent that is harmless to a human body and liquefying, the conductive particles are stirred for a predetermined time within a range in which the conductive particles are not pulverized, and a predetermined thickness, for example, on a release film An anisotropic conductive film having a thickness of 4-40 μm may be obtained by applying a thickness of 10-50 μm and then drying for a predetermined time to volatilize the organic solvent or further ultraviolet curing.
이하, 실시예, 비교예 및 실험예를 기술함으로써 본 발명을 보다 상세히 설명한다. 다만, 하기의 실시예, 비교예 및 실험예는 본 발명의 일 예시에 불과하며 본 발명의 내용이 이에 한정되는 것으로 해석되어서는 아니된다.Hereinafter, the present invention will be described in more detail by describing Examples, Comparative Examples, and Experimental Examples. However, the following Examples, Comparative Examples and Experimental Examples are merely examples of the present invention and should not be construed as being limited thereto.
실시예 Example
실시예 1: 인체에 무해한 이방 도전성 필름용 조성물의 제조Example 1 Preparation of Composition for Anisotropic Conductive Film Harmless to Human Body
필름 형성을 위한 매트릭스 역할의 바인더 수지부로서는 조성물의 전체 고형 중량을 기준으로 NBR계 수지(N-34, 니폰제온) 10 중량%; 폴리우레탄 바인더(NPC7007T, 나눅스) 30 중량%; 우레탄 아크릴레이트(NPC7000, 나눅스) 20 중량%; 아크릴 바인더(AOF-7003, 애경화학) 10 중량%를, 에틸아세테이트/부틸아세테이트(에틸아세테이트: 한센 용해도 파라미터: 18.2; 비점: 77℃, 부틸아세테이트: 한센 용해도 파라미터: 17.4; 비점: 125 내지 127℃)에 용해시켜 사용하였다.As a binder resin part which acts as a matrix for film formation, 10 weight% of NBR-type resins (N-34, Nippon Xeon) based on the total solid weight of a composition; 30% by weight polyurethane binder (NPC7007T, Nanox); 20% by weight of urethane acrylate (NPC7000, Nanux); 10% by weight of an acrylic binder (AOF-7003, Aekyung Chemical) was prepared using ethyl acetate / butyl acetate (ethyl acetate: Hansen solubility parameter: 18.2; boiling point: 77 ° C., butyl acetate: Hansen solubility parameter: 17.4; boiling point: 125 to 127 ° C. ) And used.
반응성 모노머로서 라디칼 중합형 (메타)아크릴레이트 모노머인 펜타에리스리톨 트리(메타)아크릴레이트 2 중량%; 4-하이드록시부틸(메타)아크릴레이트 10 중량%; 디메틸올트리사이클로데칸디아크릴레이트 7.5 중량%; 및 경화제로서 라우릴 퍼옥사이드 2.5 중량%를, 에틸아세테이트/부틸아세테이트에 녹여 첨가하였고, 이방 도전성 필름에 도전 성능을 부여해주기 위한 필러로서 파우더형 니켈 입자 8%를 첨가하여 이방 도전성 필름용 조성물을 제조하였다. 2% by weight of pentaerythritol tri (meth) acrylate, which is a radical polymerization type (meth) acrylate monomer as the reactive monomer; 10% by weight of 4-hydroxybutyl (meth) acrylate; 7.5% by weight of dimethyloltricyclodecanediacrylate; And 2.5% by weight of lauryl peroxide as a curing agent was dissolved in ethyl acetate / butyl acetate and added, and 8% powdered nickel particles were added as a filler for imparting conductive performance to the anisotropic conductive film to prepare a composition for an anisotropic conductive film. It was.
실시예 2: 인체에 무해한 이방 도전성 필름용 조성물의 제조Example 2: Preparation of Composition for Anisotropic Conductive Film Harmless to Human Body
상기 실시예 1에서 경화제로 라우릴 퍼옥사이드 대신 큐멘히드로퍼옥사이드 2.5 중량%를 사용한 것을 제외하고는 동일하게 실시하여 실시예 2의 이방 도전성 필름용 조성물을 제조하였다.Except for using 2.5% by weight cumene hydroperoxide instead of lauryl peroxide as a curing agent in Example 1 to prepare a composition for an anisotropic conductive film of Example 2.
