TWI398880B - Circuit connection material and circuit connection structure - Google Patents
Circuit connection material and circuit connection structure Download PDFInfo
- Publication number
- TWI398880B TWI398880B TW098122278A TW98122278A TWI398880B TW I398880 B TWI398880 B TW I398880B TW 098122278 A TW098122278 A TW 098122278A TW 98122278 A TW98122278 A TW 98122278A TW I398880 B TWI398880 B TW I398880B
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- circuit
- conductive particles
- particles
- conductive
- electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/04—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation using electrically conductive adhesives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- 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
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Abstract
Description
本發明係關於一種電路連接材料及電路連接構造體。The present invention relates to a circuit connecting material and a circuit connecting structure.
使相對向之電路進行加熱、加壓,並使加壓方向之電極間電性連接之電路連接材料,例如,使導電粒子分散於環氧系接著劑或丙烯酸系接著劑之異方導電性黏著薄膜,係已廣泛使用於主要驅動液晶顯示器(LCD)之半導體被搭載之TCP(Tape Carrier Package)或COF(Chip On Flex)與LCD面板、或TCP或COF與印刷電路板之電性連接。A circuit connecting material that heats and presses the opposing circuit and electrically connects the electrodes in the pressurizing direction, for example, disperses the conductive particles in an anisotropic conductive adhesive of an epoxy-based adhesive or an acrylic adhesive. The film is widely used in electrical connection between a TCP (Tape Carrier Package) or a COF (Chip On Flex) on which a semiconductor that mainly drives a liquid crystal display (LCD) is mounted, and an LCD panel, or a TCP or COF, and a printed circuit board.
又,在最近,使半導體以面朝下直接封裝於LCD面板或印刷電路板時,非習知之線黏合法,亦可採用於薄型化或窄節距連接有利之覆晶封裝,此處,異方導電性黏著薄膜亦可使用來作為電路連接材料(例如,參照專利文獻1~4)。Moreover, recently, when the semiconductor is directly packaged face down on the LCD panel or the printed circuit board, the conventional wire bonding method can also be used for the flip chip package which is advantageous for thinning or narrow pitch connection. A square conductive adhesive film can also be used as a circuit connecting material (for example, refer to Patent Documents 1 to 4).
又,近年,伴隨LCD模組的COF化或微線距化,使用電路連接材料之連接時,於相鄰之電極間產生短路之問題仍存在。此等之對策,有於接著劑成分中分散絕緣粒子而防止短路之技術(例如,參照專利文獻5~9)。Further, in recent years, with the COF or micro-coil of the LCD module, when a connection of circuit connecting materials is used, a problem of short-circuiting between adjacent electrodes still exists. In the countermeasures, the insulating particles are dispersed in the adhesive component to prevent short-circuiting (for example, refer to Patent Documents 5 to 9).
又,基板黏著於由絕緣性有機物或玻璃所構成之配線構件、或於表面之至少一部分具備選自氮化矽、聚矽氧樹脂及聚醯亞胺樹脂之至少一種的配線構件等,故有於接著 劑成分含有聚矽氧粒子之技術(例如,參照專利文獻10)。又,為降低依黏著後之熱膨脹率差的內部應力,有於接著劑分散橡膠粒子之技術(例如,參照專利文獻11)。Further, the substrate is adhered to a wiring member made of an insulating organic material or glass, or a wiring member including at least one selected from the group consisting of tantalum nitride, polyoxynitride resin, and polyimide resin on at least a part of the surface. Next The agent component contains a technique of polyfluorene oxide particles (for example, refer to Patent Document 10). In addition, in order to reduce the internal stress which is inferior to the thermal expansion coefficient after adhesion, there is a technique in which rubber particles are dispersed by an adhesive (for example, refer to Patent Document 11).
進一步,就防止電路間之短路的方法,有使用於具有絕緣性之皮膜被覆表面之導電粒子的技術(例如,參照專利文獻12及13)。Further, as a method for preventing a short circuit between circuits, there is a technique of using conductive particles on an insulating coating film surface (for example, refer to Patent Documents 12 and 13).
專利文獻1:特開昭59-120436號公報Patent Document 1: JP-A-59-120436
專利文獻2:特開昭60-191228號公報Patent Document 2: JP-A-60-191228
專利文獻3:特開平01-251787號公報Patent Document 3: Japanese Patent Publication No. 01-251787
專利文獻4:特開平07-090237號公報Patent Document 4: Japanese Patent Publication No. 07-090237
專利文獻5:特開昭51-020941號公報Patent Document 5: JP-A-51-020941
專利文獻6:特開平03-029207號公報Patent Document 6: Japanese Patent Publication No. 03-029207
專利文獻7:特開平04-174980號公報Patent Document 7: Japanese Patent Publication No. 04-174980
專利文獻8:特許第3048197號公報Patent Document 8: Patent No. 3048197
專利文獻9:特許第3477367號公報Patent Document 9: Patent No. 3477367
專利文獻10:國際公開第01/014484號手冊Patent Document 10: International Publication No. 01/014484
專利文獻11:特開2001-323249號公報Patent Document 11: JP-A-2001-323249
專利文獻12:特許第2794009號公報Patent Document 12: Patent No. 2790009
專利文獻13:特開2001-195921號公報Patent Document 13: JP-A-2001-195921
但,在此等習知之電路連接材料中,藉由形成於成為基板之玻璃的玻璃邊緣部之有機膜的突起,所流動之導電粒子會被阻擋而凝集,或,即使為未形成有機膜之基板,在玻璃邊緣部中COF之光阻會阻擋接著劑的流動,致導電粒子進行凝集,產生短路之問題仍存在。However, in the conventional circuit connecting material, the conductive particles which are formed by the protrusion of the organic film formed on the edge portion of the glass which becomes the glass of the substrate are blocked or aggregated, or even if the organic film is not formed. In the substrate, the photoresist of the COF in the edge portion of the glass blocks the flow of the adhesive, causing the conductive particles to agglomerate, and the problem of short circuit still exists.
進一步,在最近,就玻璃基板之電極而言,為了降低成本,使用IZO(Zinc doped Indium Oxide)電極取代習知之ITO(Tin doped Indium Oxide)電極之製造廠商正在增加起來。IZO電極係相較於ITO電極而電阻值高,故使用含有以具有習知之絕緣性的皮膜被覆表面之導電粒子的電路連接材料時,會產生對向之電路電極間的連接電阻變高之問題。Further, recently, in order to reduce the cost of an electrode of a glass substrate, a manufacturer using an IZO (Zinc doped Indium Oxide) electrode instead of a conventional ITO (Tin doped Indium Oxide) electrode is increasing. Since the IZO electrode has a higher electric resistance value than the ITO electrode, when a circuit connecting material containing conductive particles covering the surface with a conventional insulating film is used, the connection resistance between the opposing circuit electrodes becomes high. .
本發明係有鑑於上述習知技術具有之課題而成者,目的在於提供一種電路連接材料,其係可防止在玻璃基板之邊緣部的導電粒子凝集所造成之短路發生,同時即使在使用IZO電極時亦可得到良好的連接電阻;以及提供一種電路連接構造體,其係使用其而對向配置之第一電路電極與第二電路電極電性連接而成。The present invention has been made in view of the above problems in the prior art, and an object thereof is to provide a circuit connecting material which can prevent a short circuit caused by agglomeration of conductive particles at an edge portion of a glass substrate while using an IZO electrode. A good connection resistance can also be obtained; and a circuit connection structure is provided which is electrically connected to the first circuit electrode and the second circuit electrode which are disposed opposite each other.
為達成上述目的,本發明係提供一種電路連接材料, 其係介在於相對峙之電路電極間,將相對向之電路電極加壓,使加壓方向之電極間電性連接之電路連接材料,其特徵為含有:接著劑成分、表面之至少一部分以絕緣被覆體所被覆之第一導電粒子、與表面之至少一部分以Ni或其之合金或氧化物所被覆且具有突起之第二導電粒子;上述第一導電粒子與上述第二導電粒子之個數比(第一導電粒子之個數/第二導電粒子之個數)係為0.4~3。In order to achieve the above object, the present invention provides a circuit connecting material, The invention relates to a circuit connecting material which is connected between the circuit electrodes of the opposite turns and which is pressed against the circuit electrode and electrically connected between the electrodes in the pressurizing direction, and is characterized in that: the adhesive component and at least a part of the surface are insulated. a first conductive particle covered by the covering body, and a second conductive particle coated with Ni or at least an alloy or oxide of the surface and having a protrusion; a ratio of the first conductive particle to the second conductive particle (The number of the first conductive particles / the number of the second conductive particles) is 0.4 to 3.
又本發明係提供一種電路連接材料,其係介在於相對峙之電路電極間,將相對向之電路電極加壓,使加壓方向之電極間以電性連接之電路連接材料,其特徵為含有:接著劑成分、表面之至少一部分以絕緣被覆體所被覆之第一導電粒子、與表面之至少一部分以維克斯硬度(Vicker’s hardness)300Hv以上之金屬、合金或金屬氧化物所被覆且具有突起之第二導電粒子;上述第一導電粒子與上述第二導電粒子之個數比(第一導電粒子之個數/第二導電粒子之個數)係為0.4~3。Furthermore, the present invention provides a circuit connecting material which is characterized in that a circuit connecting material is electrically pressed between electrodes of a pressing direction and a circuit electrode which is electrically connected between the electrodes of the pressing direction, and is characterized by containing : an adhesive component, at least a part of the surface of the first conductive particle covered with the insulating covering, and at least a part of the surface covered with a Vicker's hardness of 300 Hv or more of a metal, an alloy or a metal oxide and having a protrusion The second conductive particles; the number ratio of the first conductive particles to the second conductive particles (the number of the first conductive particles / the number of the second conductive particles) is 0.4 to 3.
若依此等之電路連接材料,可防止在玻璃基板之邊緣部的導電粒子凝集所造成之短路發生,同時即使在使用IZO電極時亦可得到良好的連接電阻。有關可得到如此之效果的理由,本發明人等如以下般推測。亦即,認為僅上述第一導電粒子中,缺乏基板與導電粒子之間的樹脂之排除性,無法得到充分的接觸面積,但,藉上述第二導電粒子之存在,易排除基板與導電粒子之間的樹脂,故可確保充分的接觸面積,並可得到良好的連接電阻者。According to such a circuit connecting material, it is possible to prevent a short circuit caused by aggregation of conductive particles at the edge portion of the glass substrate, and a good connection resistance can be obtained even when an IZO electrode is used. The inventors of the present invention have estimated the reason why such an effect can be obtained. In other words, it is considered that only the first conductive particles lack the resin exclusion between the substrate and the conductive particles, and a sufficient contact area cannot be obtained. However, by the presence of the second conductive particles, the substrate and the conductive particles are easily excluded. The resin is used to ensure a sufficient contact area and a good connection resistance.
本發明之電路連接材料中,上述第一導電粒子與上述第二導電粒子之體積比(第一導電粒子之體積/第二導電粒子之體積)係宜為0.4~3,更宜為0.45~2.5,最宜為0.5~2.0。藉此,可含有用以確保基板與導電粒子之充分的接觸面積所需之第二導電粒子,可得到更良好的連接電阻。In the circuit connecting material of the present invention, the volume ratio of the first conductive particles to the second conductive particles (the volume of the first conductive particles / the volume of the second conductive particles) is preferably 0.4 to 3, more preferably 0.45 to 2.5. The most suitable is 0.5~2.0. Thereby, the second conductive particles required to ensure a sufficient contact area between the substrate and the conductive particles can be obtained, and a better connection resistance can be obtained.
又,本發明之電路連接材料之上述第二導電粒子中,宜上述突起之高度為50~500nm,鄰接之上述突起間之距離為1000nm以下。藉此,可更充分降低對向之電路電極間的連接電阻,且,可更充分抑制此連接電阻的隨時間之上昇。Further, in the second conductive particles of the circuit connecting material of the present invention, it is preferable that the height of the protrusions is 50 to 500 nm, and the distance between the protrusions adjacent to each other is 1000 nm or less. Thereby, the connection resistance between the opposing circuit electrodes can be more sufficiently reduced, and the rise of the connection resistance with time can be more sufficiently suppressed.
