TWI464814B

TWI464814B - Anisotropic conductive film

Info

Publication number: TWI464814B
Application number: TW100125813A
Authority: TW
Inventors: Hyun Joo Seo; Hyun Hee Namkung; Kyoung Hun Shin; Kang Bae Yoon; Kyoung Soo Park; Kyu Bong Kim; Ja Young Hwang
Original assignee: Cheil Ind Inc
Priority date: 2010-12-31
Filing date: 2011-07-21
Publication date: 2014-12-11
Also published as: KR101397690B1; CN102533195A; CN102533195B; KR20120078461A; TW201234506A

Description

各向異性導電膜(一)Anisotropic conductive film (1)

發明領域Field of invention

本發明涉及一種各向異性導電膜。更具體地，本發明涉及一種包括彩色複合無機顏料(CICP)的各向異性導電膜，所述CICP使得在對電路元件如PCB預壓制所述膜後易於確認所述各向異性導電膜的存在，而不劣化所述膜的電性能和熱性能。The present invention relates to an anisotropic conductive film. More particularly, the present invention relates to an anisotropic conductive film including a color composite inorganic pigment (CICP) which makes it easy to confirm the existence of the anisotropic conductive film after pre-compacting the film to a circuit component such as a PCB Without degrading the electrical and thermal properties of the film.

發明背景Background of the invention

各向異性導電膜是指其中分散有導電顆粒如金屬顆粒或金屬塗覆的塑膠顆粒的膜狀黏合劑。各向異性導電膜廣泛應用於各種領域，包括平板顯示器領域中的電路連接以及半導體器件中的元件裝配。當各向異性導電膜***在待連接的電路之間，隨後在適宜的溫度、壓力和時間條件下熱壓制時，電路端子通過導電顆粒電連接，並使絕緣黏合劑樹脂填充相鄰的電路端子之間的空隙，以使得導電顆粒彼此獨立，從而實現電路端子之間的絕緣。The anisotropic conductive film refers to a film-like adhesive in which conductive particles such as metal particles or metal-coated plastic particles are dispersed. Anisotropic conductive films are widely used in various fields, including circuit connections in the field of flat panel displays and component assembly in semiconductor devices. When the anisotropic conductive film is inserted between the circuits to be connected and then hot pressed under suitable temperature, pressure and time conditions, the circuit terminals are electrically connected by the conductive particles, and the insulating adhesive resin is filled adjacent circuit terminals. The gap between them is such that the conductive particles are independent of each other, thereby achieving insulation between the circuit terminals.

各向異性導電膜的高透明性是由於包括熱塑性樹脂的黏合劑部份中分散的導電顆粒的存在，使得即使對電路元件預壓制上述膜後也難以確定該膜的存在。這還會使壓制裝置故障方面的製造成本增加。The high transparency of the anisotropic conductive film is due to the presence of the conductive particles dispersed in the binder portion including the thermoplastic resin, so that it is difficult to determine the existence of the film even after the film member is pre-compressed. This also increases the manufacturing cost in terms of failure of the pressing device.

另一方面，各向異性導電膜通常通過添加諸如顏料等著色劑著色。這種著色有助於在預壓制後確認膜的存在，但會使膜的基本電性能(包括黏合強度、接線電阻(connection resistance)和絕緣電阻)變差。On the other hand, an anisotropic conductive film is usually colored by adding a coloring agent such as a pigment. This coloring helps to confirm the presence of the film after pre-compression, but degrades the basic electrical properties of the film, including bond strength, connection resistance, and insulation resistance.

因此，需要開發即使在對電路元件進行預壓制後也保持它們的電性能並能夠容易確定其存在與否的各向異性導電膜。Therefore, there is a need to develop an anisotropic conductive film which maintains its electrical properties even after pre-pressing circuit elements and can easily determine its presence or absence.

發明概要Summary of invention

本發明的一方面提供了一種各向異性導電膜。在一個實施方式中，所述各向異性導電膜包括(A)黏合劑部份、(B)固化部份、(C)自由基引發劑、(D)導電顆粒和(E)彩色複合無機顏料(CICP)。An aspect of the invention provides an anisotropic conductive film. In one embodiment, the anisotropic conductive film comprises (A) a binder portion, (B) a cured portion, (C) a radical initiator, (D) a conductive particle, and (E) a color composite inorganic pigment. (CICP).

在一個實施方式中，所述CICP可由選自由鎳、銅、鉻、鎂、鋅、鋁、錳、鈦、鐵和銻組成的組中的兩種或更多種金屬的複合氧化物或氫氧化物製備。In one embodiment, the CICP may be a composite oxide or hydroxide of two or more metals selected from the group consisting of nickel, copper, chromium, magnesium, zinc, aluminum, manganese, titanium, iron, and ruthenium. Preparation.

在一個實施方式中，基於100重量份的所述黏合劑部份(A)、所述固化部份(B)、所述自由基引發劑(C)和所述導電顆粒(D)，所述CICP的量可為0.1至10重量份。In one embodiment, based on 100 parts by weight of the binder portion (A), the cured portion (B), the radical initiator (C), and the conductive particles (D), The amount of CICP may be from 0.1 to 10 parts by weight.

在一個實施方式中，在對電路端子預壓制所述膜後，所述各向異性導電膜的亮度可比電路端子的亮度低至少20%。In one embodiment, the brightness of the anisotropic conductive film may be at least 20% lower than the brightness of the circuit terminals after pre-compacting the film to the circuit terminals.