실시예 3:Example 3: 인체에 무해한 이방 도전성 필름용 조성물의 제조Preparation of composition for anisotropic conductive films harmless to human body
상기 실시예 1에서 용매로 에틸아세테이트/부틸아세테이트 대신 에틸아세테이트만을 사용한 것을 제외하고는 상기 실시예 1과 동일하게 실시하여 실시예 3의 이방 도전성 필름용 조성물을 제조하였다. As a solvent in Example 1 Except for using only ethyl acetate instead of ethyl acetate / butyl acetate was carried out in the same manner as in Example 1 to prepare a composition for an anisotropic conductive film of Example 3.
비교예 1: 이방 도전성 필름용 조성물의 제조Comparative Example 1: Preparation of Composition for Anisotropic Conductive Film
상기 실시예 1에 있어서, 용매를 에탄올 (한센 용해도 파라미터: 26.5, 비점: 78℃) 로 한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하여 비교예 1의 조성물을 제조하였다.In Example 1, the composition of Comparative Example 1 was prepared in the same manner as in Example 1, except that the solvent was changed to ethanol (Hansen solubility parameter: 26.5, boiling point: 78 ° C).
비교예 2: 이방 도전성 필름용 조성물의 제조Comparative Example 2: Preparation of Composition for Anisotropic Conductive Film
상기 실시예 1에 있어서, 용매를 메틸사이클로헥산 (한센 용해도 파라미터: 16, 비점: 101℃)로 한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하여 비교예 2의 조성물을 제조하였다.In Example 1, the composition of Comparative Example 2 was prepared in the same manner as in Example 1, except that the solvent was changed to methylcyclohexane (Hansen solubility parameter: 16, boiling point: 101 ° C).
비교예 3: 이방 도전성 필름용 조성물의 제조Comparative Example 3: Preparation of Composition for Anisotropic Conductive Film
상기 실시예 1에서 NBR계 수지(N-34, 니폰제온) 10 중량%를 톨루엔/메틸에틸케톤(비율 1:1(중량비))에 용해시켜 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하여 비교예 3의 조성물을 제조하였다.In the same manner as in Example 1 except that 10% by weight of NBR resin (N-34, Nipon Xeon) was dissolved in toluene / methyl ethyl ketone (ratio 1: 1 (weight ratio)) in Example 1 It carried out to manufacture the composition of Comparative Example 3.
비교예 4: 이방 도전성 필름용 조성물의 제조Comparative Example 4: Preparation of Composition for Anisotropic Conductive Film
상기 실시예 1에서 경화제로 라우릴 퍼옥사이드 대신 벤조일 퍼옥사이드 2.5 중량%를 사용한 것을 제외하고는 실시예 1과 동일하게 실시하여 비교예 4의 이방 도전성 필름용 조성물을 제조하였다.Except for using 2.5% by weight of benzoyl peroxide instead of lauryl peroxide as a curing agent in Example 1 was prepared in the same manner as in Example 1 to prepare a composition for anisotropic conductive film of Comparative Example 4.
실험예: 이방 도전성 필름의 제조 및 이의 물성 측정Experimental Example: Preparation of Anisotropic Conductive Film and Measurement of Its Physical Properties
상기 실시예와 비교예에서 제조된 이방 도전성 필름 조성물 100g을 각각 1시간 동안 25℃에서 교반하고, 이를 이형 필름 위에 35㎛의 두께로 도포한 다음 70℃에서 5분 동안 건조시켜 사용한 용매들을 휘발시킴으로써 이방 도전성 필름을 얻었다. 제조된 이방 도전성 필름에 대하여, 초기 접착력, 초기 접속저항, 신뢰성 접착력, 신뢰성 평가 후 접속저항, 조액안정성, 용매 혹은 성분의 잔류 함량을 평가하고 그 결과를 표 3 및 표 4에 나타내었다. 100 g of the anisotropic conductive film composition prepared in Examples and Comparative Examples were stirred at 25 ° C. for 1 hour, applied to a thickness of 35 μm on a release film, and then dried at 70 ° C. for 5 minutes to volatilize the solvents used. An anisotropic conductive film was obtained. For the produced anisotropic conductive film, the initial adhesion, initial connection resistance, reliable adhesion, after the evaluation of the connection resistance, crude liquid stability, the residual content of the solvent or component was evaluated and the results are shown in Table 3 and Table 4.