又,本發明之電路連接材料之上述第一導電粒子中,宜以使被覆率成為20~70%之方式設置上述絕緣被覆體。藉此,可充分確保鄰接之電路電極間的絕緣性,可更充分降低對向之電路電極間的連接電阻。又,可更充分抑制連接電阻的隨時間之上昇。Further, in the first conductive particles of the circuit connecting material of the present invention, it is preferable to provide the insulating covering so that the coating ratio is 20 to 70%. Thereby, the insulation between the adjacent circuit electrodes can be sufficiently ensured, and the connection resistance between the opposing circuit electrodes can be more sufficiently reduced. Moreover, the rise of the connection resistance with time can be more sufficiently suppressed.
又,本發明之電路連接材料中,宜上述第一導電粒子係具備具有導電性之核粒子、與含有設置於該核粒子之表面上之複數之絕緣性粒子的上述絕緣被覆體,上述絕緣性粒子之平均粒徑(D2 )與上述核粒子之平均粒徑(D1 )之比(D2 /D1 )為1/10以下。藉此,可更充分降低對向之電路電極間的連接電阻,且,可更充分抑制此連接電阻的隨時間之上昇。Further, in the circuit connecting material of the present invention, it is preferable that the first conductive particles are provided with conductive core particles and the insulating covering material containing a plurality of insulating particles provided on the surface of the core particles, and the insulating property. The ratio (D 2 /D 1 ) of the average particle diameter (D 2 ) of the particles to the average particle diameter (D 1 ) of the core particles is 1/10 or less. Thereby, the connection resistance between the opposing circuit electrodes can be more sufficiently reduced, and the rise of the connection resistance with time can be more sufficiently suppressed.
又,本發明之電路連接材料中,宜上述第一導電粒子 係具備具有導電性之核粒子、與含有設置於該核粒子之表面上之有機高分子化合物之絕緣性層的上述絕緣被覆體,上述絕緣性層之厚度(T2 )與上述核粒子之平均粒徑(D1 )之比(T2 /D1 )為1/10以下。藉此,可更充分降低對向之電路電極間的連接電阻,且,可更充分抑制此連接電阻的隨時間之上昇。Further, in the circuit connecting material of the present invention, it is preferable that the first conductive particles are provided with the conductive core particles and the insulating coating layer containing an insulating layer of an organic polymer compound provided on the surface of the core particles. The ratio (T 2 /D 1 ) of the thickness (T 2 ) of the insulating layer to the average particle diameter (D 1 ) of the core particles is 1/10 or less. Thereby, the connection resistance between the opposing circuit electrodes can be more sufficiently reduced, and the rise of the connection resistance with time can be more sufficiently suppressed.
進一步,本發明之電路連接材料中,宜上述第一導電粒子及上述第二導電粒子之平均粒徑皆為2~6μm之範圍內。藉此,可更充分確保鄰接之電路電極間的絕緣性,同時可更充分降低對向之電路電極間的連接電阻。Further, in the circuit connecting material of the present invention, it is preferable that the first conductive particles and the second conductive particles have an average particle diameter of 2 to 6 μm. Thereby, the insulation between the adjacent circuit electrodes can be more sufficiently ensured, and the connection resistance between the opposing circuit electrodes can be more sufficiently reduced.
本發明又,係提供一種電路連接構造體,其特徵為將具有第一電路電極之第一電路構件與具有第二電路電極之第二電路構件以使上述第一電路電極與上述第二電路電極對向之方式配置,且將上述本發明之電路連接材料介在於對向配置的上述第一電路電極與上述第二電路電極之間,藉由加壓加熱,使對向配置之上述第一電路電極與上述第二電路電極電性連接而成。The present invention further provides a circuit connection structure, characterized in that a first circuit member having a first circuit electrode and a second circuit member having a second circuit electrode are used to make the first circuit electrode and the second circuit electrode Arranging in a facing manner, and the circuit connecting material of the present invention is disposed between the first circuit electrode and the second circuit electrode disposed opposite to each other, and the first circuit is disposed oppositely by pressurization heating The electrode is electrically connected to the second circuit electrode.
如此之電路連接構造體係因使用上述本發明之電路連接材料而第一電路構件與第二電路構件連接,可充分抑制鄰接之電路電極間的短路發生,且可充分降低對向之電路電極間的連接電阻。In such a circuit connection structure system, since the first circuit member and the second circuit member are connected by using the circuit connecting material of the present invention described above, occurrence of a short circuit between adjacent circuit electrodes can be sufficiently suppressed, and the opposing circuit electrodes can be sufficiently reduced. Connect the resistor.
又,本發明係提供一種上述電路連接構造體,其中上述第一電路電極及上述第二電路電極之至少一者係ITO電極。Furthermore, the present invention provides the circuit connection structure described above, wherein at least one of the first circuit electrode and the second circuit electrode is an ITO electrode.
進一步,本發明係提供上述電路連接構造體,其中上述第一電路電極及上述第二電路電極之至少一者係IZO電極。Further, the present invention provides the circuit connection structure described above, wherein at least one of the first circuit electrode and the second circuit electrode is an IZO electrode.
若依本發明,可提供一種相較於習知之電路連接材料,在電路間之短路很難發生,使用IZO電極等之高電阻電極時亦可得到良好的連接電阻,且連接信賴性亦優之電路連接材料及電路連接構造體。According to the present invention, it is possible to provide a short circuit between circuits without using a conventional circuit connecting material, and a good connection resistance can be obtained even when a high-resistance electrode such as an IZO electrode is used, and the connection reliability is also excellent. Circuit connection material and circuit connection structure.
以下,一邊依需要而參照圖面,一邊詳細地說明有關本發明之適當的實施形態。Hereinafter, an appropriate embodiment of the present invention will be described in detail with reference to the drawings as needed.
本發明之電路連接材料係含有接著劑成分、第一導電粒子、與第二導電粒子者。又,在本發明中,接著劑成分係電路連接材料之構成材料中,含有導電粒子以外之全部的材料者。The circuit connecting material of the present invention contains an adhesive component, first conductive particles, and second conductive particles. Further, in the present invention, the constituent material of the adhesive component-based circuit connecting material contains all of the materials other than the conductive particles.
本發明之電路連接材料係可含有以由(a)環氧樹脂、與(b)潛在性硬化劑所構成之接著劑作為接著劑成分。The circuit connecting material of the present invention may contain an adhesive composed of (a) an epoxy resin and (b) a latent curing agent as an adhesive component.
(a)環氧樹脂係可使用表氯醇與雙酚A、雙酚F及/或雙酚AD等所衍生之雙酚型環氧樹脂、表氯醇與酚酚醛清漆或甲酚酚醛清漆所衍生之環氧酚醛清漆樹脂、具有含萘環之骨架的萘系環氧樹脂、縮水甘油基胺、縮水甘油基 醚、聯苯基、脂環式等之1分子內具有2個以上之縮水甘油基的各種之環氧化合物等。此等係可以1種單獨或混合2種以上而使用。(a) Epoxy resin can be a bisphenol type epoxy resin derived from epichlorohydrin and bisphenol A, bisphenol F and/or bisphenol AD, epichlorohydrin and phenol novolac or cresol novolac Derivative epoxy novolac resin, naphthalene epoxy resin having a naphthalene ring-containing skeleton, glycidylamine, glycidyl group A variety of epoxy compounds having two or more glycidyl groups in one molecule such as an ether, a biphenyl group or an alicyclic group. These may be used alone or in combination of two or more.
此等之環氧樹脂係為防止電子遷移,宜使用使雜質離子(Na+ 、Cl- 等)或水解性氯等降低至300ppm以下之高純度品。In order to prevent electron migration, such an epoxy resin is preferably a high-purity product in which impurity ions (Na + , Cl - , etc.) or hydrolyzable chlorine are reduced to 300 ppm or less.
(b)潛在性硬化劑可舉例如咪唑系、聯胺系、三氟化硼-胺錯合物、硫鎓鹽、胺醯亞胺、聚胺之鹽、二氰二醯胺等。此等係可以1種單獨或混合2種以上而使用。又,此等之潛在性硬化劑係亦可混合分解促進劑、抑制劑等而使用。又,使此等之潛在性硬化劑以聚胺基甲酸酯系、聚酯系之高分子物質等被覆而微膠囊化者,因可延長可使用時間,故佳。(b) The latent curing agent may, for example, be an imidazole-based compound, a hydrazine-based compound, a boron trifluoride-amine complex, a sulfonium salt, an amine sulfimine, a polyamine salt, or dicyanamide. These may be used alone or in combination of two or more. Further, these latent curing agents may be used by mixing a decomposition accelerator, an inhibitor, or the like. In addition, it is preferred that the latent curing agent is coated with a polyurethane material, a polyester-based polymer material, or the like to be microencapsulated, since the usable time can be extended.
又,使用於本發明之電路連接材料係可含有(c)藉加熱或光而產生游離自由基的硬化劑、與(d)自由基聚合性物質所構成之接著劑作為接著劑成分。Further, the circuit connecting material used in the present invention may contain (c) a curing agent which generates free radicals by heating or light, and an adhesive composed of (d) a radical polymerizable substance as an adhesive component.
(c)藉加熱或光而產生游離自由基的硬化劑(以下,視情況稱為「游離自由基產生劑」)係可舉例如過氧化化合物、偶氮系化合物等之加熱或光進行分解而產生游離自由基者。游離自由基產生劑係依目的之連接溫度、連接時間、可使用時間等而適當選定,但從高反應性與可使用時間之觀點,宜半衰期10小時之溫度為40℃以上,且半衰期1分鐘之溫度為180℃以下之有機過氧化物。(c) A curing agent that generates a free radical by heating or light (hereinafter, referred to as a "free radical generating agent" as the case), for example, heating or light decomposition of a peroxy compound or an azo compound Produce free radicals. The free radical generating agent is appropriately selected depending on the connection temperature, the connection time, the usable time, and the like, but from the viewpoint of high reactivity and usable time, the temperature at which the half life is 10 hours is 40° C. or more, and the half life is 1 minute. The organic peroxide has a temperature of 180 ° C or less.
(c)藉加熱或光而產生游離自由基的硬化劑之調配 量係宜以接著劑成分之固形分全量作為基準而為0.05~10質量%左右,更宜為0.1~5質量%。(c) Blending of hardeners that generate free radicals by heating or light The amount is preferably from 0.05 to 10% by mass, more preferably from 0.1 to 5% by mass, based on the total amount of the solid content of the adhesive component.
(c)藉加熱或光而產生游離自由基的硬化劑具体上可舉例如過氧化二醯基類、過氧化二碳酸酯類、過氧化酯類、過氧化縮酮類、過氧化二烷基類、氫過氧化物類等。此等之中,從抑制電路構件之電路電極的腐蝕之觀點,宜為過氧化酯類、過氧化二烷基類、氫過氧化物類等,進一步,從可得到高反應性之觀點,更宜為過氧化酯類。(c) A hardener which generates free radicals by heating or light, and specific examples thereof include dinonyl peroxides, peroxydicarbonates, peroxyesters, peroxyketals, and dialkyl peroxides. Classes, hydroperoxides, etc. Among these, from the viewpoint of suppressing corrosion of the circuit electrode of the circuit member, it is preferably a peroxy ester, a dialkyl peroxide or a hydroperoxide, and further, from the viewpoint of obtaining high reactivity, It is preferably a peroxyester.
過氧化二醯基類可舉例如過氧化異丁基、過氧化2,4-二氯苯甲醯基、過氧化3,5,5-三甲基己醯基、過氧化辛醯基、過氧化月桂醯基、過氧化硬脂醯基、過氧化琥珀醯基、苯甲醯基過氧化甲苯、過氧化苯甲醯基等。Examples of the dioxonium peroxide group include isobutyl peroxide, 2,4-dichlorobenzylidene peroxide, 3,5,5-trimethylhexyl peroxide, octyl peroxide, and lauric peroxide. Sulfhydryl, stearyl peroxide, amber sulfonate, benzamidine peroxide, benzoyl peroxide, and the like.
過氧化二碳酸酯類可舉例如二正丙基過氧化二碳酸酯、二異丙基過氧化二碳酸酯、雙(4-第三丁基環己基)過氧化二碳酸酯、二-2-乙氧基甲氧基過氧化二碳酸酯、二(2-乙基己基過氧化)二碳酸酯、二甲氧基丁基過氧化二碳酸酯、二(3-甲基-3-甲氧基丁基過氧化)二碳酸酯等。Examples of the peroxydicarbonate include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, and di-2-. Ethoxymethoxyperoxydicarbonate, bis(2-ethylhexylperoxy)dicarbonate, dimethoxybutylperoxydicarbonate, bis(3-methyl-3-methoxyl) Butyl peroxy) dicarbonate and the like.
