CN100509981C - Adhesive for circuit connection - Google Patents
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- CN100509981C CN100509981C CNB2004100309632A CN200410030963A CN100509981C CN 100509981 C CN100509981 C CN 100509981C CN B2004100309632 A CNB2004100309632 A CN B2004100309632A CN 200410030963 A CN200410030963 A CN 200410030963A CN 100509981 C CN100509981 C CN 100509981C
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Abstract
本发明提供了一种电路连接用粘结剂。它是将相对的电路电极经加热、加压,使加压方向的电极间实现电连接的热粘结性的粘结剂中,上述粘结剂含有热固化的反应性树脂,以DSC测得的发热开始温度最低为60℃,而固化反应的80%的结束温度最高为260℃,直到固化反应的80%结束的温度的发热量为50~140焦耳/克。The invention provides an adhesive for circuit connection. It is a heat-adhesive adhesive that heats and presses the electrodes of the opposite circuit to achieve electrical connection between the electrodes in the direction of pressure. The above-mentioned adhesive contains a thermosetting reactive resin, measured by DSC The lowest starting temperature of the exothermic reaction is 60°C, and the highest end temperature of 80% of the curing reaction is 260°C, and the calorific value until 80% of the curing reaction ends is 50-140 joules/gram.
Description
技术领域 technical field
本发明涉及用于电路基板之间或者IC芯片等电子零件同布线基板之间连接的电路连接用粘结剂。The present invention relates to an adhesive for circuit connection used between circuit boards or between electronic components such as IC chips and a wiring board.
背景技术 Background technique
当电路基板之间或者IC芯片等电子零件和电路基板之间进行电路连接时,使用将粘结剂或者导电粒子分散的各向异性的导电粘结剂。即,可以将这些粘结剂涂覆于相对设立的两电极之间,经加热、加压使电极之间连接后,再通过在加压方向使其具有导电性而实现电连接。例如,在日本特许公开公报平3-16147号中,提出使用环氧树脂作为主要成分的电路连接用粘结剂的方案。When performing circuit connection between circuit boards or between electronic components such as IC chips and circuit boards, anisotropic conductive adhesives in which adhesives or conductive particles are dispersed are used. That is, these adhesives can be applied between two opposing electrodes, heated and pressurized to connect the electrodes, and then electrically connected by making them conductive in the direction of pressurization. For example, Japanese Patent Laid-Open Publication No. Hei 3-16147 proposes an adhesive for circuit connection using an epoxy resin as a main component.
然而,以环氧树脂作为主要成分的粘结剂,在抗热冲击试验和PCT等试验等的可靠性试验中,基于连接基板的热膨胀率的不同所产生的内部应力,容易在连接处产生连接阻抗的增大以及粘结剂的剥离。However, with epoxy resin as the main component, in reliability tests such as thermal shock resistance tests and PCT tests, the internal stress generated by the difference in thermal expansion coefficient of the connection substrate is likely to cause a connection at the connection point. Increased resistance and peeling of the adhesive.
另外,在通过粘结剂将芯片直接连接到基板上时,作为连接基板若使用FR4基体材料等的印刷基板,使用聚酰亚胺及聚脂等高分子薄膜作为基体材料的挠性电路板或者玻璃基板,连接后,源于同芯片的热膨胀率的不同而产生的内部应力,容易产生芯片和基板的挠曲。再有,当将芯片向基板压接使粘结剂流动的情况下,许多孔隙发生在连接界面,存在耐湿性降低等问题。In addition, when the chip is directly connected to the substrate through an adhesive, if a printed substrate such as FR4 base material is used as the connection substrate, a flexible circuit board using a polymer film such as polyimide or polyester as the base material or After the glass substrate is connected, the chip and the substrate tend to warp due to the internal stress generated by the difference in thermal expansion coefficient between the chip and the chip. Furthermore, when the chip is pressure-bonded to the substrate and the adhesive flows, many voids are generated at the connection interface, and there is a problem that the moisture resistance is lowered.
发明内容 Contents of the invention
本发明的目的在于提供一种电路连接用粘结剂,它可抑制由于源于热膨胀率的不同所产生的内部应力使连接处的连接阻抗增大,粘结剂的剥离和芯片及基板的挠曲。The object of the present invention is to provide an adhesive for circuit connection, which can suppress the increase of the connection impedance at the connection due to the internal stress caused by the difference in thermal expansion rate, the peeling of the adhesive and the flexure of the chip and the substrate. song.
本发明的电路连接用粘结剂是将相对的电路电极经加热、加压,使加压方向的电极间实现电连接的热粘结性粘结剂中,上述粘结剂具有以下特征,即:它含有分散的平均粒径为10μm以下的橡胶粒子和热固化的反应性树脂,该粘结剂的DSC(差式扫描热分析)的发热开始温度为60℃以上,而固化反应的80%的结束温度为260℃以下。The circuit-connecting adhesive of the present invention is a heat-adhesive adhesive that electrically connects the electrodes in the pressing direction by heating and pressing the opposing circuit electrodes, and the above-mentioned adhesive has the following characteristics, that is, : It contains dispersed rubber particles with an average particle size of 10 μm or less and a thermally cured reactive resin. The DSC (differential scanning calorimetry) of the adhesive has a heating onset temperature of 60°C or more, and 80% of the curing reaction The end temperature is below 260°C.
另外,本发明的粘结剂在从发热开始温度到固化反应的80%结束的温度,用DSC测得的发热量最好为50~140焦耳/克。In addition, the adhesive of the present invention preferably has a calorific value measured by DSC of 50 to 140 J/g from the exothermic start temperature to the temperature at which 80% of the curing reaction is completed.
再有,本发明的粘结剂用DSC测得的固化反应的60%结束温度最好在160℃以下。Furthermore, the 60% end temperature of the curing reaction of the adhesive of the present invention measured by DSC is preferably below 160°C.
再有,反应性树脂最好含有环氧树脂和潜在性固化剂。Furthermore, the reactive resin preferably contains an epoxy resin and a latent curing agent.
再有,潜在性固化剂最好是锍盐。Furthermore, the latent curing agent is preferably a sulfonium salt.