1. 접착력1. Adhesion
각각의 제조된 필름을 PCB(피치 200㎛, 단자 폭 100㎛, 단자간 거리 100㎛, 단자 높이 35㎛)와 COF 필름(피치 200㎛, 단자 폭 100㎛, 단자간 거리 100㎛, 단자 높이 8㎛) 사이에 위치시키고 아래와 같은 조건으로 접속하였다.Each manufactured film was printed on PCB (pitch 200 m, terminal width 100 m, distance between terminals 100 m, terminal height 35 m) and COF film (pitch 200 m, terminal width 100 m, distance between terminals 100 m, terminal height 8 (Micrometer) and it connected under the following conditions.
1) 가압착 조건 ; 70℃, 1초, 1.0MPa1) pressurized condition; 70 ° C, 1 second, 1.0 MPa
2) 본압착 조건 ; 150℃, 4초, 4.0MPa 2) main compression conditions; 150 ° C., 4 seconds, 4.0 MPa
상기 제조된 5개의 시편에 대해 UTM(Universal Testing Machine, H5KT,The UTM (Universal Testing Machine, H5KT,
Hounsfield)을 이용하여 1) Load Cell 장착한 후, 2) Load Cell 장착이 완료 되면 grip을 설치하여 측정 준비를 마무리하고 3) 샘플을 grip에 물린 후, 90°Peel 방식으로 tensile test speed 50mm/min 조건에서 6회 반복 측정하여 그 평균값 초기 접착력으로 표 3에 나타내었다. 신뢰성 평가를 위해 상기 접속된 필름을 85℃, 85RH%로 유지되는 고온 고습 챔버에 500시간 보관한 후 상기와 같은 방법으로 접착력을 측정하여 평균값을 계산하였다.Hounsfield) 1) Load Cell installation, 2) Load Cell installation is complete, install the grip to complete the measurement preparation 3) After the sample is bitten by grip, tensile test speed 50mm / min The measurement was repeated 6 times under the conditions, and the average initial adhesion is shown in Table 3. For the evaluation of reliability, the connected film was stored in a high temperature and high humidity chamber maintained at 85 ° C. and 85 RH% for 500 hours, and then the adhesive force was measured in the same manner to calculate an average value.
2. 접속 저항2. Connection resistance
접속 저항은 상기 접착력에 기재된 조건의 가압착 및 본압착 후에 접속 저항을 측정(측정 장비: Keithley社 2000 Multimeter)하고(초기 접속저항) 또한 신뢰성 평가를 위한 항온 항습 조건에 보관 후 2 point probe 법을 이용하여 측정하였다(500 Hr 접속저항). 2 point probe법은 저항측정기기를 이용할 수 있는데 기기에 연결되어 있는 2개의 probe를 이용하여 2 point 사이에서의 저항을 측정한다. 저항측정기기는 1mA를 인가하며 이때 측정되는 전압으로 저항을 계산하여 표시한다. 신뢰성 평가는 85℃, 85RH%로 유지되는 고온 고습 챔버에 상기 회로 접속물을 500시간 보관한 후 접속저항을 측정하여 평균값을 계산하였다.The connection resistance is measured after pressurization and main compression under the conditions described in the above-mentioned adhesion force (measurement equipment: Keithley 2000 Multimeter) (initial connection resistance), and also stored in a constant temperature and humidity condition for reliability evaluation. It measured using (500 Hr connection resistance). The two-point probe method can be used as a resistance measuring instrument. Measure the resistance between two points using two probes connected to the instrument. The resistance measuring instrument applies 1mA and calculates and displays the resistance based on the measured voltage. In the reliability evaluation, the circuit connection was stored for 500 hours in a high temperature and high humidity chamber maintained at 85 ° C and 85 RH%, and then the connection resistance was measured to calculate an average value.
3. 조액 안정성3. Liquid stability
상이 분리되지 않고 액이 안정한 상태로 유지되었는지를 확인하기 위해 상기 실시예와 비교예에서 제조된 이방 도전성 필름 조성물 100g을 상온에서 8 ~ 12 시간 동안 방치 한 뒤 이형필름에 35㎛두께로 도포하여 70도의 오븐에서 5분간 건조하여 코팅 표면을 관찰한다. 도전 입자가 뭉쳐져 있는지 등을 현미경으로 확인한다. 도 2와 같이 상 분리가 일어나 도전입자가 뭉쳐진 상태로 있는 것은 '불량'으로, 도 3과 같이 상 분리 없이 도전입자가 전체에 균일하게 분산된 형태로 있는 것은 '양호'로 판정하였다.In order to confirm that the liquid was kept in a stable state without separation of the phase, 100 g of the anisotropic conductive film composition prepared in Examples and Comparative Examples was left at room temperature for 8 to 12 hours and then applied to a release film at a thickness of 35 μm. Dry for 5 minutes in the oven to observe the coating surface. Check under a microscope whether the conductive particles are agglomerated. As shown in FIG. 2, it is determined that the conductive particles are in a state in which the conductive particles are agglomerated as shown in FIG. 2, and the conductive particles are uniformly dispersed in the whole without phase separation as in FIG. 3.