圖式簡單說明Simple illustration

由以下結合附圖的詳細說明中，本發明的以上和其它方面、特徵和優點將變得明顯，其中：The above and other aspects, features, and advantages of the present invention will become apparent from the Detailed Description of the Description

第1圖是在對PCB的電路端子預壓制實施例1中製備的各向異性導電膜後拍攝的光學顯微鏡圖像，第2圖示出了各向異性導電膜亮度與電路端子亮度比較的測試結果；1 is an optical microscope image taken after pre-compacting the anisotropic conductive film prepared in Example 1 on the circuit terminal of the PCB, and FIG. 2 is a test comparing the brightness of the anisotropic conductive film with the brightness of the circuit terminal. result;

第3圖是在對PCB的電路端子預壓制對比例1中製備的各向異性導電膜後拍攝的光學顯微鏡圖像，第4圖示出了各向異性導電膜亮度與電路端子亮度比較的測試結果；Fig. 3 is an optical microscope image taken after pre-compacting the anisotropic conductive film prepared in Comparative Example 1 on the circuit terminal of the PCB, and Fig. 4 shows a test comparing the brightness of the anisotropic conductive film with the brightness of the circuit terminal. result;

第5圖是PCB的電路端子的光學顯微鏡圖像，第6圖示出了使用Image J程序的電路端子亮度；且Figure 5 is an optical microscope image of the circuit terminals of the PCB, and Figure 6 shows the brightness of the circuit terminals using the Image J program;

第7圖是根據本發明示例性實施方式的膜貼附到PCB的電路端子後拍攝的光學顯微鏡圖像，第8圖示出了使用Image J程式的電路端子亮度。Fig. 7 is an optical microscope image taken after attaching a film to a circuit terminal of a PCB according to an exemplary embodiment of the present invention, and Fig. 8 is a view showing a circuit terminal brightness using an Image J program.

較佳實施例之詳細說明Detailed description of the preferred embodiment

本發明的各方面提供了一種各向異性導電膜，該各向異性導電膜包括黏合劑部份、固化部份、自由基引發劑、導電顆粒和彩色複合無機顏料(CICP)。Aspects of the present invention provide an anisotropic conductive film including a binder portion, a solidified portion, a radical initiator, conductive particles, and a color composite inorganic pigment (CICP).

黏合劑部份Adhesive part

黏合劑部份用作各向異性導電膜的基質並在壓力下呈現出高附著性。因此，當對電路熱壓制各向異性導電膜時，黏合劑部份由於它的高黏合強度和良好的附著力而對電路端子提供良好連接。The binder portion serves as a matrix for the anisotropic conductive film and exhibits high adhesion under pressure. Therefore, when the anisotropic conductive film is thermally pressed against the circuit, the adhesive portion provides a good connection to the circuit terminals due to its high adhesive strength and good adhesion.

基於黏合劑部份、固化部份、自由基引發劑和導電顆粒的總固含量，黏合劑部份的含量可為20至58wt%。在此範圍內時，不會降低各向異性導電膜在溶劑中的溶解度，且不會劣化各向異性導電膜的連接可靠性。優選地，黏合劑部份的含量為20至50wt%。The binder portion may be contained in an amount of 20 to 58% by weight based on the total solid content of the binder portion, the solidified portion, the radical initiator, and the conductive particles. When it is in this range, the solubility of the anisotropic conductive film in a solvent is not lowered, and the connection reliability of the anisotropic conductive film is not deteriorated. Preferably, the binder portion is present in an amount of from 20 to 50% by weight.

上述黏合劑部份可為選自由丙烯腈丁二烯(NBR)共聚物、環氧樹脂、苯氧基樹脂、烯烴樹脂、羧基封端的丙烯腈丁二烯共聚物、乙烯-乙酸乙烯酯共聚物、聚乙烯基丁縮醛樹脂、聚乙烯基甲縮醛樹脂、聚酯樹脂、酚醛樹脂、可聚合的丙烯酸類樹脂、聚醯亞胺樹脂、聚醯胺樹脂、聚胺甲酸酯樹脂、聚酯樹脂、聚酯胺甲酸酯樹脂、苯乙烯-丁烯-苯乙烯樹脂、改性環氧樹脂和它們的混合物組成的組中的至少一種。The binder portion may be selected from an acrylonitrile butadiene (NBR) copolymer, an epoxy resin, a phenoxy resin, an olefin resin, a carboxyl terminated acrylonitrile butadiene copolymer, and an ethylene-vinyl acetate copolymer. , polyvinyl butyral resin, polyvinyl acetal resin, polyester resin, phenolic resin, polymerizable acrylic resin, polyimine resin, polyamide resin, polyurethane resin, poly At least one of the group consisting of an ester resin, a polyester urethane resin, a styrene-butene-styrene resin, a modified epoxy resin, and a mixture thereof.

固化部份Curing part

固化部份可包括選自由(甲基)丙烯酸酯單體、環氧丙烷-環氧樹脂和胺甲酸酯丙烯酸酯組成的組中的至少一種化合物。The cured portion may include at least one compound selected from the group consisting of a (meth) acrylate monomer, a propylene oxide-epoxy resin, and a urethane acrylate.

基於黏合劑部份、固化部份、自由基引發劑和導電顆粒的總固含量，固化部份的含量可為40至65wt%。在此範圍內時，可呈現出良好的附著性和高連接可靠性，且固化後獲得了緻密結構，從而保證了良好的長期連接可靠性而不劣化黏合強度。優選地，固化部份的含量為45至60wt%。The content of the solidified portion may be 40 to 65 wt% based on the total solid content of the binder portion, the solidified portion, the radical initiator, and the conductive particles. Within this range, good adhesion and high connection reliability can be exhibited, and a dense structure is obtained after curing, thereby ensuring good long-term connection reliability without deteriorating the bonding strength. Preferably, the content of the cured portion is from 45 to 60% by weight.