另外,本发明的粘结剂也可以含有以分散状态存在的0.1~30体积%的导电粒子。In addition, the binder of the present invention may contain 0.1 to 30% by volume of conductive particles existing in a dispersed state.
本发明的粘结剂意在包含薄膜状的粘结剂和糊状粘结剂两者,但最好是薄膜状粘结剂。The adhesives of the present invention are intended to include both film-like adhesives and paste-like adhesives, but preferably film-like adhesives.
在将本发明的粘结剂做成薄膜状的情况下,可以含有形成薄膜的高分子物质。When the adhesive of the present invention is formed into a film, it may contain a polymer substance that forms a film.
另外,本发明的薄膜在25℃时的弹性率最好为50~1000MPa。In addition, the film of the present invention preferably has an elastic modulus of 50 to 1000 MPa at 25°C.
若使用本发明,可以吸收在抗热冲击试验及PCT试验等的可靠性试验中所产生的内部应力,即使在可靠性试验后也没有连接处的连接阻抗增大及粘结剂剥离的现象,可以得到连接可靠性提高的粘结剂。另外,若使用本发明,在将芯片实际安装在LCD板时,由于降低了基板的挠曲可以抑制其对显示质量的不良影响。即,可以抑制由于挠曲的发生带来的显示面的间隙的变化而产生显示斑点的现象。If the present invention is used, the internal stress generated in reliability tests such as thermal shock resistance test and PCT test can be absorbed, and even after the reliability test, there is no increase in the connection resistance of the connection and no peeling of the adhesive. An adhesive having improved connection reliability can be obtained. In addition, according to the present invention, when the chip is actually mounted on the LCD panel, since the deflection of the substrate is reduced, its adverse effect on the display quality can be suppressed. That is, it is possible to suppress occurrence of display unevenness due to a change in the gap of the display surface due to the occurrence of warping.
因此,本发明的电路连接用粘结剂最适用于仅仅将LCB板和TAB,TAB和印刷基板,LCD板和IC芯片,IC芯片和印刷基板在连接时的加压方向进行电连接。Therefore, the adhesive for circuit connection of the present invention is most suitable for electrically connecting only the LCB board and the TAB, the TAB and the printed board, the LCD board and the IC chip, and the IC chip and the printed board in the direction of pressure at the time of connection.
具体实施方式 Detailed ways
本发明的粘结剂在粘结剂中以分散状态含有平均粒径为10μm以下的橡胶粒子。含有橡胶粒子的目的是为了缓解可靠性试验中所产生的内部应力,防止粘结剂的剥离,降低基板的挠曲。The binder of the present invention contains rubber particles having an average particle diameter of 10 μm or less in a dispersed state in the binder. The purpose of containing rubber particles is to relieve the internal stress generated in the reliability test, prevent the peeling of the adhesive, and reduce the deflection of the substrate.
橡胶粒子的平均粒径最好是0.1~10μm,尤其好的是0.1~5μm。另外,特别好的是橡胶粒子在平均粒径以下的粒子占粒径分布的80%以上。The average particle diameter of the rubber particles is preferably 0.1 to 10 μm, particularly preferably 0.1 to 5 μm. In addition, it is particularly preferable that rubber particles having an average particle diameter or less account for 80% or more of the particle diameter distribution.
作为本发明的橡胶粒子只要是玻璃化转化温度在25℃以下的橡胶粒子均可,没有特别限定,例如:可以使用丁二烯橡胶,聚丙烯橡胶,丁苯橡胶,丁腈橡胶,硅橡胶等。The rubber particles of the present invention are not particularly limited as long as they are rubber particles with a glass transition temperature below 25°C. For example, butadiene rubber, polypropylene rubber, styrene-butadiene rubber, nitrile rubber, silicone rubber, etc. can be used. .
在上述的橡胶粒子中,最好使用硅橡胶粒子,因为其除了耐溶剂性优良外,分散性也很好。硅橡胶粒子可以使用以下方法制得,即:将硅烷化合物或甲基三烷氧基硅烷及/或其部分水解缩合物加到使用苛性纳或氨等碱性物质将PH值调整到9以上的乙醇水溶液中之后,再使其水解缩聚的方法或者使其与有机硅氧烷共聚的方法。另外,为了提高反应性树脂的分散性,最好使用在分子端部或者分子内支链中含有氢氧基或环氧基,酮亚胺,羧基,巯基等官能团的硅微粒子。Among the above-mentioned rubber particles, silicone rubber particles are preferably used because they are excellent in dispersibility in addition to being excellent in solvent resistance. Silicone rubber particles can be prepared by adding silane compound or methyltrialkoxysilane and/or its partial hydrolyzed condensate to an alkaline substance such as caustic soda or ammonia to adjust the pH value to above 9. After being immersed in an aqueous ethanol solution, it is hydrolyzed and polycondensed, or it is copolymerized with organosiloxane. In addition, in order to improve the dispersibility of the reactive resin, it is best to use silicon microparticles containing functional groups such as hydroxyl groups, epoxy groups, ketimine groups, carboxyl groups, and mercapto groups at molecular ends or intramolecular branches.
在用偶合剂对橡胶粒子表面进行处理的情况下,更好的是提高对反应性树脂的分散性。In the case of treating the surface of the rubber particles with a coupling agent, it is more preferable to improve the dispersibility to the reactive resin.
橡胶粒子在室温(25℃)下的弹性率最好是1~100Mpa,考虑到橡胶粒子的分散性或降低连接时界面的应力更好的是1~30Mpa。但是,当选择反应性树脂的时候,应考虑粘结剂的反应性和发热量决定。The elastic modulus of the rubber particles at room temperature (25° C.) is preferably 1 to 100 MPa, more preferably 1 to 30 MPa in consideration of dispersion of the rubber particles or reduction of interfacial stress during connection. However, when choosing a reactive resin, the reactivity and heat generation of the binder should be considered.
橡胶粒子相对于粘结剂组合物的使用量最好是相对于粘结剂组合物为100重量份时其为10~100重量份。The amount of the rubber particles used relative to the binder composition is preferably 10 to 100 parts by weight relative to 100 parts by weight of the binder composition.