표 3
　 실시예1 실시예 2 실시예 3 비교예1 비교예2 비교예3 비교예 4
초기 접착력(gf/cm) 940 900 890 650 680 910 930
초기 접속저항(Ω) 0.35 0.37 0.39 0.57 0.63 0.35 0.35
신뢰성 접착력(gf/cm) 730 650 621 420 450 740 740
신뢰성 접속저항(Ω) 0.68 0.73 0.78 4.78 5.62 0.68 0.67
조액안정성 양호 양호 양호 불량 불량 양호 양호
TABLE 3
Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4
Initial adhesive force (gf / cm) 940 900 890 650 680 910 930
Initial connection resistance 0.35 0.37 0.39 0.57 0.63 0.35 0.35
Reliability Adhesion (gf / cm) 730 650 621 420 450 740 740
Reliability Connection Resistance 0.68 0.73 0.78 4.78 5.62 0.68 0.67
Liquid stability Good Good Good Bad Bad Good Good
4. 유해 용매 혹은 성분의 잔류량4. Residual amounts of hazardous solvents or components
또한, 상기 실시예와 비교예에서 제조된 이방 도전성 필름 100g에 대해 GC/MC을 사용해 EPA 5021, 8260에 기재된 방법으로 용매 혹은 성분의 함량에 대해 성분 분석을 하고 그 결과를 하기 표 4에 나타내었다.In addition, with respect to 100g of the anisotropic conductive film prepared in the above Examples and Comparative Examples using the GC / MC using the method described in EPA 5021, 8260, the component analysis of the content of the solvent or component and the results are shown in Table 4 below. .
표 4
　 실시예1 실시예 2 실시예 3 비교예1 비교예2 비교예3 비교예 4
톨루엔 N.D. N.D. N.D. N.D. N.D. 80ppm N.D.
메틸에틸케톤 N.D. N.D. N.D. N.D. N.D. 40ppm N.D.
벤젠 N.D. N.D. N.D. N.D. N.D. N.D. 70ppm
Table 4
Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4
toluene ND ND ND ND ND 80 ppm ND
Methyl ethyl ketone ND ND ND ND ND 40 ppm ND
benzene ND ND ND ND ND ND 70 ppm
N.D.: not detected (검출 안됨)N.D .: not detected
상기 표 3 및 표 4의 결과로부터 확인할 수 있는 바와 같이 한센 용해도 파라미터가 20초과하거나 17미만인 용매를 사용한 조성물은 라우릴 퍼옥시드 혹은 큐멘히드로퍼옥사이드와의 조액 안정성 저하로 인해 초기 및 신뢰성 평가 후 접착력 혹은 접속저항 물성이 저하되며, 용매로 톨루엔 또는 메틸에틸케톤을 사용한 필름에서 인체 유해 물질이 검출됨을 알 수 있다. 본 발명의 일 예에 따른 필름 조성물 및 필름은 인체 유해 물질을 함유하지 않아 안전하면서도 우수한 접착력, 접속 신뢰성 및 조액 안정성을 나타낸다.As can be seen from the results of Table 3 and Table 4, the composition using a solvent having a Hansen solubility parameter of more than 20 or less than 17 has an adhesive strength after initial and reliability evaluation due to a decrease in the crude liquid stability with lauryl peroxide or cumene hydroperoxide. Alternatively, the connection resistance physical properties are lowered, and it can be seen that human harmful substances are detected in the film using toluene or methyl ethyl ketone as a solvent. The film composition and the film according to an embodiment of the present invention do not contain any harmful substances to human body, and exhibit excellent adhesive strength, connection reliability, and solution stability.