過氧化酯類可舉例如枯基過氧化新癸酸酯、1,1,3,3-四甲基丁基過氧化新癸酸酯、1-環己基-1-甲基乙基過氧化新癸酸酯、第三丁基過氧化新癸酸酯、第三丁基過氧化三甲基乙酯、1,1,3,3-四甲基丁基過氧化-2-乙基己酸酯、2,5-二甲基-2,5-雙(2-乙基己醯基過氧化)己烷、1-環己基-1-甲基乙基過氧化-2-乙基己酸酯、第三己基過氧化-2- 乙基己酸酯、第三丁基過氧化-2-乙基己酸酯、第三丁基過氧化異丁酸酯、1,1-雙(第三丁基過氧化)環己烷、第三己基過氧化異丙基單碳酸酯、第三己基過氧化-3,5,5-三甲基己酸酯、第三己基過氧化月桂酸酯、2,5-二甲基-2,5-雙(間-甲苯醯基過氧化)己烷、第三丁基過氧化異丙基單碳酸酯、第三丁基過氧化-2-乙基己基單碳酸酯、第三己基過氧化苯甲酸酯、第三丁基過氧化乙酸酯等。Examples of the peroxyesters include cumyl peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, and 1-cyclohexyl-1-methylethyl peroxide. Phthalate, tert-butyl peroxy neodecanoate, tert-butyl trimethyl ethoxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate 2,5-Dimethyl-2,5-bis(2-ethylhexylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, Third hexyl peroxide-2- Ethyl hexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy isobutyrate, 1,1-bis(t-butylperoxy)cyclohexane, Trihexylperoxyisopropyl monocarbonate, third hexylperoxy-3,5,5-trimethylhexanoate, third hexylperoxylaurate, 2,5-dimethyl-2,5 - bis(m-tolylperyl peroxide) hexane, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexyl monocarbonate, third hexylperoxybenzoate An acid ester, a third butyl peroxyacetate or the like.
過氧化縮酮類可舉例如1,1-雙(第三己基過氧化)-3,5,5-三甲基環己烷、1,1-雙(第三己基過氧化)環己烷、1,1-雙(第三丁基過氧化)-3,5,5-三甲基環己烷、1,1-(第三丁基過氧化)環十二碳烷、2,2-雙(第三丁基過氧化)癸烷等。The peroxy ketals may, for example, be 1,1-bis(Third hexylperoxy)-3,5,5-trimethylcyclohexane, 1,1-bis(trihexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-(t-butylperoxy)cyclododecane, 2,2-double (Third butyl peroxidation) decane, and the like.
過氧化二烷基類可舉例如α,α’-雙(第三丁基過氧化)二異丙基苯、過氧化二枯基、2,5-二甲基-2,5-二(第三丁基過氧化)己烷、過氧化第三丁基枯基等。Examples of the dialkyl peroxides include α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, and 2,5-dimethyl-2,5-di (the Tributyl peroxy) hexane, tributyl cumyl peroxide, and the like.
氫過氧化物類可舉例如氫過氧化二異丙基苯、氫過氧化異丙苯等。Examples of the hydroperoxides include diisopropylbenzene hydroperoxide and cumene hydroperoxide.
此等之(c)藉加熱或光而產生游離自由基的硬化劑係可以1種單獨或混合2種以上而使用。又,(c)藉加熱或光而產生游離自由基的硬化劑係亦可混合分解促進劑、抑制劑等而使用。(c) The curing agent which generates free radicals by heating or light can be used singly or in combination of two or more kinds. Further, (c) a curing agent which generates free radicals by heating or light may be used by mixing a decomposition accelerator, an inhibitor or the like.
(d)自由基聚合性物質係具有藉自由基進行聚合之官能基的物質,可舉例如丙烯酸酯、甲基丙烯酸酯、馬來醯亞胺化合物等。(d) The radically polymerizable substance is a substance having a functional group which is polymerized by a radical, and examples thereof include an acrylate, a methacrylate, and a maleimide compound.
丙烯酸酯或甲基丙烯酸酯可舉例如胺基甲酸酯(甲基)丙烯酸酯、甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、異丙基(甲基)丙烯酸酯、異丁基(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、2-羥基-1,3-二(甲基)丙烯醯基丙烷、2,2-雙[4-((甲基)丙烯醯基甲氧基)苯基]丙烷、2,2-雙[4-((甲基)丙烯醯基聚乙氧基)苯基]丙烷、雙環戊烯基(甲基)丙烯酸酯、三環癸烯基(甲基)丙烯酸酯、雙((甲基)丙烯醯氧基乙基)三聚異氰酸酯、ε-己內酯改性三((甲基)丙烯醯氧基乙基)三聚異氰酸酯、三((甲基)丙烯醯氧基乙基)三聚異氰酸酯等。Examples of the acrylate or methacrylate include urethane (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and isopropyl (meth) acrylate. Isobutyl (meth) acrylate, ethylene glycol di(meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane Tris(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, 2-hydroxy-1,3-bis(methyl)propenylpropanepropane, 2,2-bis[4-((A) Acryl-mercaptomethoxy)phenyl]propane, 2,2-bis[4-((meth)acryloylpolyethoxy)phenyl]propane, dicyclopentenyl (meth) acrylate , tricyclodecenyl (meth) acrylate, bis((meth) propylene methoxyethyl) trimer isocyanate, ε-caprolactone modified tris((meth) propylene oxiranyl) Trimeric isocyanate, tris((meth)acryloxyethyl)trimeric isocyanate, and the like.
在本發明中係可使如此之自由基聚合性物質的1種單獨或2種以上組合而使用。In the present invention, one type or two or more types of such radically polymerizable substances may be used in combination.
馬來醯亞胺化合物係宜於分子中含有至少2個以上馬來醯亞胺基者,可舉例如1-甲基-2,4-雙馬來醯亞胺苯、N,N’-間苯撐基雙馬來醯亞胺、N,N’-對苯撐基雙馬來醯亞胺、N,N’-間甲苯撐基馬來醯亞胺、N,N’-4,4-聯苯撐基雙馬來醯亞胺、N,N’-4,4-(3,3’-二甲基-聯苯撐基)雙馬來醯亞胺、N,N’-4,4-(3,3’-二甲基二苯基甲烷)雙馬來醯亞胺、N,N’-4,4-(3,3’-二乙基二苯基甲烷)雙馬來醯亞胺、N,N’-4,4-二苯基甲烷雙馬來醯亞胺、N,N’-4,4-二苯基丙烷雙馬來醯亞胺、N,N’-4,4-二苯基醚雙馬來醯亞胺、 N,N’-3,3’-二苯基碸雙馬來醯亞胺、2,2-雙[4-(4-馬來醯亞胺苯氧基)苯基]丙烷、2,2-雙[3-第二丁基-4,8-(4-馬來醯亞胺苯氧基)苯基]丙烷、1,1-雙[4-(4-馬來醯亞胺苯氧基)苯基]癸烷、4,4’-環己撐基-雙[1-(4-馬來醯亞胺苯氧基)-2-環己基]苯、2,2-雙[4-(4-馬來醯亞胺苯氧基)苯基]六氟丙烷等。此等係可1種單獨或組合2種以上而使用,或亦可與烯丙基酚、烯丙基苯基醚、安息香酸烯丙酯等之烯丙酯化合物組合而使用。The maleic imine compound is preferably one having at least two maleimine groups in the molecule, and examples thereof include 1-methyl-2,4-bismaleimide benzene and N,N'-. Phenylene-based bismaleimide, N,N'-p-phenylene bismaleimide, N,N'-m-tolyl-maleimide, N,N'-4,4- Biphenylene bismaleimide, N,N'-4,4-(3,3'-dimethyl-biphenylene) bismaleimide, N,N'-4,4 -(3,3'-dimethyldiphenylmethane) bismaleimide, N,N'-4,4-(3,3'-diethyldiphenylmethane) double malayan Amine, N, N'-4,4-diphenylmethane, bismaleimide, N,N'-4,4-diphenylpropane, bismaleimide, N,N'-4,4 -diphenyl ether bismaleimide, N,N'-3,3'-diphenylfluorene bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2- Bis[3-t-butyl-4,8-(4-maleimidophenoxy)phenyl]propane, 1,1-bis[4-(4-maleimide phenoxy) Phenyl]decane, 4,4'-cyclohexylene-bis[1-(4-maleimidophenoxy)-2-cyclohexyl]benzene, 2,2-bis[4-(4 - Maleidanilide phenoxy)phenyl]hexafluoropropane, and the like. These may be used alone or in combination of two or more, or may be used in combination with an allyl ester compound such as allyl phenol, allyl phenyl ether or allyl benzoate.
又,在本發明中係可容易地使硬化電路連接材料之前的電路構件之暫固定的觀點,宜為至少含有在25℃之黏度為100000~1000000 mPa‧s之自由基聚合性物質,更宜為含有具100000~500000 mPa‧s之黏度(25℃)的自由基聚合性物質。自由基聚合性物質之黏度係使用市售之E型黏度計而測定。Further, in the present invention, it is preferable that the circuit member before the hardened circuit connecting material can be temporarily fixed, and it is preferable to contain a radical polymerizable substance having a viscosity of at least 100 ° C at 100 ° C to 1,000,000 mPa ‧ s, preferably It is a radical polymerizable substance having a viscosity (25 ° C) of 100,000 to 500,000 mPa·s. The viscosity of the radically polymerizable substance was measured using a commercially available E-type viscometer.
(c)自由基聚合性物質之中,從黏著性之觀點,宜為胺基甲酸酯丙烯酸酯或胺基甲酸酯甲基丙烯酸酯。又,為提昇耐熱性,宜併用與上述之有機過氧化物的交聯後之聚合物的Tg單獨成為100℃以上之自由基聚合性物質。如此之自由基聚合性物質係可使用具有二環戊烯基、三環癸烯基及/或三嗪環者。尤其,適宜使用具有三環癸烯基及/或三嗪環之自由基聚合性物質。(c) Among the radically polymerizable substances, from the viewpoint of adhesion, urethane acrylate or urethane methacrylate is preferable. Moreover, in order to improve heat resistance, it is preferable to use a Tg of a polymer which is crosslinked with the above-mentioned organic peroxide to form a radical polymerizable substance of 100 ° C or more. As such a radically polymerizable substance, those having a dicyclopentenyl group, a tricyclodecenyl group, and/or a triazine ring can be used. In particular, a radically polymerizable substance having a tricyclodecenyl group and/or a triazine ring is suitably used.
又,於接著劑成分依需要而亦可適當使用氫醌、甲基醚氫醌類等之聚合抑制劑。Further, a polymerization inhibitor such as hydroquinone or methyl ether hydroquinone may be suitably used as the binder component.
進一步,以接著劑成分之固形分全量作為基準(100 質量%)而使用具有磷酸酯構造之自由基聚合性物質0.1~10質量%時,金屬等之無機物表面的黏著強度會提高,故佳,更宜使用0.5~5質量%。Further, the solid content of the adhesive component is used as a reference (100) When the amount of the radical polymerizable substance having a phosphate structure is 0.1 to 10% by mass, the adhesion strength of the surface of the inorganic material such as metal is improved, so that it is preferably used in an amount of 0.5 to 5% by mass.
具有磷酸酯構造之自由基聚合性物質係可形成磷酸酐與2-羥基(甲基)丙烯酸酯之反應物而得到。具體上係可舉例如2-甲基丙烯醯氧乙基酸磷酸酯、2-丙烯醯氧乙基酸磷酸酯等。此等係可1種單獨或2種以上組合而使用。The radically polymerizable substance having a phosphate structure can be obtained by forming a reactant of phosphoric anhydride and 2-hydroxy (meth) acrylate. Specific examples thereof include 2-methacryloxyethyl acid phosphate, 2-propylene oxirane acid phosphate, and the like. These may be used alone or in combination of two or more.