作为本发明所使用的反应性树脂可以是例如,环氧树脂和潜在性固化剂的混合物,自由基反应性树脂和有机过氧化物的混合物。The reactive resin used in the present invention may be, for example, a mixture of an epoxy resin and a latent curing agent, a mixture of a radical reactive resin and an organic peroxide.
作为环氧树脂可以使用以下例子中的单独一种或将两种以上混合使用,但不受这些例子的限制。例如:由氯甲基氧丙烷和双酚A,F或AD衍生的双酚型环氧树脂;由氯甲基氧丙烷和线性酚醛清漆树脂(フユノルノボラツク)或甲酚-可溶性酚醛清漆树脂(クレゾ—ルノボラツク)衍生的环氧酚醛清漆树脂,具有含萘环结构的萘系环氧树脂,以及在缩水甘油氨络合物,缩水甘油醚,联苯或者脂环式等的一个分子中具有二个以上的缩水甘油基的环氧化合物。As the epoxy resin, one of the following examples may be used alone or two or more of them may be used in combination, but it is not limited to these examples. For example: bisphenol-type epoxy resins derived from chloromethyloxypropane and bisphenol A, F or AD; (クレゾ-ルノボラツク) derived epoxy novolac resin, a naphthalene-based epoxy resin with a naphthalene ring structure, and a glycidyl ammonia complex, glycidyl ether, biphenyl or alicyclic type, etc. in one molecule An epoxy compound with two or more glycidyl groups.
作为这些环氧树脂,为了防止电子迁移最好使用将杂质离子例如Na+,Cl-或者水解性氯的浓度降低到300PPM以下的高纯度品。As these epoxy resins, it is preferable to use high-purity products whose concentration of impurity ions such as Na + , Cl - or hydrolyzable chlorine is reduced to 300PPM or less in order to prevent electron migration.
作为潜在性固化剂可举例如下,但不受这些具体例子的限制。例如:咪唑系,酰肼系,三氟化硼~酰胺的络合物,锍盐,胺化酰亚胺,聚胺的盐以及双氰胺等。Examples of latent curing agents include the following, but are not limited to these specific examples. For example: imidazole-based, hydrazide-based, complexes of boron trifluoride-amide, sulfonium salts, aminated imides, polyamine salts, and dicyandiamide.
在这些潜在性固化剂中,锍盐的固化温度在60℃以上而其固化反应完成60%的温度在160℃以下,因其低温反应性优良,有效寿命长而最适用。作为锍盐,特别适用的是用一般式(1)表示的锍盐Among these latent curing agents, the curing temperature of sulfonium salt is above 60°C and the temperature at which 60% of its curing reaction is completed is below 160°C. It is most suitable for its excellent low-temperature reactivity and long effective life. As sulfonium salts, particularly suitable are sulfonium salts represented by the general formula (1)
但是,在式(1)中,R1为电子吸引性的基,例如:亚硝基,羰基,羧基,氰基、三烷基铵,甲氟基;R2及R3为电子供给性的基,例如:氨基,氢氧基,甲基;Y为非求核性阴离子,例如:六氟砷酸盐,六氟锑酸盐。However, in formula (1), R1 is an electron-attracting group, such as: nitroso, carbonyl, carboxyl, cyano, trialkylammonium, methyl fluoride; R2 and R3 are electron-donating groups, such as : amino, hydroxyl, methyl; Y is a non-nuclear anion, for example: hexafluoroarsenate, hexafluoroantimonate.
锍盐相对于环氧树脂的使用量最好是2~20重量份。The usage-amount of a sulfonium salt is preferably 2-20 weight part with respect to an epoxy resin.
在本发明的粘结剂中最好混入分散导电粒子,其目的是为了弥补芯片的凸缘或基板电极的高度误差而使粘结剂具有各向异性的异电性。It is preferable to mix dispersed conductive particles in the adhesive of the present invention, the purpose of which is to make the adhesive have anisotropic heteroelectricity in order to compensate for height errors of chip bumps or substrate electrodes.
反应性树脂相对于粘结剂的使用量最好是相对于粘结剂100重量份为20~100重量份。The amount of the reactive resin used with respect to the binder is preferably 20 to 100 parts by weight relative to 100 parts by weight of the binder.
作为本发明的导电粒子可以使用例如Au,Ag,Cu,焊料等金属粒子,但不受这些例子的限制。最好的是在聚苯乙烯等高分子球形芯材的表面设置Ni,Cu,Au,焊料等导电层,另外,在导电粒子的表面,还可以形成Sn,Au焊料等表面层。进一步形成表面层的目的是为了通过同底层(导电层)的结合提高导电性。导电粒子的粒径必须比基板上的电极的最小间隔还小。另外,在电极有高度误差的情况下,导电粒子的粒径最好比高度误差要大,具体的是1~10μm。另外,分散在粘结剂中的导电粒子量最好是0.1~30体积%,尤其好的是0.2~15体积%。As the conductive particles of the present invention, metal particles such as Au, Ag, Cu, and solder can be used, but are not limited to these examples. It is best to set Ni, Cu, Au, solder and other conductive layers on the surface of polystyrene and other polymer spherical core materials. In addition, on the surface of conductive particles, surface layers such as Sn and Au solder can also be formed. The purpose of further forming the surface layer is to improve conductivity by combining with the bottom layer (conductive layer). The particle size of the conductive particles must be smaller than the minimum interval between electrodes on the substrate. In addition, when the electrode has a height error, the particle size of the conductive particles is preferably larger than the height error, specifically 1-10 μm. In addition, the amount of conductive particles dispersed in the binder is preferably 0.1 to 30% by volume, particularly preferably 0.2 to 15% by volume.
在本发明的粘结剂中可以混入分散无机充填材料。A dispersed inorganic filler may be mixed in the binder of the present invention.
作为本发明中可使用的无机充填材料可列举如下材料,但不受这些材料的限制,例如:熔融的二氧化硅、晶体二氧化硅、硅酸钙、氧化铝、碳酸钙等粉末。Examples of inorganic fillers usable in the present invention include, but are not limited to, powders such as fused silica, crystalline silica, calcium silicate, alumina, and calcium carbonate.