(甲基)丙烯酸酯單體用作各向異性導電膜組合物中的反應性稀釋劑。(甲基)丙烯酸酯單體可為選自由1,6-己二醇單(甲基)丙烯酸酯、(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-2-羥丙酯、(甲基)丙烯酸-2-羥丁酯、2-羥基-3-苯氧基丙基(甲基)丙烯酸酯、1,4-丁二醇(甲基)丙烯酸酯、2-羥乙基(甲基)丙烯醯基磷酸酯、4-羥基環己基(甲基)丙烯酸酯、新戊二醇單(甲基)丙烯酸酯、三羥甲基乙烷二(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、季戊四醇六(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、氫化呋喃基(甲基)丙烯酸酯、(甲基)丙烯酸異癸酯、2-(2-乙氧基乙氧基)乙基(甲基)丙烯酸酯、(甲基)丙烯酸十八烷酯、(甲基)丙烯酸十二烷酯、2-苯氧基乙基(甲基)丙烯酸酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸十三烷酯、乙氧基化的壬基苯酚(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、乙氧基化的雙酚-A二(甲基)丙烯酸酯、環己烷二甲醇二(甲基)丙烯酸酯、苯氧基叔乙二醇(甲基)丙烯酸酯(phenoxy-t -glycol(meth)acrylate)、2-甲基丙烯醯氧基甲基磷酸酯、2-甲基丙烯醯氧基乙基磷酸酯、二羥甲基三環癸烷二(甲基)丙烯酸酯、三羥甲基丙烷苯甲酸酯丙烯酸酯、(甲基)丙烯酸二氧磷基乙酯((meth)acrylic acid phosphoxy ethyl)和它們的混合物組成的組中的至少一種，但不限於此。The (meth) acrylate monomer is used as a reactive diluent in the anisotropic conductive film composition. The (meth) acrylate monomer may be selected from the group consisting of 1,6-hexanediol mono(meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. , 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 1,4-butanediol (meth) acrylate, 2-hydroxyethyl (Meth) propylene decyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolethane di (meth) acrylate, tris Methyl propane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin Di(meth)acrylate, hydrogenated furyl (meth) acrylate, isodecyl (meth) acrylate, 2-(2-ethoxyethoxy)ethyl (meth) acrylate, (A) Octadecyl acrylate, dodecyl (meth)acrylate, 2-phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tridecyl (meth) acrylate Ethoxylated nonylphenol (meth) acrylate, Diol (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3- Butanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethoxylated bisphenol-A di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate , t-phenoxy glycol (meth) acrylate (phenoxy- t -glycol (meth) acrylate ), 2- methyl-Bing Xixi yloxymethyl phosphate, 2-oxyethyl phosphoryl Bing Xixi Ester, dimethylol tricyclodecane di(meth) acrylate, trimethylolpropane benzoate acrylate, (meth)acrylic acid phosphoxy ethyl At least one of the group consisting of and a mixture thereof, but is not limited thereto.

環氧丙烷-環氧樹脂沒有限制，只要它在一個分子中具有兩個或更多個環氧基並在分子鏈中包含至少一個環氧丙烷部份。The propylene oxide-epoxy resin is not limited as long as it has two or more epoxy groups in one molecule and at least one propylene oxide moiety in the molecular chain.

適用於固化部份的環氧丙烷-環氧樹脂的實例包括：雙酚型環氧樹脂，如雙酚A型環氧樹脂、雙酚A型環氧丙烯酸酯樹脂和雙酚F型環氧樹脂；芳族環氧化合物，如聚縮水甘油醚環氧樹脂和聚縮水甘油酯環氧樹脂；脂環族環氧化合物；酚醛型環氧樹脂，如甲酚酚醛清漆型環氧樹脂和苯酚酚醛清漆型環氧樹脂；縮水甘油基胺型環氧化合物；縮水甘油酯型環氧化合物；聯苯基二縮水甘油醚環氧化合物。Examples of propylene oxide-epoxy resins suitable for the cured portion include: bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol A type epoxy acrylate resin, and bisphenol F type epoxy resin. Aromatic epoxy compounds such as polyglycidyl ether epoxy resins and polyglycidyl epoxy resins; alicyclic epoxy compounds; phenolic epoxy resins such as cresol novolak type epoxy resins and phenol novolacs Epoxy resin; glycidylamine type epoxy compound; glycidyl ester type epoxy compound; biphenyl diglycidyl ether epoxy compound.

胺甲酸酯丙烯酸酯在兩端包括胺甲酸酯鍵和雙鍵。用於製備胺甲酸酯丙烯酸酯的聚合方法沒有特別限制。The urethane acrylate includes a urethane bond and a double bond at both ends. The polymerization method for preparing the urethane acrylate is not particularly limited.

胺甲酸酯丙烯酸酯可具有1000至50000g/mol的重均分子量。在此範圍內時，能令人滿意地形成該膜並高度相容。The urethane acrylate may have a weight average molecular weight of from 1,000 to 50,000 g/mol. Within this range, the film can be satisfactorily formed and highly compatible.

上述固化部份可進一步包括縮醛化合物和/或碳二亞胺化合物。The above cured portion may further include an acetal compound and/or a carbodiimide compound.