[부호의 설명][Description of the code]
10 이방 도전성 필름10 anisotropic conductive film
30 반도체 장치30 semiconductor devices
3 도전 입자3 conductive particles
50 제1 피접속부재50 first connected member
60 제2 피접속부재60 2nd member to be connected
70 제1 전극70 first electrode
80 제2 전극80 second electrode

Claims (23)

  1. 바인더부, 경화부, 경화제, 도전성 입자, 및 한센 용해도 파라미터(Hansen Solubility Parameter)가 17 내지 20인 용매를 포함하며, 단, 상기 용매가 톨루엔 혹은 메틸에틸케톤은 아닌, 이방 도전성 필름용 조성물.A binder part, a hardening part, a hardening | curing agent, electroconductive particle, and the solvent of Hansen Solubility Parameter of 17-20, Comprising: The said composition for an anisotropic conductive films in which the said solvent is not toluene or methyl ethyl ketone.
  2. 제1항에 있어서, 상기 경화제가 라우릴 퍼옥시드 및 큐멘히드로퍼옥시드 중 1종 이상 선택된, 이방 도전성 필름용 조성물.The composition for anisotropic conductive films according to claim 1, wherein the curing agent is selected from at least one of lauryl peroxide and cumene hydroperoxide.
  3. 제1항에 있어서, 상기 용매가 메틸 아세테이트, 에틸 아세테이트, 부틸 아세테이트, 이소프로필알코올, 및 이소부틸알코올 중 1종 이상인 이방 도전성 필름용 조성물.The composition for anisotropic conductive films according to claim 1, wherein the solvent is at least one of methyl acetate, ethyl acetate, butyl acetate, isopropyl alcohol, and isobutyl alcohol.
  4. 제3항에 있어서, 상기 용매가 에틸 아세테이트 및 부틸 아세테이트 중 1종 이상인 이방 도전성 필름용 조성물. The composition for anisotropic conductive films according to claim 3, wherein the solvent is at least one of ethyl acetate and butyl acetate.
  5. 제1항에 있어서, 상기 용매의 비점이 70 내지 130℃인 이방 도전성 필름용 조성물.The composition for anisotropic conductive films of Claim 1 whose boiling point of the said solvent is 70-130 degreeC.
  6. 제1항에 있어서, 상기 바인더부가 아크릴계 수지, 우레탄 아크릴레이트계 수지, 아크릴로니트릴계 수지, 스티렌-아크릴로니트릴계 수지, 부타디엔계 수지, 폴리아미드계 수지, 올레핀계 수지, 페녹시계 수지, 우레탄계 수지 및 실리콘계 수지로 이루어진 1종 이상의 수지를 포함하는, 이방 도전성 필름용 조성물.The method of claim 1, wherein the binder portion is acrylic resin, urethane acrylate resin, acrylonitrile resin, styrene-acrylonitrile resin, butadiene resin, polyamide resin, olefin resin, phenoxy resin, urethane The composition for anisotropic conductive films containing 1 or more types of resin which consists of resin and silicone-type resin.
  7. 제1항에 있어서, 상기 경화부가 우레탄 (메타)아크릴레이트, 1,6-헥산디올 모노(메타)아크릴레이트, 2-히드록시에틸 (메타)아크릴레이트, 2-히드록시프로필 (메타)아크릴레이트, 2-히드록시부틸 (메타)아크릴레이트, 2-히드록시-3-페닐옥시프로필 (메타)아크릴레이트, 1,4-부탄디올 (메타)아크릴레이트, 2-히드록시에틸 (메타)아크릴로일 포스페이트, 4-히드록시부틸(메타)아크릴레이트, 4-히드록시사이클로헥실 (메타)아크릴레이트, 네오펜틸글리콜 모노(메타)아크릴레이트, 트리메틸올에탄 디(메타)아크릴레이트, 트리메틸올프로판 디(메타)아크릴레이트, 펜타에리스리톨 트리(메타)아크릴레이트, 디펜타에리스리톨 펜타(메타)아크릴레이트, 펜타에리스리톨 헥사(메타)아크릴레이트, 디펜타에리스리톨 헥사(메타)아크릴레이트, 글리세린 디(메타)아크릴레이트, 히드로퍼퓨릴 (메타)아크릴레이트, 이소데실 (메타)아크릴레이트, 2-(2-에톡시에톡시)에틸 (메타)아크릴레이트, 스테아릴 (메타)아크릴레이트, 라우릴 (메타)아크릴레이트, 2-페녹시에틸 (메타)아크릴레이트, 이소보닐 (메타)아크릴레이트, 트리데실 (메타)아크릴레이트, 에톡시 부가형 노닐페놀 (메타)아크릴레이트, 에틸렌글리콜 디(메타)아크릴레이트, 트리에틸렌글리콜 디(메타)아크릴레이트, 테트라에틸렌글리콜 디(메타)아크릴레이트, 폴리에틸렌글리콜 디(메타)아크릴레이트, 1,3-부틸렌글리콜 디(메타)아크릴레이트, 트리프로필렌글리콜 디(메타)아크릴레이트, 에톡시 부가형 비스페놀-A 디(메타)아크릴레이트, 시클로헥산디메탄올 디(메타)아크릴레이트, 페녹시-t-글리콜 (메타)아크릴레이트, 2-메타아크릴로일록시메틸 포스페이트, 2-메타아크릴로일록시에틸 포스페이트, 