无机充填材料的使用量最好是相对于粘结剂组合物100重量份为10~200重量份。尤其好的是20~90重量份。为了降低热膨胀系数,无机充填材料的使用量越大效果越好;然而,用量过大有产生粘结性降低或者电极间导电不良的倾向,用量过小则有不能充分降低热膨胀系数的倾向。The amount of the inorganic filler used is preferably 10 to 200 parts by weight relative to 100 parts by weight of the binder composition. Especially preferably, it is 20-90 weight part. In order to reduce the coefficient of thermal expansion, the greater the amount of inorganic filler used, the better the effect; however, if the amount is too large, the adhesion will decrease or the conductivity between electrodes will be poor, and if the amount is too small, the coefficient of thermal expansion will not be sufficiently reduced.
无机充填材料的平均粒径从防止连接处导电不良的观点来看最好在3μm以下。另外,从防止在连接时树脂的流动性降低的观点和防止对芯片的钝化膜的损伤的观点来看,最好使用球状填料作为无机充填材料。无机充填材料无论粘结剂是否含有导电粒子都可混入、分散。The average particle size of the inorganic filler is preferably 3 μm or less from the viewpoint of preventing poor electrical conduction at the junction. In addition, it is preferable to use a spherical filler as the inorganic filler from the viewpoint of preventing a decrease in fluidity of the resin during connection and preventing damage to the passivation film of the chip. Inorganic fillers can be mixed and dispersed regardless of whether the binder contains conductive particles or not.
为了更容易形成薄膜,还可以将苯氧基树脂,聚脂树脂,聚酰胺树脂等热塑性树脂(以下称为薄膜形成性高分子)加入到本发明的粘结剂中。这些薄膜形成性高分子具有缓解反应性树脂固化时的应力的效果。尤其好的是当其具有氢氧基等官能团时,薄膜形成性高分子有利于提高粘结性。In order to form a film more easily, thermoplastic resins such as phenoxy resins, polyester resins, and polyamide resins (hereinafter referred to as film-forming polymers) may also be added to the binder of the present invention. These film-forming polymers have the effect of relieving stress during curing of the reactive resin. It is especially preferable that the film-forming polymer contributes to improvement of adhesion when it has a functional group such as a hydroxyl group.
为了将本发明的粘结剂做成薄膜形状可以采用以下的方法进行,即:将至少由这些反应性树脂,潜在性固化剂组成的粘结剂组合物溶解或者分散在有机溶剂中使其成液体状,然后涂覆在可以剥离的基体材料上,在固化剂的活性温度以下除去溶剂即可。这时所用的溶剂最好是有利于提高材料溶解性的芳香族烃系和含氧系的混合溶剂。In order to make the adhesive of the present invention into a film shape, the following method can be adopted, that is, the adhesive composition composed of these reactive resins and latent curing agents is dissolved or dispersed in an organic solvent to form a thin film. Liquid, and then coated on the base material that can be peeled off, the solvent can be removed below the active temperature of the curing agent. The solvent used at this time is preferably a mixed solvent of an aromatic hydrocarbon system and an oxygen-containing system that is beneficial to improve the solubility of the material.
本发明的粘结薄膜可以通过调整反应性树脂,橡胶粒子,薄膜形成性高分子材料等的使用量使薄膜的弹性率(25℃)为50~1000MPa,最好是70~500MPa。粘结薄膜的弹性率一超过1000MPa就不能将薄膜粘贴到电路板上,在将薄膜按规定的宽度切断加工时存在粘结薄膜由基体材料薄膜上剥离的倾向。另外,若弹性率不足50MPa,当同基体材料薄膜一起卷成10M以上的卷状物时,存在粘结薄膜粘贴在基体材料薄膜的背面而难于进行将粘结薄膜粘贴到电路基板上的作业的倾向。另外,这时,由于低分子的反应性树脂的含量增多,在压接时存在产生许多孔隙的倾向。再有,粘结薄膜的弹性率(储存弹性率:测定用薄膜厚度:10μm)可以用粘弹性测定装置(升温速度:10℃/分,频率:1Hz)求得。The adhesive film of the present invention can have an elastic modulus (25° C.) of 50-1000 MPa, preferably 70-500 MPa, by adjusting the amount of reactive resin, rubber particles, and film-forming polymer materials used. When the elastic modulus of the adhesive film exceeds 1000 MPa, the film cannot be attached to the circuit board, and the adhesive film tends to be peeled off from the base material film when the film is cut to a predetermined width. In addition, if the elastic modulus is less than 50 MPa, when the base material film is rolled into a roll of 10M or more, the adhesive film will stick to the back of the base material film, making it difficult to stick the adhesive film to the circuit board. tendency. In addition, at this time, since the content of the low-molecular reactive resin increases, many voids tend to be generated during crimping. In addition, the elastic modulus of the adhesive film (storage elastic modulus: film thickness for measurement: 10 μm) can be obtained with a viscoelasticity measuring device (heating rate: 10° C./min., frequency: 1 Hz).
粘结剂的反应性可以用DSC(升温速度:10℃/分)测定。本发明的粘结剂使用DSC的发热开始温度是60℃以上,粘结剂的固化反应的80%的结束温度在260℃以下。通过选择加入粘结剂中的反应性树脂进行调整使其达到这些温度。再有,固化反应的60%的结束温度最好在160℃以下。The reactivity of the binder can be measured by DSC (rate of temperature increase: 10° C./minute). The heating start temperature of the adhesive of the present invention using DSC is above 60°C, and the end temperature of 80% of the curing reaction of the adhesive is below 260°C. Adjustments to these temperatures are made by the choice of reactive resins added to the binder. In addition, the temperature at which 60% of the curing reaction is completed is preferably 160°C or lower.