自由基引發劑Free radical initiator

自由基引發劑可為光聚合引發劑、熱固化劑或它們的組合。優選熱固化劑。The radical initiator may be a photopolymerization initiator, a heat curing agent, or a combination thereof. A heat curing agent is preferred.

基於黏合劑部份、固化部份、自由基引發劑和導電顆粒的總固含量，自由基引發劑的含量可為0.1至5wt%。在此範圍內時，可持續地保持接線電阻的長期可靠性。優選地，自由基引發劑的含量為0.5至3wt%。The content of the radical initiator may be from 0.1 to 5 wt% based on the total solid content of the binder portion, the solidified portion, the radical initiator, and the conductive particles. Within this range, the long-term reliability of the wiring resistance can be maintained continuously. Preferably, the free radical initiator is present in an amount of from 0.5 to 3% by weight.

適用於上述各向異性導電膜中的熱固化劑的實例包括但不限於過氧化物引發劑，如過氧化月桂醯、過氧化苯甲醯和異丙苯過氧化氫。根據固化條件可使用兩種或更多種引發劑的混合物。在此情況下，引發劑的比例沒有限制。Examples of the thermosetting agent suitable for use in the anisotropic conductive film described above include, but are not limited to, peroxide initiators such as laurel peroxide, benzammonium peroxide, and cumene hydroperoxide. A mixture of two or more initiators may be used depending on the curing conditions. In this case, the ratio of the initiator is not limited.

導電顆粒Conductive particles

導電顆粒用作填料，以賦予各向異性導電膜導電性能。Conductive particles are used as a filler to impart electrical conductivity to the anisotropic conductive film.

基於黏合劑部份、固化部份、自由基引發劑和導電顆粒的總固含量，導電顆粒的含量可為1至20wt%。在此範圍內時，可持續地保持可靠性測試後的膜的接線電阻。優選地，導電顆粒的含量為3至10wt%。The conductive particles may be included in an amount of from 1 to 20% by weight based on the total solid content of the binder portion, the solidified portion, the radical initiator, and the conductive particles. Within this range, the wiring resistance of the film after the reliability test is continuously maintained. Preferably, the conductive particles are contained in an amount of from 3 to 10% by weight.

適用於各向異性導電膜中的導電顆粒的實例包括：金屬顆粒，如鎳(Ni)、金(Au)、銀(Ag)、銅(Cu)和焊料金屬顆粒；碳顆粒；金屬塗覆的樹脂顆粒，如塗覆有金(Au)、銀(Ag)、鎳(Ni)、銅(Cu)和焊料金屬的聚乙烯、聚丙稀、聚酯、聚苯乙烯、聚乙烯醇和它們的改性樹脂的顆粒；以及塗覆有絕緣顆粒的導電顆粒。Examples of the conductive particles suitable for use in the anisotropic conductive film include: metal particles such as nickel (Ni), gold (Au), silver (Ag), copper (Cu), and solder metal particles; carbon particles; metal coated Resin particles such as polyethylene coated with gold (Au), silver (Ag), nickel (Ni), copper (Cu) and solder metal, polypropylene, polyester, polystyrene, polyvinyl alcohol and their modification Particles of the resin; and conductive particles coated with insulating particles.

對導電顆粒的尺寸沒有特別限制。例如，在黏合強度和連接可靠性方面優選的導電顆粒具有1至20μm的直徑。There is no particular limitation on the size of the conductive particles. For example, preferred conductive particles in terms of adhesive strength and connection reliability have a diameter of 1 to 20 μm.

彩色複合無機顏料(CICP)Color composite inorganic pigment (CICP)

CICP是指通過在1000℃或更高的溫度下燒結兩種或更多種金屬的複合氧化物或氫氧化物製備的無機著色劑。該高溫燒結使得CICP具有非常穩定的結晶結構，如尖晶石或金紅石。CICP refers to an inorganic colorant prepared by sintering a composite oxide or hydroxide of two or more metals at a temperature of 1000 ° C or higher. This high temperature sintering allows the CICP to have a very stable crystalline structure such as spinel or rutile.

為了在預壓制後確認上述膜的存在，通常向各向異性導電膜添加著色劑，如顏料。然而，各向異性導電膜不應包括隨意使用任何著色劑，因為它們要求改善的可識別性，同時保持它們固有的電性能和熱性能。例如，公知為著黑色的著色劑的碳黑相當地改善了各向異性導電膜的可識別性，但它會使膜的物理性能(如接線電阻、絕緣電阻和黏合強度)變差。In order to confirm the existence of the above film after the pre-pressing, a coloring agent such as a pigment is usually added to the anisotropic conductive film. However, anisotropic conductive films should not include the arbitrary use of any colorants because they require improved recognizability while maintaining their inherent electrical and thermal properties. For example, carbon black, which is known as a black coloring agent, considerably improves the recognizability of an anisotropic conductive film, but it deteriorates physical properties of the film such as wiring resistance, insulation resistance, and bonding strength.

相比而言，CICP在各向異性導電膜中的使用在實現改善的膜的可識別性，同時保持膜的接線電阻、絕緣電阻和黏合強度方面是有效的。In contrast, the use of CICP in an anisotropic conductive film is effective in achieving improved film recognizability while maintaining film wiring resistance, insulation resistance, and bonding strength.

CICP可由選自由鎳、銅、鉻、鎂、鋅、鋁、錳、鈦、鐵和銻組成的組中的兩種或更多種金屬的複合氧化物或氫氧化物製備。根據所用複合金屬氧化物或氫氧化物的顏色，CICP的顏色可為黑色、黃色、藍色、綠色或棕色。The CICP can be prepared from a composite oxide or hydroxide of two or more metals selected from the group consisting of nickel, copper, chromium, magnesium, zinc, aluminum, manganese, titanium, iron, and ruthenium. The color of the CICP may be black, yellow, blue, green or brown depending on the color of the composite metal oxide or hydroxide used.