本發明之電路連接材料係含有;表面之至少一部分被絕緣被覆體被覆之第一導電粒子、表面之至少一部分被Ni或其合金或氧化物、或、維克斯(Vicker’s)硬度300Hv以上之金屬、合金或金屬氧化物被覆且具有突起之第二導電粒子的至少2種類的導電粒子。又,電路連接材料含有之第一導電粒子與第二導電粒子之個數比(第一導電粒子之個數/第二導電粒子之個數)為0.4~3。以下,分別一邊參照圖面一邊說明有關第一導電粒子與第二導電粒子。The circuit connecting material of the present invention comprises: a first conductive particle coated on at least a part of the surface by the insulating covering, at least a part of the surface is made of Ni or an alloy or oxide thereof, or a metal having a Vicker's hardness of 300 Hv or more At least two types of conductive particles coated with an alloy or a metal oxide and having protruding second conductive particles. Moreover, the number ratio of the first conductive particles to the second conductive particles (the number of the first conductive particles / the number of the second conductive particles) included in the circuit connecting material is 0.4 to 3. Hereinafter, the first conductive particles and the second conductive particles will be described with reference to the drawings.
首先,說明有關表面之至少一部分被絕緣被覆體被覆之第一導電粒子。第一導電粒子係宜具備具有導電性之核粒子、與設於該核粒子之表面上的絕緣被覆體者。第一導電粒子係宜以被覆率成為20~70%之範圍的方式設有絕緣被覆體者。此處,上述被覆率係以下述式(1)定義。First, the first conductive particles in which at least a part of the surface is covered with the insulating covering will be described. It is preferable that the first conductive particles are provided with conductive core particles and an insulating coating provided on the surface of the core particles. It is preferable that the first conductive particles are provided with an insulating coating so that the coverage ratio is in the range of 20 to 70%. Here, the above coverage ratio is defined by the following formula (1).
第一導電粒子之上述被覆率宜為20~70%,但更宜為20~60%。若第一導電粒子之被覆率為20~70%,可於電路連接材料中含有足夠得到充分低之初期電阻值之量之導電粒子。此係伴隨導電粒子之含量的增大,即使產生導電粒子之凝集,藉由設於各別之導電粒子的絕緣被覆體,可充分防止鄰接之電路電極間的電氣連接。The coverage of the first conductive particles is preferably from 20 to 70%, more preferably from 20 to 60%. When the coverage of the first conductive particles is 20 to 70%, the conductive material may be contained in the circuit connecting material in an amount sufficient to obtain a sufficiently low initial resistance value. This is accompanied by an increase in the content of the conductive particles, and even if the agglomerates of the conductive particles are generated, the electrical connection between the adjacent circuit electrodes can be sufficiently prevented by the insulating coating provided on the respective conductive particles.
又,使用全表面以絕緣被覆體被覆之導電粒子時,於核粒子與電路電極表面之間存在絕緣被覆體,電性經路介入絕緣被覆體。然而,上述被覆率為20~70%之第一導電粒子係絕緣被覆為部份性,故可充分降低介入於電性經路之絕緣被覆體。因此,可充分抑制存在於經路之絕緣被覆體的影響。因此,相較於全表面以絕緣被覆體被覆之導電粒子,可降低連接部分之初期電阻值,且,可更確實地抑制此電阻值之隨時間的上昇。Further, when the conductive particles coated with the insulating covering on the entire surface are used, an insulating coating is present between the core particles and the surface of the circuit electrode, and the electrical insulating path is interposed between the insulating coatings. However, the first conductive particles having a coverage ratio of 20 to 70% are partially covered with insulation, so that the insulating covering body interposed in the electrical path can be sufficiently reduced. Therefore, the influence of the insulating covering existing in the path can be sufficiently suppressed. Therefore, compared with the conductive particles coated with the insulating covering on the entire surface, the initial resistance value of the connection portion can be lowered, and the increase in the resistance value with time can be more reliably suppressed.
第一導電粒子具備之絕緣被覆體係可以設於核粒子表面上之複數的絕緣性粒子構成。此時,絕緣性粒子之平均粒徑(D2 )與核粒子之平均粒徑(D1 )的比率(D2 /D1 )宜為1/10以下。若此比率為1/10以下,可更確實地達成連接部分的低電阻值及此電阻值之隨時間上昇的抑制兩者。The insulating coating system of the first conductive particles may be composed of a plurality of insulating particles provided on the surface of the core particles. In this case, the ratio of the average particle diameter of the insulating particles (D 2) of the core particles with an average particle diameter (D 1) of the (D 2 / D 1) should be 1/10 or less. When the ratio is 1/10 or less, both the low resistance value of the connection portion and the suppression of the increase in the resistance value with time can be more surely achieved.
又,第一導電粒子具備之絕緣被覆體係設於核電粒子表面上且以含有有機高分子化合物之絕緣性層構成。此時,絕緣性層之厚度(T2 )與核粒子之平均粒徑(D1 )的比率(T2 /D1 )宜為1/10以下。若此比率為1/10以下,可更確實地達成連接部分的低電阻值及此電阻值之隨時間上昇的抑制兩者。Moreover, the insulating coating system provided in the first conductive particles is provided on the surface of the nuclear power particles and is composed of an insulating layer containing an organic polymer compound. At this time, the ratio (T 2 /D 1 ) of the thickness (T 2 ) of the insulating layer to the average particle diameter (D 1 ) of the core particles is preferably 1/10 or less. When the ratio is 1/10 or less, both the low resistance value of the connection portion and the suppression of the increase in the resistance value with time can be more surely achieved.
圖1係表示第一導電粒子適當的一形態之模式截面圖。圖1所示之第一導電粒子10A係藉由具有導電性之核粒子1及設於此核粒子1之表面上的複數絕緣性粒子2A來構成。Fig. 1 is a schematic cross-sectional view showing an appropriate form of a first conductive particle. The first conductive particles 10A shown in FIG. 1 are composed of core particles 1 having conductivity and a plurality of insulating particles 2A provided on the surface of the core particles 1.
核粒子1係藉由構成中心部分之基材粒子1a及此基材粒子1a之表面上的導電層1b來構成。The core particles 1 are composed of the base material particles 1a constituting the center portion and the conductive layer 1b on the surface of the base material particles 1a.
基材粒子1a之材質係可舉例如玻璃、陶瓷、有機高分子化合物等。此等之材質中,宜藉由加熱及/或加壓而變形者(例如有機高分子化合物)。若為基材粒子1a變形者,導電粒子10A被電路電極押壓時,與電路電極之面積會增加。又,可吸收電路電極之表面的凹凸。因此,電路電極間之連接信賴性會提高。The material of the substrate particles 1a may, for example, be glass, ceramics or an organic polymer compound. Among these materials, those which are deformed by heating and/or pressurization (for example, an organic polymer compound) are preferred. When the substrate particle 1a is deformed, when the conductive particle 10A is pressed by the circuit electrode, the area of the circuit electrode increases. Further, the unevenness of the surface of the circuit electrode can be absorbed. Therefore, the connection reliability between the circuit electrodes is improved.
從如此之觀點,作為構成基材粒子1a之材質適宜者係例如丙烯酸樹脂、苯乙烯樹脂、苯並胍胺(benzoguanamine)樹脂、聚矽氧樹脂、聚丁二烯樹脂或此等之共聚物及使此等交聯者。基材粒子1a係於粒子間可為同一或相異之種類的材質,亦可於同一粒子使1種之材質單獨或混合2種以上之材質混合而使用。From such a viewpoint, as a material constituting the substrate particle 1a, for example, an acrylic resin, a styrene resin, a benzoguanamine resin, a polyoxyxylene resin, a polybutadiene resin or a copolymer thereof may be used. Make these crosslinkers. The substrate particles 1a may be of the same or different types of materials, and may be used by mixing one or more kinds of materials of the same particle alone or in combination.
基材粒子1a之平均粒徑係可依用途等而適當設計,但宜為0.5~20μm,更宜為1~10μm,最宜為2~5μm。若使用平均粒徑為未達0.5μm之基材粒子而製作導電粒子,會產生粒子之二次凝集,有鄰接之電路電極間的絕緣性不充分之傾向,若使用超過20μm之基材粒子而製作導電粒子,有起因於其大小而鄰接之電路電極間的絕緣性不充分之傾向。The average particle diameter of the substrate particles 1a can be appropriately designed depending on the use, etc., but is preferably 0.5 to 20 μm, more preferably 1 to 10 μm, and most preferably 2 to 5 μm. When conductive particles are produced using substrate particles having an average particle diameter of less than 0.5 μm, secondary aggregation of particles occurs, and insulation between adjacent circuit electrodes tends to be insufficient, and when substrate particles larger than 20 μm are used, When the conductive particles are produced, the insulation between the adjacent circuit electrodes due to their size tends to be insufficient.
導電層1b係以被覆基材粒子1a之表面之方式所設的具有導電性之材質所構成的層。從充分確保導電性之觀點,導電層1b係宜為被覆基材粒子1a之全表面。The conductive layer 1b is a layer made of a conductive material provided to cover the surface of the substrate particles 1a. From the viewpoint of sufficiently ensuring conductivity, the conductive layer 1b is preferably the entire surface of the coated substrate particles 1a.
導電層1b之材質可舉例如金、銀、鉑、鎳、銅及此等之合金、含有錫之焊料等的合金、以及具有碳等之導電性的非金屬。對於基材粒子1a,可以無電解電鍍進行被覆,故導電層1b之材質宜為金屬。又,為得到充分之可使用時間,更宜為金、銀、鉑及此等之合金,最宜為金。又,此等係可1種單獨或組合2種以上而使用。The material of the conductive layer 1b may, for example, be gold, silver, platinum, nickel, copper, an alloy thereof, an alloy containing tin or the like, and a non-metal having conductivity such as carbon. Since the base material particles 1a can be coated by electroless plating, the material of the conductive layer 1b is preferably metal. Further, in order to obtain a sufficient usable time, it is more preferably gold, silver, platinum or the like, and it is most preferably gold. Further, these may be used alone or in combination of two or more.
導電層1b之厚度係可依照使用於此之材質或用途等而適當設計,但宜為50~200nm,更宜為80~150nm。若厚度未達50nm,有無法得到連接部分充分低之電阻值的傾向。另外,超過200mm之厚度的導電層1b係有製造效率降低之傾向。The thickness of the conductive layer 1b can be appropriately designed according to the material or use used therein, but is preferably 50 to 200 nm, more preferably 80 to 150 nm. If the thickness is less than 50 nm, there is a tendency that a sufficiently low resistance value of the connection portion cannot be obtained. Further, the conductive layer 1b having a thickness of more than 200 mm tends to have a low manufacturing efficiency.
導電層1b係可以1層或二層以上構成。即使任一者的情形,從使用此所製造之電路連接材料的保存性的觀點,核粒子1之表面層係宜以金、銀、鉑、鈀或此等之合金 構成,更宜以金構成。導電層1b由以金、銀、鉑、鈀或此等之合金(以下稱為「金等之金屬」)所構成之一層構成時,為得到連接部分充分低之電阻值,其厚度宜為10~200nm。The conductive layer 1b may be composed of one layer or two or more layers. Even in the case of any one, the surface layer of the core particle 1 is preferably gold, silver, platinum, palladium or an alloy thereof from the viewpoint of preservability of the circuit connecting material manufactured using the substrate. The composition is more preferably made of gold. When the conductive layer 1b is made of a layer composed of gold, silver, platinum, palladium or the like (hereinafter referred to as "metal such as gold"), the thickness of the connecting portion is preferably sufficiently low to obtain a resistance value of 10. ~200nm.
另外,導電層1b以二層以上所構成時,導電層1b之最外層係宜以金等之金屬所構成,但最外層與基材粒子1a之間的層,亦可以含有例如鎳、銅、錫或此等之合金的金屬層構成。此時,由構成導電層1b之最外層之金等的金屬所構成的金屬層之厚度從黏著劑成分之保存性的觀點,宜為30~200nm。Further, when the conductive layer 1b is composed of two or more layers, the outermost layer of the conductive layer 1b is preferably made of a metal such as gold, but the layer between the outermost layer and the substrate particles 1a may contain, for example, nickel or copper. Tin or a metal layer of these alloys. In this case, the thickness of the metal layer composed of a metal such as gold constituting the outermost layer of the conductive layer 1b is preferably 30 to 200 nm from the viewpoint of storage stability of the adhesive component.