基于本发明的粘结剂的固化反应的发热量也可以用DSC(升温速度:10℃/分)求得。发热量最好为50~140焦耳/克,尤其好的是60~120焦耳/克,特别好的是60~100焦耳/克,通过改变反应性树脂,橡胶粒子,薄膜形成性高分子等的使用量进行调整。粘结剂的发热量若超过140焦耳/克,则由于粘结剂的固化收缩力及弹性率的增大等因素使内部应力增大,电路之间连接时,存在电路基板挠曲导致连接可靠性降低或者电子零件的特性降低等倾向。另外,在发热量不足50焦耳/克时,存在由于粘结剂的固化不充分,导致粘结性及连接可靠性降低的倾向。The calorific value of the curing reaction of the adhesive of the present invention can also be obtained by DSC (rate of temperature increase: 10°C/min). The calorific value is preferably 50-140 J/g, especially 60-120 J/g, especially 60-100 J/g. By changing the reactive resin, rubber particles, film-forming polymers, etc. The amount used is adjusted. If the calorific value of the adhesive exceeds 140 joules/g, the internal stress will increase due to factors such as the curing shrinkage force of the adhesive and the increase in elastic modulus. When connecting circuits, there will be circuit board flexures, resulting in reliable connections. There is a tendency to reduce the performance or the characteristics of electronic parts. In addition, when the calorific value is less than 50 joules/g, there is a tendency for adhesiveness and connection reliability to decrease due to insufficient curing of the adhesive.
DSC是将供给或除去热量的零位法作为测定原理使得在测定温度范围内不断地消除同没有发热、吸热的标准试样的温度差,也可以使用市售的测定装置进行测定。粘结剂的反应是发热反应,若以一定的升温速度升温,试样反应就产生热量。将该发热量输出到图表中,将基线作为基准,由发热曲线和基线求得所围的面积,将其作为发热量。以10℃/分的升温速度从室温(25℃)到300℃左右进行测定,求得上述的发热量。这些都是完全自动地进行的,若使用它可以很容易地进行。另外,固化反应的80%的结束温度可以由发热量的面积求得。DSC uses the zero point method of supplying or removing heat as the measurement principle to continuously eliminate the temperature difference with a standard sample that does not generate heat or absorb heat within the measurement temperature range. It can also be measured using a commercially available measurement device. The reaction of the binder is an exothermic reaction. If the temperature is raised at a certain heating rate, the reaction of the sample will generate heat. This calorific value is output to a graph, and the baseline is used as a reference, and the area enclosed by the calorific curve and the baseline is obtained, and this is regarded as a calorific value. Measurement was performed from room temperature (25°C) to about 300°C at a temperature increase rate of 10°C/min to obtain the above-mentioned calorific value. This is done completely automatically and can be easily done using it. In addition, the completion temperature of 80% of the curing reaction can be obtained from the area of the heat generation.
实施例一Embodiment one
将苯氧基树脂(ユニオンカ—バイド社制,PKHC)50克溶解在醋酸乙酯115克中,得到30重量%的苯氧基树脂溶液。In 115 g of ethyl acetate, 50 g of phenoxy resin (manufactured by Unionka Bird Co., Ltd., PKHC) was dissolved to obtain a 30% by weight phenoxy resin solution.
作为硅酮,在20℃将甲基三甲氧基硅烷加入到以300转/分钟搅拌的PH值为12的乙醇水溶液中使其水解、缩合,制得25℃的储存弹性率为8MPa,平均粒径为2μm的球形微粒子。As silicone, add methyltrimethoxysilane to ethanol aqueous solution with pH value of 12 stirred at 300 rpm at 20°C to hydrolyze and condense to obtain a storage elastic modulus of 8 MPa at 25°C and an average particle size Spherical microparticles with a diameter of 2 μm.
将含有苯氧基树脂溶液(以固态重量比苯氧基树脂45克)硅酮微粒子30克,微胶囊型潜在性固化剂的液体环氧树脂(环氧当量185,旭化成工业株式会社制,ノバキユアHX--3941)20克,双酚A型环氧树脂(环氧当量180)50克混合,将在聚苯乙烯系核芯(直径:5μm)的表面形成Au层的导电粒子以6体积%分散在其中从而制得薄膜涂覆用溶液。随后,用涂覆装置将该溶液涂覆到对厚度为50μm的薄膜的单面进行表面处理的PET(聚对苯二甲酸乙酯,基体材料薄膜,分离器)薄膜上,经70℃热风干燥10分钟,得到粘结剂层厚度为45μm的薄膜状粘结剂。关于该粘结剂,对反应开始时间,反应结束时间,固化反应的60%和80%的结束温度,直到固化反应的80%结束的DSC的发热量,以及直到固化反应完全结束的DSC的发热量及弹性率进行测定,其结果示于表1。30 grams of silicone microparticles containing phenoxy resin solution (45 grams of phenoxy resin by solid weight ratio), liquid epoxy resin of microcapsule type latent curing agent (epoxy equivalent 185, manufactured by Asahi Kasei Co., Ltd., Nobakuyua HX--3941) 20 grams, 50 grams of bisphenol A type epoxy resin (epoxy equivalent 180) are mixed, will form the conductive particle of Au layer on the surface of polystyrene core (diameter: 5 μ m) with 6 volume % dispersed therein to prepare a solution for film coating. Subsequently, the solution is coated on a PET (polyethylene terephthalate, base material film, separator) film with a thickness of 50 μm on one side of the film with a coating device, and dried by hot air at 70 ° C. After 10 minutes, a film-like adhesive having an adhesive layer thickness of 45 μm was obtained. Regarding the adhesive, the reaction start time, the reaction end time, the end temperature of 60% and 80% of the curing reaction, the heat generation of DSC until the end of 80% of the curing reaction, and the heat generation of DSC until the complete end of the curing reaction The heat and modulus of elasticity were measured, and the results are shown in Table 1.
其次,使用所得的薄膜状粘结剂如以下所示地将带金凸缘(面积80×80μm,间隔30μm,高度15μm,凸缘数288)的芯片(10×10mm,厚度500μm)同具有和芯片的电极相对应的电路电极的镀Ni/Au的Cu电路印刷板进行连接。Next, a chip (10×10 mm, thickness 500 μm) with gold bumps (area 80×80 μm, interval 30 μm, height 15 μm, number of bumps 288) was bonded to a chip (10×10 mm, thickness 500 μm) with the chip as follows using the obtained film-like adhesive. The electrodes corresponding to the circuit electrodes are connected to the Ni/Au plated Cu circuit printed board.