基於100重量份的黏合劑部份、固化部份、自由基引發劑和導電顆粒，CICP的含量可為0.1至10重量份。CICP用量小於0.1重量份導致預壓制後膜的可識別性的改善很少。同時，CICP用量大於10重量份會導致膜的過度硬化或黏附性差，並可導致可靠性測試後接線電阻增大。優選地，CICP的含量為1至5重量份。The CICP may be contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the binder portion, the curing portion, the radical initiator, and the conductive particles. A CICP dosage of less than 0.1 parts by weight results in little improvement in the recognizability of the film after pre-compression. At the same time, a CICP dosage of more than 10 parts by weight may result in excessive hardening or poor adhesion of the film and may result in an increase in wiring resistance after the reliability test. Preferably, the CICP is contained in an amount of from 1 to 5 parts by weight.

CICP是目前市場上可購得的。CICP的可商購產品實例包括，但不限於Black 30C965、Black 20C980、Black 20C920、Black 444、Black 10C909、Black 411、Violet 11、Blue 385、Blue 211、Green 187B、Green 410、Green 223、Green 260、Yellow 10C112、Yellow 10C242、Yellow 10C272和Brown 20C819。CICP is currently available on the market. Examples of commercially available products of CICP include, but are not limited to, Black 30C965, Black 20C980, Black 20C920, Black 444, Black 10C909, Black 411, Violet 11, Blue 385, Blue 211, Green 187B, Green 410, Green 223, Green 260 Yellow 10C112, Yellow 10C242, Yellow 10C272 and Brown 20C819.

CICP可選自由表1所示產品組成的組，但不限於此。The CICP may be selected from the group consisting of the products shown in Table 1, but is not limited thereto.

在對電路端子預壓制上述膜之後，各向異性導電膜的亮度可比電路端子的亮度低至少20%。由於各向異性導電膜在預壓制後的低亮度，因而能辨別它的存在。優選地，各向異性導電膜的亮度比電路端子的亮度低至少25%。After the film is pre-compressed to the circuit terminals, the brightness of the anisotropic conductive film may be at least 20% lower than the brightness of the circuit terminals. Due to the low brightness of the anisotropic conductive film after pre-compression, it can be discerned. Preferably, the brightness of the anisotropic conductive film is at least 25% lower than the brightness of the circuit terminals.

亮度可通過本領域已知的適宜方法測定。例如，亮度可通過在光學顯微鏡下觀察各向異性導電膜和電路端子，並用Image J程式分析圖像對比度的長條圖來測定，該光學顯微鏡裝有以反射模式在最大光強下20×放大倍數的鏡頭，而不用介質篩檢程式以獲得圖像。Brightness can be determined by suitable methods known in the art. For example, brightness can be determined by observing an anisotropic conductive film and circuit terminals under an optical microscope and analyzing the bar graph of the image contrast using an Image J program equipped with a reflection mode at a maximum light intensity of 20× magnification. Multiple lenses without the media screening program to get the image.

電路端子沒有特別限制，只要可對其預壓制上述各向異性導電膜。這種電路端子的實例包括PCB、ITO、IZO、COF和FPC。預壓制方法沒有特別限制。例如，預壓制可在0.5至3MPa的壓力和40至100℃的溫度下進行0.5至10秒。The circuit terminal is not particularly limited as long as the above anisotropic conductive film can be pre-compressed. Examples of such circuit terminals include PCB, ITO, IZO, COF, and FPC. The pre-pressing method is not particularly limited. For example, the pre-pressing can be carried out at a pressure of 0.5 to 3 MPa and a temperature of 40 to 100 ° C for 0.5 to 10 seconds.

各向異性導電膜可用包括黏合劑部份、固化部份、自由基引發劑、導電顆粒和CICP的膜組合物製造。可使用本領域已知的任何適宜方法來製備上述各向異性導電膜。The anisotropic conductive film can be fabricated using a film composition including a binder portion, a curing portion, a radical initiator, conductive particles, and CICP. The anisotropic conductive film described above can be prepared by any suitable method known in the art.

製造各向異性導電膜不需要特別的裝置或設備。例如，各向異性導電膜可製造如下：將膜組合物溶解在適宜的有機溶劑(例如甲苯)中，以不會導致導電顆粒粉碎的速率攪拌該溶液一段時間，在離型膜上將該溶液塗佈至適宜的厚度(例如10～50μm)，並乾燥該溶液一段時間至足以蒸發有機溶劑。No special device or equipment is required to manufacture the anisotropic conductive film. For example, the anisotropic conductive film can be produced by dissolving the film composition in a suitable organic solvent (for example, toluene), stirring the solution at a rate that does not cause the conductive particles to be pulverized, and applying the solution on the release film. It is applied to a suitable thickness (for example, 10 to 50 μm), and the solution is dried for a period of time sufficient to evaporate the organic solvent.

各向異性導電膜可進一步包括一種或多種添加劑以提供其它物理性能，只要各向異性導電膜的基本物理性能不受損。這些添加劑的實例包括聚合抑制劑、抗氧化劑和熱穩定劑。基於100重量份的各向異性導電膜組合物，添加劑的量可為0.03至0.3重量份。The anisotropic conductive film may further include one or more additives to provide other physical properties as long as the basic physical properties of the anisotropic conductive film are not impaired. Examples of such additives include polymerization inhibitors, antioxidants, and heat stabilizers. The amount of the additive may be from 0.03 to 0.3 parts by weight based on 100 parts by weight of the anisotropic conductive film composition.