鎳、銅、錫或此等之合金係有時以氧化還原作用產生游離自由基。因此,若金等的金屬所構成的最外層之厚度為未達30nm,與具有自由基聚合性之接著劑成分併用時,有很難充分防止游離自由基之影響的傾向。Nickel, copper, tin or these alloys sometimes produce free radicals by redox. Therefore, when the thickness of the outermost layer formed of a metal such as gold is less than 30 nm, it is difficult to sufficiently prevent the influence of free radicals when used in combination with a radical polymerizable adhesive component.
使導電層1b形成於基材粒子1a表面上之方法係可舉例如無電解電鍍處理或物理性塗佈處理。從導電層1b之形成的容易性之觀點,宜使由金屬所構成之導電層1b藉無電解電鍍處理而形成於基材粒子1a之表面上。The method of forming the conductive layer 1b on the surface of the substrate particle 1a is, for example, an electroless plating treatment or a physical coating treatment. From the viewpoint of easiness of formation of the conductive layer 1b, it is preferable that the conductive layer 1b made of a metal is formed on the surface of the substrate particle 1a by electroless plating treatment.
絕緣性粒子2A係藉由氧化矽、玻璃、陶瓷、等之絕緣性的材料或有機高分子化合物所構成。有機高分子化合物宜為具有熱軟化性者。The insulating particles 2A are made of an insulating material such as cerium oxide, glass, ceramics, or the like, or an organic polymer compound. The organic polymer compound is preferably one having thermal softening properties.
絕緣性粒子之適當材料係聚乙烯、乙烯-醋酸乙烯酯共聚物、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物、聚酯、聚醯胺、聚胺基甲酸酯、聚苯乙烯 、苯乙烯-二乙烯基苯共聚物、苯乙烯-異丁烯共聚物、苯乙烯-丁二烯共聚物、苯乙烯-(甲基)丙烯酸酯共聚物、乙烯-丙烯共聚物、(甲基)丙烯酸酯系橡膠、苯乙烯-乙烯-丁烯共聚物、苯氧樹脂、固形環氧樹脂等。此等係可1種單獨使用亦可組合2種以上而使用。又,從粒度分布之分散度、耐溶劑性及耐熱性之觀點,尤其適宜為苯乙烯-(甲基)丙烯酸酯共聚物。就絕緣性粒子2A之製造方法可舉例如晶種聚合法等。Suitable materials for the insulating particles are polyethylene, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, polyester, polyamine, polyamine Acid ester, polystyrene , styrene-divinylbenzene copolymer, styrene-isobutylene copolymer, styrene-butadiene copolymer, styrene-(meth)acrylate copolymer, ethylene-propylene copolymer, (meth)acrylic acid Ester rubber, styrene-ethylene-butene copolymer, phenoxy resin, solid epoxy resin, and the like. These may be used alone or in combination of two or more. Further, from the viewpoint of the degree of dispersion of the particle size distribution, solvent resistance and heat resistance, a styrene-(meth)acrylate copolymer is particularly preferable. The method for producing the insulating particles 2A may, for example, be a seed polymerization method or the like.
構成絕緣性粒子2A之有機高分子化合物的軟化點,宜為電路構件彼此間之連接時的加熱溫度以上。若軟化點未達連接時的加熱溫度,起因於連接時絕緣性粒子2A過度變形,有無法得到良好的電氣連接之傾向。The softening point of the organic polymer compound constituting the insulating particles 2A is preferably equal to or higher than the heating temperature when the circuit members are connected to each other. If the softening point does not reach the heating temperature at the time of connection, the insulating particles 2A are excessively deformed due to the connection, and there is a tendency that a good electrical connection cannot be obtained.
構成絕緣性粒子2A之有機高分子化合物之交聯度宜為5~20%,更宜為5~15%,最宜為8~13%。交聯度為上述範圍內之有機高分子化合物係與範圍外之有機高分子化合物相較,具有連接信賴性與絕緣性之兩者優異之特性。因此,若交聯度未達5%,有鄰接之電極電路間之絕緣性變成不充分的傾向。另外,若交聯度超過20%,有很難達成連接部分充分低之初期電阻值及電阻值隨時間上昇之抑制的兩者之傾向。The degree of crosslinking of the organic polymer compound constituting the insulating particles 2A is preferably from 5 to 20%, more preferably from 5 to 15%, most preferably from 8 to 13%. The organic polymer compound having a degree of crosslinking within the above range is superior to both of the organic polymer compounds outside the range, and has excellent connection reliability and insulating properties. Therefore, if the degree of crosslinking is less than 5%, the insulation between the adjacent electrode circuits tends to be insufficient. Further, when the degree of crosslinking exceeds 20%, it is difficult to achieve both of the initial resistance value at which the connection portion is sufficiently low and the suppression of the increase in the resistance value with time.
有機高分子化合物之交聯度係可藉由交聯性單體與非交聯性單體之組成比來調整。在本發明所謂之交聯度係意指以交聯性單體與非交聯性單體之組成比(饋入質量比)所得到的理論計算值。亦即,合成有機高分子化合物時而 調配之交聯性單體的饋入質量以交聯性單體與非交聯性之單體的合計饋入質量比除而算出之值。The degree of crosslinking of the organic polymer compound can be adjusted by the composition ratio of the crosslinkable monomer to the non-crosslinkable monomer. The degree of crosslinking referred to in the present invention means a theoretically calculated value obtained by the composition ratio (feeding mass ratio) of a crosslinkable monomer and a non-crosslinkable monomer. That is, synthetic organic polymer compounds sometimes The feed quality of the blended crosslinkable monomer is a value calculated by dividing the feed ratio by the total of the crosslinkable monomer and the non-crosslinkable monomer.
構成絕緣性粒子2A之有機高分子化合物的凝膠分率宜為90%以上,更宜為95%以上。若凝膠分率未達90%,使導電粒子10A分散於接著劑成分中而製作電路連接材料時,有接著劑成分之絕緣電阻隨時間降低之傾向。The gel fraction of the organic polymer compound constituting the insulating particles 2A is preferably 90% or more, and more preferably 95% or more. When the gel fraction is less than 90% and the conductive particles 10A are dispersed in the adhesive component to form a circuit connecting material, the insulation resistance of the adhesive component tends to decrease with time.
此處所謂凝膠分率係表示有機高分子化合物對溶劑之耐性的指標,以下說明其測定方法。測定要測定凝膠分率之有機高分子化合物(被測定試料)之質量(質量A)。將被測定試料收容於容器內,再置入溶劑。在溫度23℃中,使被測定試料於溶劑中攪拌24小時,並進行浸漬。其後,使溶劑揮發等而除去,測定攪拌浸漬後之被測定試料的質量(質量B)。凝膠分率(%)係依下式所算出之值。Here, the gel fraction is an index indicating the resistance of the organic polymer compound to the solvent, and the measurement method will be described below. The mass (mass A) of the organic polymer compound (measured sample) for which the gel fraction was to be measured was measured. The sample to be measured is stored in a container, and the solvent is placed. The sample to be measured was stirred in a solvent at a temperature of 23 ° C for 24 hours, and immersed. Thereafter, the solvent was removed by volatilization or the like, and the mass (mass B) of the sample to be measured after the stirring and immersion was measured. The gel fraction (%) is a value calculated by the following formula.
凝膠分率(%)=(質量B/質量A)×100Gel fraction (%) = (mass B / mass A) × 100
使用於凝膠分率(%)之測定的溶劑係甲苯。又,於電路連接材料之溶液的調製,一般係可使用甲苯、二甲苯、醋酸乙酯、醋酸丁酯、甲乙酮、甲基異丁基酮、四氫呋喃。電路連接材料之溶液的調製係從此等之中,可1種單獨或混合2種以上而使用。The solvent used for the measurement of the gel fraction (%) was toluene. Further, in the preparation of the solution of the circuit connecting material, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone or tetrahydrofuran can be generally used. The preparation of the solution of the circuit-connecting material may be used alone or in combination of two or more kinds.
絕緣性粒子2A之平均粒徑係可依用途等而適當設計,但宜為50~500nm,更宜為50~400nm,最宜為 100~300nm。若平均粒徑未達50nm,有鄰接之電路間之絕緣性變成不充分的傾向,另外,若超過500nm,有很難達成連接部分充分低之初期電阻值及電阻值隨時間上昇之抑制的兩者之傾向。The average particle diameter of the insulating particles 2A can be appropriately designed depending on the use, etc., but it is preferably 50 to 500 nm, more preferably 50 to 400 nm, and most preferably 100~300nm. When the average particle diameter is less than 50 nm, the insulation between the adjacent circuits tends to be insufficient. When the average particle diameter is less than 500 nm, it is difficult to achieve an initial resistance value at which the connection portion is sufficiently low and the resistance value is suppressed from increasing with time. The tendency of the person.
絕緣性粒子2A係宜上述式(1)所定義的被覆率成為20~70%之方式形成於核粒子1之表面上。從更確實地得到絕緣與導電之效果的觀點,被覆率宜為20~60%,更宜為25~60%,最宜為28~55%。若被覆率未達20%,有鄰接之電路電極間之絕緣性變成不充分的傾向,另外,若超過70%,有很難達成連接部分充分低之初期電阻值及電阻值隨時間上昇之抑制的兩者之傾向。又,被覆核粒子1之複數的絕緣性粒子2A係在核粒子1之表面上,宜充分分散。The insulating particles 2A are preferably formed on the surface of the core particle 1 so that the coating ratio defined by the above formula (1) is 20 to 70%. From the viewpoint of more reliably obtaining the effect of insulation and conduction, the coverage rate is preferably 20 to 60%, more preferably 25 to 60%, and most preferably 28 to 55%. When the coverage is less than 20%, the insulation between the adjacent circuit electrodes tends to be insufficient, and if it exceeds 70%, it is difficult to achieve an initial resistance value at which the connection portion is sufficiently low and the resistance value is suppressed from increasing with time. The tendency of both. Further, the plurality of insulating particles 2A covering the core particles 1 are preferably on the surface of the core particles 1, and are preferably sufficiently dispersed.
在本發明所謂的被覆率係可藉由以掃描型電子顯微鏡(倍率8000倍)之觀察而得到,為依據下述之測定值者。亦即,被覆率係依據核粒子及絕緣性粒子之各別的平均粒徑、以及附著於1個的核粒子之絕緣性粒子的個數,所算出之值。對於任意選擇之粒子50個而如上述做法進行測定,算出其平均值。The coverage ratio in the present invention can be obtained by observation with a scanning electron microscope (magnification: 8000 times), and is based on the following measurement values. In other words, the coverage ratio is a value calculated based on the respective average particle diameters of the core particles and the insulating particles and the number of insulating particles attached to one of the core particles. 50 particles were arbitrarily selected and measured as described above, and the average value was calculated.
核粒子1之平均粒徑係如以下做法而進行測定。亦即,任意選擇1個之核粒子,再以掃描型電子顯微鏡進行觀察而測定其最大徑及最小徑。以此最大徑及最小徑之積的平方根作為其粒子之粒徑。對於任意選擇之粒子50個而如上述做法進行測定粒徑,以其平均值作為核粒子1之平 均粒徑(D1 )。絕緣性粒子2A之平均粒徑,亦與此同樣做法而對於任意之絕緣性粒子50個而測定其粒徑,以其平均值作為核粒子2A之平均粒徑(D2 )。The average particle diameter of the core particles 1 was measured as follows. That is, one of the core particles was arbitrarily selected, and the maximum diameter and the minimum diameter were measured by observation with a scanning electron microscope. The square root of the product of the largest diameter and the minimum diameter is taken as the particle diameter of the particles. The particle size was measured as described above for 50 particles arbitrarily selected, and the average value thereof was used as the average particle diameter (D 1 ) of the core particle 1. In the same manner as in the above, the average particle diameter of the insulating particles 2A was measured for 50 particles of any of the insulating particles, and the average value thereof was defined as the average particle diameter (D 2 ) of the core particles 2A.