将薄膜状粘结剂(12×12mm)在80℃,1.0MPa(10公斤力/厘米2)的压力下粘贴在镀Ni/Au的Cu电路印刷板(电极高度20mm,厚度0.8mm),剥离分离器,使芯片的凸缘和镀Ni/Au的Cu电路印刷板(厚度0.8mm)的位置吻合。随后,在180℃,75克/每个凸缘,20秒的条件下由芯片上方进行加热、加压,从而实现本连接。Paste the film-like adhesive (12×12mm) on the Ni/Au-plated Cu circuit printed board (electrode height 20mm, thickness 0.8mm) at 80°C, under the pressure of 1.0MPa (10kg force/ cm2 ), peel off Separator, so that the position of the flange of the chip and the Cu circuit printed board (thickness 0.8mm) plated with Ni/Au coincide. Subsequently, heating and pressure were carried out from above the chip under the conditions of 180° C., 75 g/each flange, and 20 seconds, so as to realize the connection.
本连接后芯片的挠曲为1μm(向芯片方向凸起的挠曲)。另外,本连接后的连接阻抗,每个凸缘为最高15MΩ,平均为8MΩ,绝缘阻抗在188Ω以上。这些值即使在进行-55--125℃的抗热冲击试验1000次循环处理,PCT试验(121℃,0.2MPa(2个大气压))200小时,260℃钎焊浴中浸渍10秒钟后也没有变化,表明其良好的连接可靠性。The deflection of the chip after this connection was 1 μm (deflection convex toward the chip). In addition, the connection impedance after this connection is up to 15MΩ per flange, 8MΩ on average, and the insulation resistance is above 188Ω . These values are even after 1000 cycles of thermal shock resistance test at -55--125°C, PCT test (121°C, 0.2MPa (2 atmospheres)) for 200 hours, and immersion in 260°C brazing bath for 10 seconds. No change, indicating its good connection reliability.
实施例二Embodiment two
除了将10体积%的导电粒子分散在粘结剂中外,其余同实施例一相同,得到薄膜涂覆用溶液。Except that 10% by volume of conductive particles was dispersed in the binder, the rest was the same as that of Example 1 to obtain a film coating solution.
随后,使用涂覆装置将该溶液涂覆在对厚度为50μm的薄膜的单面进行表面处理的PET薄膜上,经70℃热风干燥10分钟,得到粘结剂层厚度为10μm的薄膜状粘结剂a。Subsequently, use the coating device to coat the solution on the surface-treated PET film on one side of the film with a thickness of 50 μm, and dry it with hot air at 70°C for 10 minutes to obtain a film-like bond with an adhesive layer thickness of 10 μm. Agent a.
随后,在上述制作涂覆用溶液的过程中,除了没有将形成Au层的导电离子分散在溶液中这一点外,使用与上相同的方法制作薄膜涂覆用溶液,使用涂覆装置将该溶液涂覆在对厚度为50μm的薄膜的单面进行表面处理的PET薄膜上,经70℃热风干燥10分钟,得到粘结剂层厚度为15μm的薄膜状粘结剂b。再将所得到的薄膜状粘结剂a和b在40℃一边加热,一边用辊式层压装置制成层压的二层结构的各向导性的导电薄膜。Subsequently, in the process of preparing the solution for coating as described above, except that the conductive ions forming the Au layer were not dispersed in the solution, the solution for thin film coating was prepared by the same method as above, and the solution was prepared using a coating device. Coated on a PET film surface-treated on one side of a film with a thickness of 50 μm, and dried with hot air at 70° C. for 10 minutes to obtain a film-shaped adhesive b with an adhesive layer thickness of 15 μm. Further, the obtained film-like adhesives a and b were heated at 40° C., and were laminated with a roll laminator to form an anisotropic conductive film with a two-layer structure.
关于这种粘结剂,同实施例一同样地进行测定,其结果示于表1。About this binder, it measured similarly to Example 1, and the result is shown in Table 1.
其次,使用所制得的各向异向导电薄膜,如以下所示地将带金凸缘(面积:50×50μm,间隔:20μm,高度:15μm,凸缘数362)的芯片(1.7×17mm,厚度:500μm)同带ITO电路的玻璃基板(厚度:1.1mm)进行连接。将各向异性导电薄膜(2×20mm)在80℃,1MPa(10公斤力/厘米2)的压力下粘贴到带ITO电路的玻璃基板上后,剥离分离器,使芯片的凸缘和带ITO电路的玻璃基板的位置吻合。随后,在190℃,40克/每个凸缘,10秒的条件下由芯片上方进行加热,加压,从而实现本连接。本连接后芯片的挠曲为2.5μm。另外,连接阻抗每一个凸缘为最高80MΩ,平均为30MΩ,绝缘阻抗在108Ω以上。这些值即使在进行-40--100℃的抗热冲击试验1000次循环处理,高温,高湿(85℃,85%RH,1000小时)试验后也没有变化,表明其良好的连接可靠性。Next, using the obtained anisotropic conductive film, chips (1.7×17 mm, thickness: 1.7×17 mm, thickness: 1.7×17 mm, thickness: : 500μm) is connected to a glass substrate (thickness: 1.1mm) with an ITO circuit. After pasting the anisotropic conductive film (2×20mm) on the glass substrate with the ITO circuit under the pressure of 1MPa (10kg/ cm2 ) at 80°C, peel off the separator to make the flange of the chip and the ITO circuit The position of the glass substrate of the circuit coincides. Subsequently, under the conditions of 190° C., 40 g/each flange, and 10 seconds, heating and pressing are carried out from above the chip, so as to realize this connection. The deflection of the chip after this connection was 2.5 μm. In addition, the connection impedance is 80MΩ at the highest per flange, 30MΩ on average, and the insulation resistance is above 10 8 Ω. These values do not change even after 1000 cycles of thermal shock resistance test at -40--100 °C, high temperature, high humidity (85 °C, 85% RH, 1000 hours) test, indicating its good connection reliability.