下文中，將參照以下實施例更詳細地解釋本發明的組成和功能。提供這些實施例僅用於說明的目的，而不以任何方式理解為限制本發明。Hereinafter, the composition and function of the present invention will be explained in more detail with reference to the following examples. The examples are provided for illustrative purposes only and are not to be construed as limiting the invention in any way.

對本領域技術人員而言，未包括在文中的公開是容易認識和理解的，因此省略其解釋。The disclosures not included in the text are easily recognized and understood by those skilled in the art, and thus the explanation thereof is omitted.

實施例1～7和對比例1～3中所用的組分詳細如下：The components used in Examples 1 to 7 and Comparative Examples 1 to 3 are as follows:

1.黏合劑部份1. Adhesive part

丙烯腈丁二烯橡膠(NBR)(N34,NIPPON ZEON)Acrylonitrile Butadiene Rubber (NBR) (N34, NIPPON ZEON)

2.固化部份2. Curing part

雙酚A型環氧樹脂(Bis-A-E)(E4275,JAPAN Epoxy Resins Co.,Ltd.)Bisphenol A type epoxy resin (Bis-A-E) (E4275, JAPAN Epoxy Resins Co., Ltd.)

雙酚A型環氧丙烯酸酯樹脂(Bis-A-EA)(3002A,KYOEISHA)Bisphenol A type epoxy acrylate resin (Bis-A-EA) (3002A, KYOEISHA)

(甲基)丙烯酸二氧磷基乙酯(MAM)(Phosmer-M,Uni-chemical)Phosphorus (meth) acrylate (MAM) (Phosmer-M, Uni-chemical)

3.自由基引發劑3. Free radical initiator

過氧化月桂醯(Peroyl-L,Nippon Oils and Fats)Peroyl-L, Nippon Oils and Fats

過氧化苯甲醯(PEROX-B95,Hosung Chemex,Co.,Ltd.(韓國))Benzoyl peroxide (PEROX-B95, Hosung Chemex, Co., Ltd. (Korea))

4.導電顆粒4. Conductive particles

平均粒徑(D50)為5μm的鎳顆粒(N525,Novamet)Nickel particles with an average particle diameter (D50) of 5 μm (N525, Novamet)

5.CICP5.CICP

銅-鉻氧化物(黑30C965,Shepherd)Copper-chromium oxide (Black 30C965, Shepherd)

金屬-粗粉氧化物(metal-meal oxides)(黑444(Cu,Fe,Mn)，黑20C920(Cu,Cr,Mn)，藍30C527(Co,Cr,Al)，棕20C819(Fe,Al,Ti),Shepherd)Metal-meal oxides (black 444 (Cu, Fe, Mn), black 20C920 (Cu, Cr, Mn), blue 30C527 (Co, Cr, Al), brown 20C819 (Fe, Al, Ti), Shepherd)

實施例1：各向異性導電膜的製備Example 1: Preparation of an anisotropic conductive film

將丙烯腈丁二烯橡膠(重均分子量=30000000g/mol)在甲苯/甲基乙基酮2:1(v/v))中的30g溶液(25vol%)、15g雙酚A型環氧樹脂、33g雙酚A環氧丙烯酸酯樹脂、5g(甲基)丙烯酸二氧磷基乙酯、1g過氧化月桂醯、1g過氧化苯甲醯、8g平均粒徑(D50)為5μm的鎳顆粒和1g銅-鉻氧化物(黑30C965，Shepherd)共混以製備各向異性導電膜組合物。將該組合物塗佈在為離型膜的聚對苯二甲酸乙二醇酯膜上，並乾燥以製得具有35μm塗層厚度的各向異性導電膜。30 g solution (25 vol%) of acrylonitrile butadiene rubber (weight average molecular weight = 30,000,000 g/mol) in toluene/methyl ethyl ketone 2:1 (v/v), 15 g of bisphenol A type epoxy resin , 33 g of bisphenol A epoxy acrylate resin, 5 g of (di)phosphoryl (meth) acrylate, 1 g of lauricium laurate, 1 g of benzoyl peroxide, 8 g of nickel particles having an average particle diameter (D50) of 5 μm 1 g of copper-chromium oxide (Black 30C965, Shepherd) was blended to prepare an anisotropic conductive film composition. This composition was coated on a polyethylene terephthalate film which is a release film, and dried to obtain an anisotropic conductive film having a coating thickness of 35 μm.

實施例2～7：各向異性導電膜的製造Examples 2 to 7: Fabrication of an anisotropic conductive film

用與實施例1相同的方法製造各向異性導電膜，區別在於如表2所示改變各組分的含量和/或種類。An anisotropic conductive film was produced in the same manner as in Example 1 except that the content and/or kind of each component was changed as shown in Table 2.

對比例1～3：各向異性導電膜的製造Comparative Examples 1 to 3: Fabrication of an anisotropic conductive film

用與實施例1相同的方法製造各向異性導電膜，區別在於如表3所示改變各組分的含量和/或種類。An anisotropic conductive film was produced in the same manner as in Example 1 except that the content and/or kind of each component was changed as shown in Table 3.