1個之導電粒子具備的絕緣性粒子之個數係如以下做法而進行測定。亦即,任意地選擇表面之一部分被覆複數之絕緣性粒子2A的導電粒子1個。繼而,再以掃描型電子顯微鏡進行攝影,計算附著於可觀察之核粒子表面上的絕緣性粒子之數目。藉此,使所得到之計數為2倍,以算出附著於1個核粒子之絕緣性粒子的數目。對於任意選擇之導電粒子50個而如上述做法進行測定絕緣性粒子的數目,以其平均值作為1個之導電粒子具備的絕緣性粒子的個數。The number of insulating particles included in one conductive particle was measured as follows. That is, one of the conductive particles of the insulating particles 2A which is partially covered with a plurality of surfaces is arbitrarily selected. Then, photography was carried out by a scanning electron microscope to calculate the number of insulating particles attached to the surface of the observable core particles. Thereby, the count obtained was doubled, and the number of insulating particles adhering to one core particle was calculated. The number of the insulating particles was measured by 50 arbitrarily selected conductive particles, and the average value was used as the number of insulating particles included in one conductive particle.
核粒子之全表面積係意指以上述(D1 )作為直徑之球的表面積。另外,被核粒子表面的絕緣被覆體被覆之部分的面積,係對以上述(D2 )作為直徑之圓的面積之值乘上1個之導電粒子具備的絕緣性粒子的個數所得到之值。The total surface area of the core particles means the surface area of the sphere having the diameter (D 1 ) described above. In addition, the area of the portion covered with the insulating coating on the surface of the core particle is obtained by multiplying the value of the area of the circle having the diameter of (D 2 ) by one of the number of insulating particles included in the conductive particle. value.
絕緣性粒子2A之平均粒徑(D2 )與核粒子1之平均粒徑(D1 )的比率(D2 /D1 )宜為1/10以下,更宜為1/15以下。又,此比率(D2 /D1 )之下限宜為1/20。若D2 /D1 超過1/10,有很難達成連接部分充分低之初期電阻值及電阻值隨時間上昇之抑制的兩者之傾向。另外,若為未達1/20,鄰接之電路間的絕緣性有不充分的傾向。The ratio of the insulating particles 2A of the average particle diameter (D 2) with an average particle diameter of the core particles 1 (D 1) of the (D 2 / D 1) should be 1/10 or less, 1/15 or less is more desirable. Further, the lower limit of the ratio (D 2 /D 1 ) is preferably 1/20. When D 2 /D 1 exceeds 1/10, it is difficult to achieve both of the initial resistance value at which the connection portion is sufficiently low and the suppression of the resistance value with time. In addition, if it is less than 1/20, the insulation between adjacent circuits tends to be insufficient.
又,形成於核粒子1之表面上的絕緣被覆體係如絕緣性粒子2A般不限制於球狀者。絕緣被覆體係亦可為由與 絕緣性粒子2A同樣的材質所構成之絕緣性層。例如,圖2所示之第一導電粒子10B係具備部分地設置於該粒子1的表面上之絕緣性層2B。Moreover, the insulating coating system formed on the surface of the core particle 1 is not limited to a spherical shape like the insulating particle 2A. Insulation coating system can also be used An insulating layer made of the same material as the insulating particles 2A. For example, the first conductive particles 10B shown in FIG. 2 include an insulating layer 2B partially provided on the surface of the particles 1.
絕緣性層2B係宜以被覆率成為20~70%之方式形成於核粒子1的表面上。從更確實地得到本發明之效果的觀點,被覆率宜為20~60%,更宜為25~60%,最宜為28~55%。若被覆率未達20%,有鄰接之電路電極間之絕緣性變成不充分的傾向,另外,若超過70%,有很難達成連接部分充分低之初期電阻值及電阻值隨時間上昇之抑制的兩者之傾向。又,被覆核粒子1之絕緣性粒子2B的各被覆區域係在核粒子1之表面上,宜充分分散。各被覆區域亦可分別孤立,亦可連續。The insulating layer 2B is preferably formed on the surface of the core particle 1 so that the coverage ratio is 20 to 70%. From the viewpoint of more reliably obtaining the effects of the present invention, the coverage ratio is preferably from 20 to 60%, more preferably from 25 to 60%, most preferably from 28 to 55%. When the coverage is less than 20%, the insulation between the adjacent circuit electrodes tends to be insufficient, and if it exceeds 70%, it is difficult to achieve an initial resistance value at which the connection portion is sufficiently low and the resistance value is suppressed from increasing with time. The tendency of both. Moreover, each of the covering regions of the insulating particles 2B covering the core particles 1 is on the surface of the core particle 1, and is preferably sufficiently dispersed. Each covered area can also be isolated or continuous.
絕緣性層2B之厚度(T2 )與核粒子1之平均粒徑(D1 )的比率(T2 /D1 )宜為1/10以下,更宜為1/15以下。又,此比率(T2 /D1 )之下限宜為1/20。若T2 /D1 超過1110,有很難達成連接部分充分低之初期電阻值及電阻值隨時間上昇之抑制的兩者之傾向。另外,若為未達1/20,鄰接之電路間的絕緣性有不充分的傾向。The ratio (T 2 /D 1 ) of the thickness (T 2 ) of the insulating layer 2B to the average particle diameter (D 1 ) of the core particles 1 is preferably 1/10 or less, more preferably 1/15 or less. Further, the lower limit of the ratio (T 2 /D 1 ) is preferably 1/20. When T 2 /D 1 exceeds 1110, it is difficult to achieve both of the initial resistance value at which the connection portion is sufficiently low and the suppression of the increase in the resistance value with time. In addition, if it is less than 1/20, the insulation between adjacent circuits tends to be insufficient.
絕緣被覆體以絕緣性層2B所構成之時的被覆率係可依以下之順序算出。亦即,使任意選擇之導電粒子50個以掃描型電子顯微鏡分別攝影,使附著於可觀察之核粒子表面上之絕緣性層的面積之測定值進行相加平均來得到。The coverage ratio when the insulating coating is composed of the insulating layer 2B can be calculated in the following order. In other words, 50 randomly selected conductive particles are imaged by a scanning electron microscope, and the measured values of the area of the insulating layer adhering to the surface of the observable core particle are added and averaged.
又,有關絕緣性層2B之厚度(T2 ),使任意選擇之導電粒子50個以掃描型電子顯微鏡分別攝影,使各導電 粒子之表面上的絕緣性層2B的厚度之測定值進行相加平均來得到。Further, regarding the thickness (T 2 ) of the insulating layer 2B, 50 pieces of arbitrarily selected conductive particles are respectively imaged by a scanning electron microscope, and the measured values of the thickness of the insulating layer 2B on the surface of each conductive particle are added. Average to get.
於核粒子1之表面形成絕緣被覆體(絕緣性粒子2A或絕緣性層2B)之方法,係可使用公知之方法,可舉例如利用以有機溶劑或分散劑所產生的化學變化之濕式方法及利用以機械能量所產生之物理化學變化的乾式方式。可舉例如噴霧法、高速攪拌法、噴塗吹乾法等。A method of forming an insulating coating (insulating particle 2A or insulating layer 2B) on the surface of the core particle 1 may be a known method, and for example, a wet method using a chemical change by an organic solvent or a dispersing agent may be used. And a dry method that utilizes physicochemical changes produced by mechanical energy. For example, a spray method, a high-speed stirring method, a spray drying method, or the like can be given.
為更確實地得到本發明之效果,宜使粒徑被非常均一化之複數絕緣性粒子2A設於核粒子1之表面上,藉此構成絕緣被覆體。又,與其採用溶劑或分散劑很難完全除去之濕式方法,不如採用不使用溶劑之乾式方式。In order to obtain the effect of the present invention more reliably, it is preferable that the plurality of insulating particles 2A having a very uniform particle diameter are provided on the surface of the core particle 1 to constitute an insulating coating. Further, rather than a wet method in which it is difficult to completely remove a solvent or a dispersant, it is preferable to use a dry method in which no solvent is used.
可以乾式方式於核粒子1之表面形成絕緣被覆體的裝置,可舉例如Mechanomill(商品名,(股)德壽工作所製)、Hybridizer((股)奈良機械製作所製、商品名:NHS系列)等。其中,使絕緣被覆體形成於核粒子1之表面上時使核粒子1之表面改質成適當的狀態,故宜使用Hybridizer。若依此裝置,可進行以粒子程度之精密被覆,使粒徑被非常均一化之絕緣性粒子2A形成於核粒子1之表面上。A device for forming an insulating coating on the surface of the core particle 1 in a dry manner, for example, a Mechanomill (trade name, manufactured by Deshou Works Co., Ltd.), a Hybridizer (manufactured by Nara Machinery Co., Ltd., trade name: NHS series) Wait. However, when the insulating coating is formed on the surface of the core particle 1, the surface of the core particle 1 is modified to an appropriate state. Therefore, a Hybridizer is preferably used. According to this apparatus, the insulating particles 2A having a very uniform particle diameter can be formed on the surface of the core particle 1 by precisely coating the particles.
絕緣被覆體之形狀的控制係可藉由例如調整被覆處理之條件來實施。被覆處理之條件係例如溫度、旋轉速度。又,絕緣性粒子2A之平均粒徑或絕緣性層2B之厚度係可藉由調整被覆處理之條件或供給至該處理之核粒子1與有機高分子化合物(絕緣被覆體之材質)的調配比率來實 施。The control of the shape of the insulating covering can be carried out, for example, by adjusting the conditions of the coating treatment. The conditions of the coating treatment are, for example, temperature and rotational speed. Further, the average particle diameter of the insulating particles 2A or the thickness of the insulating layer 2B can be adjusted by adjusting the conditions of the coating treatment or the ratio of the core particles 1 and the organic polymer compound (material of the insulating covering) supplied to the treatment. Come true Shi.
被覆處理(乾式方式)的溫度宜為30~90℃,更宜為50~70℃。The temperature of the coating treatment (dry mode) is preferably 30 to 90 ° C, more preferably 50 to 70 ° C.
又,被覆處理(乾式方式)之旋轉速度宜為6000~20000/分,更宜為10000~17000/分。Further, the rotation speed of the coating treatment (dry method) is preferably 6,000 to 20,000/min, more preferably 10,000 to 17,000/min.
以上,說明有關實施絕緣被覆處理之第一導電粒子的適當形態,但,本發明之第一導電粒子係不限制於上述之形態者。本發明之第一導電粒子係在不超出其要旨之範圍可做各種變形。例如,在上述實施形態中,係例示以基材粒子1a及導電層1b所構成之核粒子1,但,核粒子係亦可為以具有導電性之材質(例如,與導電層1b同樣材質)所構成者。又,亦可使用由熱熔融金屬所構成之粒子作為核粒子。此時,可受加熱及加壓而使核粒子充分變形。Although the appropriate form of the first conductive particles to be subjected to the insulating coating treatment has been described above, the first conductive particles of the present invention are not limited to the above-described ones. The first conductive particles of the present invention can be variously modified without departing from the gist thereof. For example, in the above embodiment, the core particles 1 composed of the substrate particles 1a and the conductive layer 1b are exemplified, but the core particles may be made of a conductive material (for example, the same material as the conductive layer 1b). The constituents. Further, particles composed of a hot molten metal may be used as the core particles. At this time, the core particles can be sufficiently deformed by heating and pressurization.
又,第一導電粒子係就絕緣被覆體而言亦可為使絕緣性粒子2A及絕緣性層2B之兩者設於核粒子1之表面上者。Further, the first conductive particles may be such that the insulating particles 2A and the insulating layer 2B are provided on the surface of the core particle 1 in the insulating coating.
其次,說明有關第二導電粒子,其係表面之至少一部分以Ni或其合金或氧化物、或維克斯(Vicker’s)硬度300Hv以上之金屬、合金或金屬氧化物被覆,且具有突起。Next, the description will be made regarding the second conductive particles, at least a part of which is covered with Ni or an alloy or oxide thereof, or a metal, alloy or metal oxide having a Vicker's hardness of 300 Hv or more, and has protrusions.
圖3(a)及(b)係表示第二導電粒子之適當的一形態之截面斷面圖。如圖3(a)所示,第二導電粒子20A係以由有機高分子化合物所構成之核體21、形成於核體21之表面上的金屬22所構成。核體21係以中核部21a、 與形成於中核部21a之表面上的突起部21b所構成。金屬層22係於其表面側具有複數之突起部14。3(a) and 3(b) are cross-sectional views showing a suitable one of the second conductive particles. As shown in FIG. 3(a), the second conductive particles 20A are composed of a core body 21 composed of an organic polymer compound and a metal 22 formed on the surface of the core body 21. The core body 21 is a core portion 21a, It is constituted by a projection 21b formed on the surface of the core portion 21a. The metal layer 22 has a plurality of protrusions 14 on its surface side.