实施例三Embodiment three
将苯氧基树脂(ユニオンカ—バイド社制,PKHC)50克,溶解在醋酸乙酯115克中,制得30%的溶液。50 g of phenoxy resin (manufactured by Unionka Bird, PKHC) was dissolved in 115 g of ethyl acetate to prepare a 30% solution.
将具有固态重量比的苯氧基树脂60克,20重量%的平均粒径为0.2μm的丙烯酸粒子(储存弹性率为3MPa)分散在其中的双酚A型环氧树脂(环氧当量180)25克,双酚A型固态环氧树脂(环氧当量:185)5克,P~醋酸苯基甲磺酸盐(非求核性阴离子:六氟锑酸盐)3克混合,再将在聚苯乙烯系核芯(直径:3μm)的表面形成金层的10体积%的导电粒子分散混合于其中而制得薄膜涂覆用溶液。Bisphenol A type epoxy resin (epoxy equivalent 180) in which 60 g of phenoxy resin having a solid weight ratio and 20% by weight of acrylic particles (storage modulus of elasticity 3 MPa) having an average particle diameter of 0.2 μm are dispersed 25 grams, 5 grams of bisphenol A type solid epoxy resin (epoxy equivalent: 185), 3 grams of P~acetate phenyl methanesulfonate (non-nuclear anion: hexafluoroantimonate) are mixed, and then mixed in 10% by volume of conductive particles forming a gold layer on the surface of a polystyrene-based core (diameter: 3 μm) was dispersed and mixed therein to prepare a thin film coating solution.
随后,使用涂覆装置将该溶液涂覆在将厚度为50μm的薄膜的单面进行表面处理后的PET薄膜上,在70℃经热风干燥10分钟,从而制得粘结剂层的厚度为10μm的薄膜状粘结剂c。Subsequently, the solution was coated on a surface-treated PET film on one side of a film with a thickness of 50 μm using a coating device, and dried by hot air at 70° C. for 10 minutes to obtain an adhesive layer with a thickness of 10 μm. film-like adhesive c.
随后,在上述制作薄膜涂覆用溶液的过程中,除了没有将形成Au层的导电粒子分散在溶液中这一点外,其余用同上相同的方法制得薄膜涂覆用溶液,使用涂覆装置将该溶液涂覆到对厚度为50μm的薄膜的单面进行表面处理后的PET薄膜上,在70℃经热风干燥10分钟,从而制得粘结剂层的厚度为15μm的薄膜状粘结剂d。Subsequently, in the above-mentioned process of making the solution for thin film coating, except that the conductive particles forming the Au layer were not dispersed in the solution, the same method as above was used to prepare the solution for thin film coating. This solution is coated on the PET film after surface treatment on one side of the film with a thickness of 50 μm, and dried by hot air at 70°C for 10 minutes to obtain a film-like adhesive with an adhesive layer thickness of 15 μm. .
将所制得的薄膜状粘结剂c和d在40℃一边加热,一边用辊式层压装置制作层压成二层结构的各向异性导电薄膜。关于该粘结薄膜同实施例一同样地进行测定。其结果示于表1。While heating the obtained film-like adhesives c and d at 40° C., an anisotropic conductive film laminated in a two-layer structure was produced with a roll laminator. About this adhesive film, it measured similarly to Example 1. The results are shown in Table 1.
其次,使用所制得的各向异性导电薄膜,如以下所示将带金凸缘(面积:50×50μm,间隔:20μm,高度:15μm,凸缘数362)的芯片(1.7×17mm,厚度:500μm)同带ITO电路的玻璃基板(厚度:1.1mm)进行连接。将各向异性导电薄膜(2×20mm)在80℃,以1MPA(10公斤力/厘米2)的压力粘贴到带ITO电路的玻璃基板上,剥离分离器,使芯片的凸缘和带ITO电路的玻璃基板的位置吻合。随后,在150℃,40克/每个凸缘,10秒的条件下由芯片上方进行加热、加压,从而实现本连接。本连接后芯片的挠曲为1.5μm。另外,连接阻抗每一个凸缘最高为50MΩ,平均为20MΩ,饱缘阻抗在108Ω以上,这些值即使经-40~100℃抗热冲击试验1000次循环处理,高温、高湿(85℃/85%RH,1000小时)试验后也没有变化,表明良好的连接可靠性。Next, using the prepared anisotropic conductive film, chips (1.7×17 mm, thickness: 500 μm) with gold bumps (area: 50×50 μm, interval: 20 μm, height: 15 μm, number of bumps: 362) were fabricated as follows ) is connected to a glass substrate (thickness: 1.1mm) with an ITO circuit. Paste the anisotropic conductive film (2×20mm) on the glass substrate with ITO circuit at 80°C with a pressure of 1MPA (10kg force/ cm2 ), peel off the separator, and make the flange of the chip and the ITO circuit The position of the glass substrate matches. Subsequently, heating and pressure were carried out from above the chip under the conditions of 150° C., 40 g/each flange, and 10 seconds, so as to realize this connection. The deflection of the chip after this connection was 1.5 μm. In addition, the maximum connection impedance of each flange is 50MΩ, the average is 20MΩ, and the saturated edge resistance is above 10 8 Ω. Even if these values are subjected to 1000 cycles of thermal shock resistance tests at -40 to 100°C, high temperature and high humidity (85°C /85%RH, 1000 hours) test also showed no change, indicating good connection reliability.
比较例一Comparative example one
使用没有混合橡胶粒子的各向异性导电薄膜FC--110A(日立化成工业株式会社制,膜厚:45μm)同实施例一进行比较试验,其结果示于表1。Table 1 shows the results of a comparison test with Example 1 using an anisotropic conductive film FC-110A (manufactured by Hitachi Chemical Industries, Ltd., film thickness: 45 μm) not mixed with rubber particles.