測試例1：各向異性導電膜的物理性能評價Test Example 1: Evaluation of physical properties of anisotropic conductive film

測定實施例1～7和對比例1～3製造的各向異性導電膜的物理性能，且其結果示於表4和表5中。The physical properties of the anisotropic conductive films produced in Examples 1 to 7 and Comparative Examples 1 to 3 were measured, and the results are shown in Tables 4 and 5.

<物理性能的測定方法><Method for measuring physical properties>

1.接線電阻和可靠性：使用PCB(間距=200μm，端子寬度=100μm，端子之間的間隔=100μm)和COF(端子寬度=100μm，端子之間的間隔=100μm)。在1MPa、70℃下對PCB電路端子預壓制實施例1～7和對比例1～3中製備的每個各向異性導電膜1秒後，去除離型膜。之後，佈置COF電路端子與PCB電路端子相對，隨後在3MPa、180℃下最終壓制5秒。用2點探針法測定樣品的接線電阻。在85℃和RH 85%下儲存500小時後，測定樣品的接線電阻。1. Wiring resistance and reliability: PCB (pitch=200 μm, terminal width=100 μm, interval between terminals=100 μm) and COF (terminal width=100 μm, interval between terminals=100 μm) were used. The release film was removed by pre-compacting each of the anisotropic conductive films prepared in Examples 1 to 7 and Comparative Examples 1 to 3 to the PCB circuit terminals at 1 MPa and 70 ° C for 1 second. Thereafter, the COF circuit terminals were arranged to be opposed to the PCB circuit terminals, and then finally pressed at 3 MPa and 180 ° C for 5 seconds. The wiring resistance of the sample was measured by a 2-point probe method. After 500 hours of storage at 85 ° C and RH 85%, the wiring resistance of the sample was measured.

2.絕緣電阻和可靠性：用與上述1中相同的方式製備用於絕緣電阻測定的樣品。2. Insulation resistance and reliability: A sample for insulation resistance measurement was prepared in the same manner as in the above 1.

在對樣品施加100V的DC電壓的同時，使用SM8215型(TOADK)和2點探針法測定各樣品的絕緣電阻60秒。與接線電阻測定中一樣，在85℃和RH 85%下儲存500小時後，測定樣品的絕緣電阻。The insulation resistance of each sample was measured for 60 seconds using a SM8215 type (TOADK) and a 2-point probe method while applying a DC voltage of 100 V to the sample. As in the measurement of the wiring resistance, the insulation resistance of the sample was measured after storage at 85 ° C and RH 85% for 500 hours.

3.光密度(OD)：用比重計(型號：301X，X-Rite，美國)測定各向異性導電膜的OD值。3. Optical Density (OD): The OD value of the anisotropic conductive film was measured with a hydrometer (Model: 301X, X-Rite, USA).

4.可識別性：用與上述相同的方式預壓制各向異性導電膜。在光學顯微鏡(BX51，Olympus)下觀察PCB端子和各向異性導電膜以確定這些膜是否為可識別的。4. Recognizability: The anisotropic conductive film was pre-compressed in the same manner as described above. The PCB terminals and anisotropic conductive films were observed under an optical microscope (BX51, Olympus) to determine whether the films were identifiable.

5.預壓制後的亮度：用與上述相同的方式預壓制各向異性導電膜之後，用Image J程式評價各個膜的亮度相比PCB端子的亮度的降低率。亮度值用0(黑色)至255(白色)的級別表示。5. Brightness after pre-compression: After the anisotropic conductive film was pre-compressed in the same manner as above, the brightness of each film was evaluated as compared with the brightness of the PCB terminal by Image J. The brightness value is represented by a level of 0 (black) to 255 (white).

6.黏合強度：用與接線電阻測定中相同的方式製備樣品。測定各樣品的90°黏合強度。6. Adhesive strength: Samples were prepared in the same manner as in the measurement of the wiring resistance. The 90° adhesion strength of each sample was measured.

由表4和表5中的結果可看出，實施例1～7中製備的分別包括上述範圍內的黏合劑部份、固化部份、自由基引發劑和導電顆粒的各向異性導電膜在接線電阻、絕緣電阻、接線電阻可靠性、絕緣電阻可靠性和黏合強度方面表現出優異的特性，同時保持了它們的電性能。此外，這些各向異性導電膜具有高OD值(即高濁度)，暗示了改善的可識別性。As can be seen from the results in Tables 4 and 5, the anisotropic conductive films prepared in Examples 1 to 7 respectively including the binder portion, the solidified portion, the radical initiator, and the conductive particles in the above range were Excellent characteristics in terms of wiring resistance, insulation resistance, wiring resistance reliability, insulation resistance reliability, and bonding strength while maintaining their electrical properties. In addition, these anisotropic conductive films have high OD values (i.e., high haze), suggesting improved recognizability.

第1圖表示對PCB電路端子預壓制實施例1中製備的各向異性導電膜後的狀態，第2圖表示與PCB電路端子的亮度相比的所述各向異性導電膜的亮度。如第2圖所示，所述膜的亮度比PCB電路端子的亮度低至少20%，使得能夠確定該膜的存在。Fig. 1 shows a state in which the anisotropic conductive film prepared in Example 1 is pre-compressed to the PCB circuit terminal, and Fig. 2 shows the brightness of the anisotropic conductive film in comparison with the brightness of the PCB circuit terminal. As shown in Fig. 2, the brightness of the film is at least 20% lower than the brightness of the PCB circuit terminals, making it possible to determine the presence of the film.

相比而言，對比例1～3中製備的不含CICP的各向異性導電膜在接線電阻和絕緣電阻方面表現出低可靠性。此外，膜的可識別性差。In contrast, the CICP-free anisotropic conductive film prepared in Comparative Examples 1 to 3 exhibited low reliability in terms of wiring resistance and insulation resistance. In addition, the film is poorly identifiable.