디메틸올 트리시클로데케인 디(메타)아크릴레이트, 및 트리메틸올 프로판 벤조에이트 아크릴레이트로 이루어진 군으로부터 선택된 1종 이상을 포함하는, 이방 도전성 필름용 조성물.The said hardening part is a urethane (meth) acrylate, a 1, 6- hexanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate of Claim 1 , 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol (meth) acrylate, 2-hydroxyethyl (meth) acryloyl Phosphate, 4-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentylglycol mono (meth) acrylate, trimethylolethane di (meth) acrylate, trimethylolpropane di ( Meta) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin di (meth) acrylate , Hydroperfuryl (meth) acrylate, isodecyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate , 2-phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tridecyl (meth) acrylate, ethoxy addition nonylphenol (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Ethoxy addition type bisphenol-A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, phenoxy-t-glycol (meth) acrylate, 2-methacryloyloxymethyl phosphate, 2-metha With acrylic A composition for an anisotropic conductive film comprising at least one selected from the group consisting of hydroxyethyl phosphate, dimethylol tricyclodecane di (meth) acrylate, and trimethylol propane benzoate acrylate.
  8. 제1항에 있어서, 상기 경화부가 수첨 비스페놀 수지, 페놀계 에폭시 수지, 나프탈렌계 에폭시 수지, 노볼락계 에폭시 수지, 및 비스페놀계 에폭시 수지로 이루어진 군으로부터 선택된 1종 이상을 포함하는, 이방 도전성 필름용 조성물.The anisotropic conductive film according to claim 1, wherein the curing part comprises at least one selected from the group consisting of a hydrogenated bisphenol resin, a phenol epoxy resin, a naphthalene epoxy resin, a novolac epoxy resin, and a bisphenol epoxy resin. Composition.
  9. 제1항 또는 제2항에 있어서, 상기 용매가 한센 용해도 파라미터가 17 내지 20이면서 비점이 70℃ 내지 100℃인 제1 용매와 한센 용해도 파라미터가 17 내지 20이면서 비점이 100℃ 내지 130℃인 제2 용매를 포함하는, 이방 도전성 필름용 조성물.The agent according to claim 1 or 2, wherein the solvent has a Hansen solubility parameter of 17 to 20 and a boiling point of 70 to 100 ° C., and the first solvent and a Hansen solubility parameter of 17 to 20 and a boiling point of 100 to 130 ° C. The composition for anisotropic conductive films containing 2 solvents.
  10. 제9항에 있어서, 상기 제1 용매가 메틸 아세테이트 또는 에틸 아세테이트 중 1종 이상이며 상기 제2 용매가 부틸 아세테이트, 이소프로필알코올, 이소부틸알코올 중 1종 이상인 이방 도전성 필름용 조성물.The composition for anisotropic conductive films according to claim 9, wherein the first solvent is at least one of methyl acetate or ethyl acetate and the second solvent is at least one of butyl acetate, isopropyl alcohol, and isobutyl alcohol.
  11. 바인더부, 경화부, 경화제 및 도전성 입자를 포함하고, 0 내지 1 ppm의 메틸에틸케톤, 및 0 내지 10 ppm의 톨루엔을 포함하는, 이방 도전성 필름.An anisotropic conductive film containing a binder portion, a curing portion, a curing agent, and conductive particles, and containing 0 to 1 ppm of methyl ethyl ketone, and 0 to 10 ppm of toluene.
  12. 제11항에 있어서, 상기 이방 도전성 필름이 0 내지 1 ppm의 벤젠을 추가로 포함하는, 이방 도전성 필름. The anisotropic conductive film of Claim 11 in which the said anisotropic conductive film further contains 0-1 ppm of benzene.