構成核體21之中核部21a的有機高分子化合物係可舉例如丙烯酸樹脂、苯乙烯樹脂、苯並胍胺樹脂、聚矽氧樹脂、聚丁二烯樹脂或此等之共聚物,亦可使用交聯此等者。The organic polymer compound constituting the core portion 21a of the core body 21 may, for example, be an acrylic resin, a styrene resin, a benzoguanamine resin, a polyoxyl resin, a polybutadiene resin or a copolymer thereof, or may be used. Crosslink these people.
構成突起部21b之有機高分子化合物係亦可與構成中核部21a的有機高分子化合物同一亦可相異。又,突起部21b之平均粒徑宜為50~500nm。The organic polymer compound constituting the protrusion portion 21b may be the same as or different from the organic polymer compound constituting the core portion 21a. Further, the average diameter of the projections 21b is preferably 50 to 500 nm.
核體21係可藉由於中核部21a之表面吸附複數個具有小於中核部21a之徑的突起部21b來形成。The core body 21 can be formed by adsorbing a plurality of protrusions 21b having a smaller diameter than the core portion 21a due to the surface of the core portion 21a.
金屬層22之材料係Ni或其合金或氧化物或維克斯(Vicker’s)硬度300Hv以上之金屬、合金或金屬氧化物。維克斯(Vicker’s)硬度300Hv以上之金屬、合金或金屬氧化物可舉例如Ni、Pd、Rh、以及其等之合金及氧化物。此等之中金屬層22之材料係從汎用性之觀點,宜為Ni或其合金或氧化物,更宜為Ni。The material of the metal layer 22 is Ni, or an alloy or oxide thereof, or a metal, alloy or metal oxide having a Vicker's hardness of 300 Hv or more. Examples of the metal, alloy or metal oxide of Vicker's hardness of 300 Hv or more include alloys and oxides of Ni, Pd, Rh, and the like. The material of the metal layer 22 among these is preferably Ni or an alloy or oxide thereof, more preferably Ni, from the viewpoint of versatility.
成為金屬層22之材料的金屬、合金或金屬氧化物的維克斯(Vicker’s)硬度為300Hv以上,但從與樹脂排除性與變形性之觀點,宜為300~800Hv,更宜為300~600Hv。The Vicker's hardness of the metal, alloy or metal oxide which is the material of the metal layer 22 is 300 Hv or more, but from the viewpoint of resin exclusion and deformability, it is preferably 300 to 800 Hv, more preferably 300 to 600 Hv. .
金屬層22係可使用例如無電解電鍍法而形成於核體21之表面。The metal layer 22 can be formed on the surface of the core body 21 by, for example, electroless plating.
又,鎳合金係依於電鍍浴中所調配之添加劑有各種者 。更已為人知之鎳合金係可舉例如鎳-磷、鎳-硼等。In addition, nickel alloys are various depending on the additives formulated in the plating bath. . Further known nickel alloys are, for example, nickel-phosphorus, nickel-boron or the like.
金屬層22之厚度(電鍍之厚度)宜為50~170nm,更宜為50~150nm。使金屬層22之厚度為如此之範圍,可使電路電極間之連接電阻為更良好的者。金屬層22之厚度未達50nm,係有產生電鍍之缺損等而有連接電阻變大之傾向,若超過170nm,有於導電粒子間產生凝結而鄰接之電路電極間產生短路的傾向。The thickness of the metal layer 22 (thickness of plating) is preferably 50 to 170 nm, more preferably 50 to 150 nm. When the thickness of the metal layer 22 is in such a range, the connection resistance between the circuit electrodes can be made better. When the thickness of the metal layer 22 is less than 50 nm, the connection resistance tends to increase due to defects such as plating, and when it exceeds 170 nm, condensation occurs between the conductive particles, and a short circuit occurs between adjacent circuit electrodes.
導電粒子20A之突起部14的高度(H)係宜為50~500nm,更宜為75~300nm。突起部之高度未達50nm時,高溫高濕處理後,有連接電阻變高之傾向,若超過500nm時係因與導電粒子之電路電極的接觸面積變小,故有連接電阻變高之傾向。The height (H) of the projections 14 of the conductive particles 20A is preferably 50 to 500 nm, more preferably 75 to 300 nm. When the height of the protrusions is less than 50 nm, the connection resistance tends to be high after the high-temperature and high-humidity treatment. When the thickness exceeds 500 nm, the contact area with the circuit electrodes of the conductive particles is small, so that the connection resistance tends to be high.
鄰接之突起部14間的距離(S)係宜為1000nm以下,更宜為500nm以下。若突起部14間之距離超過1000nm,因突起變疏,導電粒子與電路電極之接觸面積變小,有連接電阻變高之傾向。又,鄰接之突起部14間的距離(S)係從於導電粒子與電路電極之間未進入接著劑成分,而使導電粒子與電路電極充分接觸之觀點,宜為50nm以上。又導電粒子20A之突起部14之高度(H)及鄰接之突起部14間的距離(S)係可藉由電子顯微鏡進行測定。The distance (S) between the adjacent projections 14 is preferably 1000 nm or less, more preferably 500 nm or less. When the distance between the protrusions 14 exceeds 1000 nm, the contact area between the conductive particles and the circuit electrode becomes small due to the unevenness of the protrusions, and the connection resistance tends to be high. Further, the distance (S) between the adjacent protrusions 14 is preferably 50 nm or more from the viewpoint that the conductive particles and the circuit electrode do not enter the adhesive component and the conductive particles are sufficiently in contact with the circuit electrode. Further, the height (H) of the protruding portion 14 of the conductive particle 20A and the distance (S) between the adjacent protruding portions 14 can be measured by an electron microscope.
又,第二導電粒子係如示於圖3(b),核體21亦可僅以中核部21a所構成。此第二導電粒子20B係金屬電鍍核體21之表面,可藉由於核體21之表面上形成金屬層 22來得到。但,突起部14係金屬電鍍時,改變電鍍條件而改變金屬層22之厚度以形成於金屬層22。又,電鍍條件之變更例如於最初所使用之電鍍液中,追加濃度高於此之電鍍液,以使電鍍液濃度形成不均一來實施。Further, the second conductive particles are as shown in Fig. 3(b), and the core body 21 may be constituted only by the core portion 21a. The second conductive particle 20B is a surface of the metal plated core body 21, and a metal layer is formed on the surface of the core body 21. 22 to get. However, when the protrusions 14 are metal plated, the plating conditions are changed to change the thickness of the metal layer 22 to be formed on the metal layer 22. Further, the plating conditions are changed, for example, in the plating solution used first, and the plating solution having a higher concentration than the plating solution is formed so that the plating solution concentration is not uniform.
又,第二導電粒子係亦可於非導電性之玻璃、陶瓷、塑膠等之絕緣粒子被覆Ni或其合金或氧化物、或維克斯(Vicker’s)硬度300Hv以上的金屬、合金或金屬氧化物者。第二導電粒子為於絕緣粒子被覆導電性物質者,使最外層為Ni,使成為核之絕緣粒子為塑膠時,或,第二導電粒子為熱熔融金屬粒子時,具有以加熱加壓所造成之變形性,連接時與電路電極之連接面積增加而信賴性提高,故佳。Further, the second conductive particles may be coated with Ni, an alloy or an oxide thereof, or a metal, alloy or metal oxide having a Vicker's hardness of 300 Hv or more, in insulating particles such as non-conductive glass, ceramics, and plastic. By. The second conductive particles are those in which the conductive particles are coated with the insulating particles, and the outermost layer is Ni, and the insulating particles that are the core are plastic, or the second conductive particles are hot-melted metal particles, which are caused by heat and pressure. The deformability is improved because the connection area with the circuit electrodes at the time of connection increases and the reliability is improved.
在電路連接材料中,第一及第二導電粒子之合計的調配量宜相對於接著劑成分100體積份,在0.1~30體積份之範圍依用途分開使用。為更充分防止第一及第二導電粒子所產生之鄰接電路之短路等,調配量更宜為0.1~10體積份。In the circuit connecting material, the total amount of the first and second conductive particles is preferably used in an amount of 0.1 to 30 parts by volume based on 100 parts by volume of the adhesive component. In order to more sufficiently prevent the short circuit of the adjacent circuit generated by the first and second conductive particles, the compounding amount is preferably 0.1 to 10 parts by volume.
又,第一及第二導電粒子之平均粒徑係任一者均,從若小於連接之電路的電極高度則鄰接電極間之短路會減少等的觀點,宜為1~10μm,更宜為2~8μm,最宜為2~6μm。又,第一導電粒子之平均粒徑小於第二導電粒子之平均粒徑,可使對向之電路電極間連接電阻更充分降低之效果提高,故佳。又,第一導電粒子之平均粒徑大於第二導電粒子之平均粒徑,可使鄰接之電路電極間之絕緣性充分確 保,故佳。尤其,認為全表面被絕緣被覆體被覆之導電粒子或被覆率超過70%之導電粒子,效果出現很大。又,認為被覆率為20%~70%之導電粒子,或絕緣性微粒子設於具有導電性之各粒子表面上之時,依絕緣性微粒子之大小或被覆率而傾向改變,故宜進行適當調整。此等係可例如依用途相異之本發明的電路連接材料所需求的特性而進行選擇。Further, the average particle diameter of the first and second conductive particles is preferably 1 to 10 μm, more preferably 2, from the viewpoint that the short circuit between adjacent electrodes is smaller than the height of the electrode of the connected circuit. ~8μm, most preferably 2~6μm. Further, since the average particle diameter of the first conductive particles is smaller than the average particle diameter of the second conductive particles, the effect of further reducing the connection resistance between the opposing circuit electrodes can be improved, which is preferable. Moreover, the average particle diameter of the first conductive particles is larger than the average particle diameter of the second conductive particles, so that the insulation between the adjacent circuit electrodes can be sufficiently confirmed. Guarantee, so good. In particular, it is considered that the conductive particles coated with the insulating coating on the entire surface or the conductive particles having a coverage of more than 70% have a large effect. In addition, when the conductive particles having a coverage of 20% to 70% or the insulating fine particles are provided on the surface of each of the conductive particles, the size of the insulating fine particles or the coverage ratio tends to change, so it is preferable to appropriately adjust . These can be selected, for example, according to the characteristics required for the circuit connecting material of the present invention which differs in use.
又,第一及第二之導電粒子係宜從10%壓縮彈性率(K值)為100~1000kgf/mm2 者適當選擇而使用。Further, the first and second conductive particles are preferably used as appropriate from a 10% compression modulus (K value) of 100 to 1000 kgf/mm 2 .
此處,第二導電粒子之平均粒徑亦如以下做法而測定。亦即,任意選擇1個之導電粒子,再以掃描型電子顯微鏡進行觀察而測定其最大值及最小值。以此最大值及最小值之積的平方根作為其粒子的粒徑。對於任意選擇之導電粒子50個而如以下做法進行測定,以其平均值作為導電粒子之平均粒徑。Here, the average particle diameter of the second conductive particles was also measured as follows. That is, one conductive particle was arbitrarily selected, and the maximum value and the minimum value were measured by observation with a scanning electron microscope. The square root of the product of the maximum and minimum values is taken as the particle diameter of the particles. For 50 arbitrarily selected conductive particles, the measurement was carried out as follows, and the average value thereof was used as the average particle diameter of the conductive particles.
以上,說明有關表面之至少一部分以Ni或其合金或氧化物,或以維克斯硬度(Vicker’s hardness)300Hv以上之金屬、合金或金屬氧化物所被覆,且具有突起之第二導電粒子的適當形態,但本發明中之第二導電粒子係不限制於上述之形態。In the above, it is explained that at least a part of the surface is coated with Ni or an alloy or an oxide thereof, or a metal, an alloy or a metal oxide having a Vicker's hardness of 300 Hv or more, and having a protruding second conductive particle. The form, but the second conductive particles in the present invention are not limited to the above-described form.
本發明之電路連接材料中的第一及第二導電粒子的個數係使形成電路連接材料之接著劑成分中的樹脂成分溶解於可溶解的溶劑中,從所得到之不溶成分除去多餘之溶劑成分等之後,可以掃描型電子顯微鏡進行觀察來確認。The number of the first and second conductive particles in the circuit connecting material of the present invention is such that the resin component in the adhesive component forming the circuit connecting material is dissolved in a soluble solvent, and the excess solvent is removed from the obtained insoluble component. After the component or the like, it can be confirmed by observation with a scanning electron microscope.