第3圖表示對PCB電路端子預壓制對比例1中製備的各向異性導電膜後的狀態，第4圖表示與PCB電路端子的亮度相比的所述各向異性導電膜的亮度。在第4圖中，所述膜的亮度與PCB電路端子的亮度幾乎一樣，使得難以確定該膜的存在。Fig. 3 shows a state in which the anisotropic conductive film prepared in Comparative Example 1 is pre-compressed to the PCB circuit terminal, and Fig. 4 shows the luminance of the anisotropic conductive film in comparison with the luminance of the PCB circuit terminal. In Fig. 4, the brightness of the film is almost the same as the brightness of the PCB circuit terminals, making it difficult to determine the presence of the film.

分別包括碳黑代替CICP的對比例2和3的各向異性導電膜在可識別性方面令人滿意，但電性能變差。The anisotropic conductive films of Comparative Examples 2 and 3 including carbon black instead of CICP, respectively, were satisfactory in recognizability, but the electrical properties were deteriorated.

儘管已結合附圖和表說明了本發明的前述實施方式，本發明不限於這些實施方式，並可以各種不同形式實施。本領域技術人員應理解的是，除了以具體說明的實施方式以外還可實施本發明而不改變本發明的技術精神或必要特徵。因此，應理解的是，這些實施方式應認為在各方面都是說明性的而不認為是限制目的。Although the foregoing embodiments of the present invention have been described in conjunction with the drawings and the drawings, the present invention is not limited to these embodiments and may be embodied in various forms. It is to be understood by those skilled in the art that the present invention may be practiced without departing from the spirit and scope of the invention. Therefore, it should be understood that the embodiments are to be considered in all respects

Claims

一種各向異性導電膜，包括：(A)黏合劑部份、(B)固化部份、(C)自由基引發劑、(D)導電顆粒和(E)彩色複合無機顏料，其中，基於100重量份的組分(A)、(B)、(C)和(D)，所述彩色複合無機顏料的含量為0.1至10重量份。 An anisotropic conductive film comprising: (A) a binder portion, (B) a cured portion, (C) a radical initiator, (D) a conductive particle, and (E) a color composite inorganic pigment, wherein The color composite inorganic pigment is contained in an amount of 0.1 to 10 parts by weight based on parts by weight of the components (A), (B), (C) and (D).

如申請專利範圍第1項所述的各向異性導電膜，其中，基於100重量份的組分(A)、(B)、(C)和(D)，所述彩色複合無機顏料的含量為1至5重量份。 The anisotropic conductive film according to claim 1, wherein the content of the color composite inorganic pigment is based on 100 parts by weight of the components (A), (B), (C) and (D). 1 to 5 parts by weight.

如申請專利範圍第1項所述的各向異性導電膜，其中，所述彩色複合無機顏料由選自由鎳、銅、鉻、鎂、鋅、鋁、錳、鈦、鐵和銻組成的組中的兩種或更多種金屬的複合氧化物或氫氧化物來製備。 The anisotropic conductive film according to claim 1, wherein the color composite inorganic pigment is selected from the group consisting of nickel, copper, chromium, magnesium, zinc, aluminum, manganese, titanium, iron, and lanthanum. A composite oxide or hydroxide of two or more metals is prepared.

如申請專利範圍第3項所述的各向異性導電膜，其中，所述彩色複合無機顏料通過在1000℃或更高的溫度下燒結所述複合金屬氧化物或氫氧化物來製備。 The anisotropic conductive film according to claim 3, wherein the color composite inorganic pigment is prepared by sintering the composite metal oxide or hydroxide at a temperature of 1000 ° C or higher.

如申請專利範圍第1項所述的各向異性導電膜，其中，所述彩色複合無機顏料具有尖晶石或金紅石晶體結構。 The anisotropic conductive film according to claim 1, wherein the color composite inorganic pigment has a spinel or rutile crystal structure.

如申請專利範圍第1項所述的各向異性導電膜，其中，基於所述黏合劑部份、所述固化部份、所述自由基引發劑和所述導電顆粒的總固含量，所述黏合劑部份、所述固化部份、所述自由基引發劑和所述導電顆粒的含量分別為20至58wt%、40至65wt%、0.1至5wt%和1至20wt%。 The anisotropic conductive film according to claim 1, wherein the total solid content of the binder portion, the solidified portion, the radical initiator, and the conductive particles is The content of the binder portion, the curing portion, the radical initiator, and the conductive particles are 20 to 58 wt%, 40 to 65 wt%, 0.1 to 5 wt%, and 1 to 20 wt%, respectively.

如申請專利範圍第1項所述的各向異性導電膜，其中，所述固化部份包括選自由(甲基)丙烯酸酯單體、環氧丙烷-環氧樹脂和胺甲酸酯丙烯酸酯組成的組中的至少一種化合物。 The anisotropic conductive film of claim 1, wherein the cured portion comprises a monomer selected from the group consisting of (meth) acrylate monomers and propylene oxide At least one compound of the group consisting of an alkane-epoxy resin and a urethane acrylate.

如申請專利範圍第1項所述的各向異性導電膜，其中，在對電路端子預壓制所述膜後，所述各向異性導電膜的亮度比所述電路端子的亮度低至少20%。The anisotropic conductive film according to claim 1, wherein the anisotropic conductive film has a luminance lower than a luminance of the circuit terminal by at least 20% after the film is pre-compressed to the circuit terminal.