  13. 제11항에 있어서, 상기 이방 도전성 필름이 한센 용해도 파라미터(Hansen Solubility Parameter)가 17 내지 20인 용매를 포함하는, 이방 도전성 필름.The anisotropic conductive film of Claim 11 in which the said anisotropic conductive film contains the solvent whose Hansen Solubility Parameter is 17-20.
  14. 제13항에 있어서, 상기 용매가 메틸 아세테이트, 에틸 아세테이트, 부틸 아세테이트, 이소프로필알코올, 및 이소부틸알코올 중 1종 이상인 이방 도전성 필름.The anisotropic conductive film of claim 13, wherein the solvent is at least one of methyl acetate, ethyl acetate, butyl acetate, isopropyl alcohol, and isobutyl alcohol.
  15. 제11항에 있어서, 상기 경화제가 라우릴 퍼옥시드 및 큐멘 히드로퍼옥시드 중 1종 이상인 이방 도전성 필름.The anisotropic conductive film according to claim 11, wherein the curing agent is at least one of lauryl peroxide and cumene hydroperoxide.
  16. 제11항에 있어서, 상기 바인더부가 아크릴계 수지, 우레탄 아크릴레이트계 수지, 아크릴로니트릴계 수지, 스티렌-아크릴로니트릴계 수지, 부타디엔계 수지, 폴리아미드계 수지, 올레핀계 수지, 페녹시계 수지, 우레탄계 수지 및 실리콘계 수지로 이루어진 1종 이상의 수지를 포함하는, 이방 도전성 필름.The method of claim 11, wherein the binder portion is acrylic resin, urethane acrylate resin, acrylonitrile resin, styrene-acrylonitrile resin, butadiene resin, polyamide resin, olefin resin, phenoxy resin, urethane An anisotropic conductive film containing at least one resin made of a resin and a silicone resin.
  17. 제11항에 있어서, 상기 경화부가 우레탄 (메타)아크릴레이트, 1,6-헥산디올 모노(메타)아크릴레이트, 2-히드록시에틸 (메타)아크릴레이트, 2-히드록시프로필 (메타)아크릴레이트, 2-히드록시부틸 (메타)아크릴레이트, 2-히드록시-3-페닐옥시프로필 (메타)아크릴레이트, 1,4-부탄디올 (메타)아크릴레이트, 2-히드록시에틸 (메타)아크릴로일 포스페이트, 4-히드록시부틸(메타)아크릴레이트, 4-히드록시사이클로헥실 (메타)아크릴레이트, 네오펜틸글리콜 모노(메타)아크릴레이트, 트리메틸올에탄 디(메타)아크릴레이트, 트리메틸올프로판 디(메타)아크릴레이트, 펜타에리스리톨 트리(메타)아크릴레이트, 디펜타에리스리톨 펜타(메타)아크릴레이트, 펜타에리스리톨 헥사(메타)아크릴레이트, 디펜타에리스리톨 헥사(메타)아크릴레이트, 글리세린 디(메타)아크릴레이트, 히드로퍼퓨릴 (메타)아크릴레이트, 이소데실 (메타)아크릴레이트, 2-(2-에톡시에톡시)에틸 (메타)아크릴레이트, 스테아릴 (메타)아크릴레이트, 라우릴 (메타)아크릴레이트, 2-페녹시에틸 (메타)아크릴레이트, 이소보닐 (메타)아크릴레이트, 트리데실 (메타)아크릴레이트, 에톡시 부가형 노닐페놀 (메타)아크릴레이트, 에틸렌글리콜 디(메타)아크릴레이트, 트리에틸렌글리콜 디(메타)아크릴레이트, 테트라에틸렌글리콜 디(메타)아크릴레이트, 폴리에틸렌글리콜 디(메타)아크릴레이트, 1,3-부틸렌글리콜 디(메타)아크릴레이트, 트리프로필렌글리콜 디(메타)아크릴레이트, 에톡시 부가형 비스페놀-A 디(메타)아크릴레이트, 시클로헥산디메탄올 디(메타)아크릴레이트, 페녹시-t-글리콜 (메타)아크릴레이트, 2-메타아크릴로일록시메틸 포스페이트, 2-메타아크릴로일록시에틸 포스페이트, 디메틸올 트리시클로데케인 디(메타)아크릴레이트, 및 트리메틸올 프로판 벤조에이트 아크릴레이트로 이루어진 군으로부터 선택된 1종 이상을 포함하는, 이방 도전성 필름.The said hardening part is a urethane (meth) acrylate, a 1, 6- hexanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate of Claim 11 , 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol (meth) acrylate, 2-hydroxyethyl (meth) acryloyl Phosphate, 4-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentylglycol mono (meth) acrylate, trimethylolethane di (meth) acrylate, trimethylolpropane di ( Meta) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin di (meth) acrylate , Hydroperfuryl (meth) acrylate, isodecyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate , 2-phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tridecyl (meth) acrylate, ethoxy addition nonylphenol (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Ethoxy addition type bisphenol-A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, phenoxy-t-glycol (meth) acrylate, 2-methacryloyloxymethyl phosphate, 2-metha acryl One hydroxyethyl phosphate, dimethylol-tricyclo decane di (meth) acrylate, and trimethylolpropane benzoate comprising at least one member selected from the group consisting of acrylates, the anisotropic conductive film.