其次,使用上述薄膜状粘结剂,如以下所示,将带金凸缘(面积:80×80μm,间隔:30μm,高度:15μm,凸缘数288)的芯片(10×10mm,厚度:500μm)同镀Ni/Au的Cu电路印刷板进行连接。将薄膜粘结剂(12×12mm)在80℃,1MPa(10公斤/厘米2)的压力下粘贴到镀Ni/Au的Cu电路印刷板上(电极高度:20μm,厚度:0.8mm),剥离分离器后,使芯片的凸缘同镀Ni/Au的Cu电路印刷板的位置吻合。随后,在190℃,75克/每个凸缘,10秒的条件下由芯片上方进行加热,加压,从而实现本连接。本连接后芯片的挠曲为7.2μm(向芯片方向凸起的挠曲)。另外,本连接后的连接阻抗为每一个凸缘最高为20MΩ,平均为10MΩ,绝缘阻抗在108Ω以上。连接阻抗经—55~125℃的抗热冲击试验1000次循环处理,PCT试验(121℃,2MPA(2个大气压))200小时,260℃的钎焊浴浸渍10秒钟后除了增大之外还产生一些连接不良的情况。Next, using the above-mentioned film-like adhesive, a chip (10×10 mm, thickness: 500 μm) with gold bumps (area: 80×80 μm, pitch: 30 μm, height: 15 μm, number of bumps: 288) was placed as follows Ni/Au plated Cu circuit printed board for connection. Paste the film adhesive (12×12mm) on the Ni/Au-plated Cu circuit printed board (electrode height: 20μm, thickness: 0.8mm) at 80°C, under the pressure of 1MPa (10kg/ cm2 ), peel off After the separator, align the flange of the chip with the position of the Ni/Au-plated Cu circuit printed board. Subsequently, under the conditions of 190° C., 75 g/each flange, and 10 seconds, heating and pressing are carried out from above the chip, so as to realize this connection. The deflection of the chip after this connection was 7.2 μm (deflection convex toward the chip). In addition, the connection impedance after this connection is a maximum of 20 MΩ per flange, an average of 10 MΩ, and an insulation resistance of 10 8 Ω or more. The connection impedance has been subjected to 1000 cycles of thermal shock resistance test at -55 to 125°C, PCT test (121°C, 2MPA (2 atmospheres)) for 200 hours, and immersion in a brazing bath at 260°C for 10 seconds, in addition to increasing Also produced some cases of poor connection.
比较例二Comparative example two
使用将由厚度为8μm的含有导电粒子的薄膜层和厚度为15μm的不含导电粒子的薄膜层构成的两层结构的不含橡胶粒子的各向异性导电薄膜AC-8401(日立化成工业株式会社制,膜厚:23μm)相对实施例二进行比较试验,其结果示于表1。Anisotropic conductive film AC-8401 (manufactured by Hitachi Chemical Industry Co., Ltd. , Film thickness: 23 μm) comparative test was carried out relative to Example 2, and the results are shown in Table 1.
其次,使用该各向异性导电薄膜,如以下所述将带金凸缘(面积:50×50μm,间隔20μm,高度:15μm,凸缘数362)的芯片(1.7×17mm,厚度:500μm)和带ITO电路的玻璃基板(厚度:1.1mm)进行连接。将各向异性导电薄膜(2×20mm)在80℃,以1MPa的压力粘贴到带ITO电路的玻璃基板上后,剥离分离器,使芯片的凸缘和带ITO电路的玻璃基板的位置吻合。随后,在190℃,40克/每个凸缘,10秒的条件下由芯片上方进行加热、加压,实现本连接。本连接的芯片的挠曲为8.2μm,同实施例二相比挠曲增大。Next, using this anisotropic conductive film, a chip (1.7×17 mm, thickness: 500 μm) with gold bumps (area: 50×50 μm, interval 20 μm, height: 15 μm, number of bumps: 362) and a chip with ITO The glass substrate (thickness: 1.1mm) of the circuit is connected. After pasting the anisotropic conductive film (2×20mm) on the glass substrate with ITO circuit at 80°C with a pressure of 1 MPa, the separator was peeled off to align the flange of the chip with the glass substrate with ITO circuit. Subsequently, heat and pressurize from above the chip under the conditions of 190° C., 40 g/each flange, and 10 seconds, to realize the connection. The deflection of the chip connected in this case was 8.2 μm, and the deflection was larger than that of Example 2.
表1Table 1
Claims (6)
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Publication number | Priority date | Publication date | Assignee | Title |
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JPH1112545A (en) | 1997-06-25 | 1999-01-19 | Hitachi Chem Co Ltd | Bonding film for insulating layer |
JPH1150032A (en) | 1997-08-04 | 1999-02-23 | Hitachi Chem Co Ltd | Connection member for circuit and circuit board |
JPH1161088A (en) | 1997-08-25 | 1999-03-05 | Hitachi Chem Co Ltd | Adhesive for connecting circuit member |
JPH11246742A (en) | 1998-02-27 | 1999-09-14 | Hitachi Chem Co Ltd | Paste composition and semiconductor device prepared by using same |
JP2001123143A (en) * | 1999-10-27 | 2001-05-08 | Hitachi Chem Co Ltd | Insulation film for additive process printed circuit board |
CN1310848A (en) * | 1999-04-01 | 2001-08-29 | 三井化学株式会社 | Anisotropically conductive paste |
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JPH1112545A (en) | 1997-06-25 | 1999-01-19 | Hitachi Chem Co Ltd | Bonding film for insulating layer |
JPH1150032A (en) | 1997-08-04 | 1999-02-23 | Hitachi Chem Co Ltd | Connection member for circuit and circuit board |
JPH1161088A (en) | 1997-08-25 | 1999-03-05 | Hitachi Chem Co Ltd | Adhesive for connecting circuit member |
JPH11246742A (en) | 1998-02-27 | 1999-09-14 | Hitachi Chem Co Ltd | Paste composition and semiconductor device prepared by using same |
CN1310848A (en) * | 1999-04-01 | 2001-08-29 | 三井化学株式会社 | Anisotropically conductive paste |
JP2001123143A (en) * | 1999-10-27 | 2001-05-08 | Hitachi Chem Co Ltd | Insulation film for additive process printed circuit board |
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