  18. 제11항에 있어서, 상기 경화부가 수첨 비스페놀 수지, 페놀계 에폭시 수지, 나프탈렌계 에폭시 수지, 노볼락계 에폭시 수지, 및 비스페놀계 에폭시 수지로 이루어진 군으로부터 선택된 1종 이상을 포함하는, 이방 도전성 필름용 조성물.12. The anisotropic conductive film according to claim 11, wherein the curing part comprises at least one selected from the group consisting of a hydrogenated bisphenol resin, a phenol epoxy resin, a naphthalene epoxy resin, a novolac epoxy resin, and a bisphenol epoxy resin. Composition.
  19. 제13항에 있어서, 상기 용매의 비점이 70 내지 130℃인 이방 도전성 필름.The anisotropic conductive film of claim 13, wherein the solvent has a boiling point of 70 to 130 ° C. 15.
  20. 제11항 또는 제12항에 있어서, 상기 이방 도전성 필름이 한센 용해도 파라미터(Hansen Solubility Parameter)가 17 내지 20이면서 비점이 70℃ 내지 100℃인 제1 용매와 한센 용해도 파라미터(Hansen Solubility Parameter)가 17 내지 20이면서 비점이 100℃ 내지 130℃이하인 제2 용매를 포함하는, 이방 도전성 필름.The first solvent and Hansen solubility parameter of claim 11 or 12, wherein the anisotropic conductive film has a Hansen Solubility Parameter of 17 to 20 and a boiling point of 70 ° C to 100 ° C. It is an anisotropic conductive film containing 2nd solvent whose boiling point is 100 degreeC-130 degreeC or less, being 20-20.
  21. 제20항에 있어서, 상기 제1 용매가 메틸 아세테이트 또는 에틸 아세테이트 중 1종 이상이며 상기 제2 용매가 부틸 아세테이트, 이소프로필알코올, 이소부틸알코올 중 1종 이상인, 이방 도전성 필름.21. The anisotropic conductive film of claim 20, wherein the first solvent is at least one of methyl acetate or ethyl acetate and the second solvent is at least one of butyl acetate, isopropyl alcohol, isobutyl alcohol.
  22. 바인더부, 경화부, 라우릴 퍼옥시드 및 큐멘 히드로퍼옥시드 중 1종 이상 선택된 경화제; 도전성 입자; 에틸 아세테이트 및 부틸 아세테이트 중 1종 이상 선택된 용매를 포함하는 이방 도전성 필름용 조성물.A curing agent selected from at least one of a binder portion, a curing portion, lauryl peroxide and cumene hydroperoxide; Electroconductive particle; Composition for an anisotropic conductive film comprising at least one solvent selected from ethyl acetate and butyl acetate.
  23. 제1 전극을 함유하는 제1 피접속부재; A first to-be-connected member containing a first electrode;
    제2 전극을 함유하는 제2 피접속부재; 및A second to-be-connected member containing a second electrode; And
    상기 제1 피접속부재와 상기 제2 피접속부재 사이에 위치하여 상기 제1 전극 및 상기 제2 전극을 접속시키는 제1항 내지 제8항 중 어느 하나의 항에 따른 이방 도전성 필름용 조성물로부터 형성된 이방 도전성 필름 또는 제11항 내지 제19항 중 어느 하나의 항에 따른 이방 도전성 필름을 포함하는 반도체 장치.It is formed from the composition for anisotropic conductive films of any one of Claims 1-8 which is located between the said 1st to-be-connected member and the said 2nd to-be-connected member, and connects the said 1st electrode and the said 2nd electrode. The semiconductor device containing the anisotropically conductive film or the anisotropically conductive film in any one of Claims 11-19.
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