可使樹脂成分溶解之溶劑係有例如MEK(甲基乙基酮)、甲苯等,但不限於此等之溶劑中。The solvent which can dissolve the resin component is, for example, MEK (methyl ethyl ketone), toluene or the like, but is not limited to such a solvent.
觀察存在於所得到之不溶成分中的導電粒子100個以上,測定第一導電粒子與第二導電粒子之個數比(第一導電粒子之個數/第二導電粒子之個數)。在本發明之電路連接材料中係必須上述個數比(第一導電粒子之個數/第二導電粒子之個數)為0.4~3,更宜為0.45~2.5,最宜為0.5~2.0。100 or more kinds of conductive particles existing in the obtained insoluble component were observed, and the ratio of the number of the first conductive particles to the second conductive particles (the number of the first conductive particles / the number of the second conductive particles) was measured. In the circuit connecting material of the present invention, the number ratio (the number of the first conductive particles / the number of the second conductive particles) must be 0.4 to 3, more preferably 0.45 to 2.5, and most preferably 0.5 to 2.0.
在本發明中,有關電路連接材料中之導電粒子的體積係可從電路連接材料中所含有之導電粒子的平均粒徑與每單位面積之導電粒子個數換算成體積比,可求出第一導電粒子與第二導電粒子之體積比(第一導電粒子的體積/第二導電粒子之體積)。在本發明之電路連接材料中係宜為上述體積比(第一導電粒子之體積/第二導電粒子之體積)為0.4~3,更宜為0.45~2.5,最宜為0.5~2.0。In the present invention, the volume of the conductive particles in the circuit connecting material can be obtained by converting the average particle diameter of the conductive particles contained in the circuit connecting material and the number of conductive particles per unit area into a volume ratio. a volume ratio of the conductive particles to the second conductive particles (volume of the first conductive particles / volume of the second conductive particles). In the circuit connecting material of the present invention, the volume ratio (volume of the first conductive particles / volume of the second conductive particles) is preferably 0.4 to 3, more preferably 0.45 to 2.5, and most preferably 0.5 to 2.0.
有關導電粒子之體積的定義係對於突起部或絕緣性層占有之導電粒子全體的體積之比率很微小,故在本案發明中之導電粒子的體積之測定中,絕緣性粒子2A、絕緣性層2B及突起部14係不算出。The definition of the volume of the conductive particles is such that the ratio of the volume of the entire conductive particles occupied by the protrusions or the insulating layer is small. Therefore, in the measurement of the volume of the conductive particles in the invention of the present invention, the insulating particles 2A and the insulating layer 2B are used. The protrusions 14 are not calculated.
又,本發明之電路連接材料係亦可含有第一導電粒子及第二導電粒子以外之其他的導電粒子。其他之導電粒子的含有比率係相對於第一導電粒子及第二導電粒子之總個數,宜為50%以下,更宜為30%以下,尤宜為20%以下。Further, the circuit connecting material of the present invention may further contain conductive particles other than the first conductive particles and the second conductive particles. The content ratio of the other conductive particles is preferably 50% or less, more preferably 30% or less, and particularly preferably 20% or less, based on the total number of the first conductive particles and the second conductive particles.
其他之導電粒子係無特別限定,但可舉例如Au、Ag 、Ni、Cu及焊料等之金屬粒子或碳等。又,其他之導電粒子係使成為核之粒子以1層或2層以上的層被覆,亦可為其最外層具有導電性者。此時,於最外層係組合Ni、Cu等之過渡金屬、或Au、Ag、鉑族金屬等之貴金屬的1種或2種以上而使用。又,最外層宜為以貴金屬作為主成分之層。The other conductive particles are not particularly limited, but may, for example, be Au or Ag. Metal particles such as Ni, Cu, and solder, or carbon. Further, in the other conductive particles, the particles which become the core are coated with one or two or more layers, or the outermost layer may be electrically conductive. In this case, one or two or more kinds of a transition metal such as Ni or Cu or a noble metal such as Au, Ag or a platinum group metal may be used in the outermost layer. Further, the outermost layer is preferably a layer having a noble metal as a main component.
其他之導電粒子係亦可使以作為核之過渡金屬作為主成分之粒子或以被覆核之過渡金屬作為主成分的層之表面,進一步以使貴金屬作為主成分之層進行被覆而成者。又,其他之導電粒子係可以非導電性之玻璃、陶瓷、塑膠等作為主成分之絕緣性粒子作為核,亦可使此核之表面以上述金屬或碳作為主成分之層被覆者。The other conductive particles may be formed by coating a surface of a layer containing a transition metal as a core or a transition metal containing a core as a main component, and further coating a layer having a noble metal as a main component. Further, the other conductive particles may be made of insulating particles having a non-conductive glass, ceramics, plastic or the like as a main component, or the surface of the core may be covered with a layer containing the metal or carbon as a main component.
其他之導電粒子為以導電層被覆絕緣性粒子之核而成者之時,宜為以塑膠作為主成分之絕緣性粒子作為核,以使此核之表面以Ni等之過渡金屬作為主成分的層被覆,進一步,使此層之表面以Au等之貴金屬作為主成分之最外層被覆者。When the other conductive particles are formed by coating the core of the insulating particles with a conductive layer, it is preferable that the insulating particles having a plastic as a main component serve as a core, and the surface of the core is made of a transition metal such as Ni as a main component. The layer is coated, and further, the surface of the layer is coated with the noble metal such as Au as the outermost layer of the main component.
又,本發明之電路連接材料係因處理性優異,故宜以薄膜狀使用,其時,亦可於接著劑成分中含有薄膜形成性高分子。薄膜形成性高分子係可使用聚苯乙烯、聚乙烯、聚乙烯丁縮醛、聚乙烯甲醛、聚醯亞胺、聚醯胺、聚酯、聚氯化乙烯、聚苯醚、尿素樹脂、三聚氰胺樹脂、酚樹脂、二甲苯樹脂、環氧樹脂、聚異氰酸酯樹脂、苯氧樹脂、聚醯亞胺樹脂、聚酯胺基甲酸酯樹脂等。此等之中,具有 羥基之官能基的樹脂可提昇黏著性,故更佳。又,亦可使用使此等之高分子以自由基聚合性的官能基改性者。Moreover, since the circuit connecting material of the present invention is excellent in handleability, it is preferably used in the form of a film, and in the meantime, a film-forming polymer may be contained in the adhesive component. As the film-forming polymer, polystyrene, polyethylene, polyvinyl butyral, polyethylene formaldehyde, polyimide, polyamide, polyester, polyvinyl chloride, polyphenylene ether, urea resin, melamine can be used. Resin, phenol resin, xylene resin, epoxy resin, polyisocyanate resin, phenoxy resin, polyimide resin, polyester urethane resin, and the like. Among these A resin having a hydroxyl group functional group improves adhesion, and is therefore more preferable. Further, those in which these polymers are modified by a radical polymerizable functional group can also be used.
此等薄膜形成性高分子的重量平均分子量宜為10000以上。又,若重量平均分子量超過1000000,混合性降低,故宜未達1000000。The weight average molecular weight of these film-forming polymers is preferably 10,000 or more. Further, if the weight average molecular weight exceeds 1,000,000, the miscibility is lowered, so it is preferably less than 1,000,000.
進一步,本發明之電路連接材料係亦可於接著劑成分中含有橡膠微粒子、填充材、軟化劑、促進劑、抗老化劑、著色劑、難燃劑、觸變劑、偶合劑、酚樹脂、三聚氰胺樹脂、異氰酸酯類等。Further, the circuit connecting material of the present invention may further comprise rubber microparticles, a filler, a softener, an accelerator, an anti-aging agent, a coloring agent, a flame retardant, a thixotropic agent, a coupling agent, a phenol resin, and the like. Melamine resin, isocyanate, and the like.
橡膠微粒子係只要粒子之平均粒徑為調配之第一及第二導電粒子的各平均粒徑之2倍以下,且在室溫(25℃)之貯存彈性率為第一及第二導電粒子以及接著劑成分之室溫的貯存彈性率之1/2以下者即可。尤其,橡膠微粒子之材質為聚矽氧、丙烯酸乳化液、SBR、NBR、聚丁二烯橡膠之微粒子係適宜1種單獨或混合2種以上而使用。3次元交聯之此等橡膠微粒子係耐溶劑性優異,可容易分散於接著劑成分中。The rubber fine particle system is characterized in that the average particle diameter of the particles is twice or less of the average particle diameter of the first and second conductive particles to be blended, and the storage elastic modulus at room temperature (25 ° C) is the first and second conductive particles and The storage component of the subsequent component may have a storage elastic modulus of 1/2 or less. In particular, the material of the rubber fine particles is a polysulfonium oxide, an acrylic acid emulsion, or a fine particle system of an SBR, an NBR, or a polybutadiene rubber, and it is suitable for use alone or in combination of two or more. These rubber fine particles having a three-dimensional crosslink are excellent in solvent resistance and can be easily dispersed in the adhesive component.
於電路連接材料中含有填充材時,連接信賴性等會提高,故佳。填充材係只要其最大徑未達第一及第二導電粒子之各平均粒徑即可使用。填充劑之調配量係宜以電路連接材料之固形分全量作為基準而為5~60體積%的範圍。若調配量超過60體積%,有信賴性提昇之效果飽和的傾向,未達5體積%時係無法充分得到填充劑添加之效果的傾向。When the filler material is contained in the circuit connecting material, the reliability of the connection and the like are improved, which is preferable. The filler material can be used as long as its maximum diameter is less than the average particle diameter of the first and second conductive particles. The amount of the filler to be added is preferably in the range of 5 to 60% by volume based on the total solid content of the circuit connecting material. When the blending amount exceeds 60% by volume, the effect of improving the reliability tends to be saturated, and when it is less than 5% by volume, the effect of adding the filler tends not to be sufficiently obtained.
偶合劑係從黏著性之提昇的觀點,宜為含有選自乙烯基、丙烯酸基、胺基、環氧基及異氰酸酯基所構成之群的1種以上之基的化合物。The coupling agent is preferably a compound containing one or more groups selected from the group consisting of a vinyl group, an acryl group, an amine group, an epoxy group, and an isocyanate group, from the viewpoint of improving the adhesion.
圖4係表示本發明之電路連接材料之一實施形態的薄膜狀之電路連接材料的模式截面圖。薄膜狀之電路連接材料50係至少含有接著劑成分51、第一導電粒子10、及第二導電粒子20。如此地,藉由使電路連接材料為薄膜狀,可容易進行處理。Fig. 4 is a schematic cross-sectional view showing a film-like circuit connecting material of an embodiment of the circuit connecting material of the present invention. The film-shaped circuit connecting material 50 contains at least the adhesive component 51, the first conductive particles 10, and the second conductive particles 20. Thus, the processing can be easily performed by making the circuit connecting material into a film shape.
又,本發明之電路連接材料係亦可分離成含有反應性樹脂之層、與含有潛在性硬化劑之層,或分離成含有可產生游離自由基之硬化劑的層與含有導電粒子之層。形成如此之構造時,可得到高精細化與可使用時間提昇之效果。Further, the circuit connecting material of the present invention may be separated into a layer containing a reactive resin, a layer containing a latent curing agent, or a layer containing a hardener capable of generating free radicals and a layer containing conductive particles. When such a structure is formed, an effect of high definition and usable time increase can be obtained.
本發明之電路連接材料係亦可用來作為IC晶片與基板之黏著或電性電路相互黏著用之薄膜狀接著劑。亦即,具有第一電路電極(連接端子)之第1電路構件、與具有第二電路電極(連接端子)之第二電路構件,使第一電路電極及第二電路電極對向而配置,於所對向配置之第一電路電極與第二電路電極之間介入本發明之電路連接材料而進行加熱加壓,俾使所對向配置之第一電路電極與第二電路電極電性連接,可構成電路連接構造體。The circuit connecting material of the present invention can also be used as a film-like adhesive for bonding an IC wafer to a substrate or an electrical circuit. That is, the first circuit member having the first circuit electrode (connection terminal) and the second circuit member having the second circuit electrode (connection terminal) are disposed such that the first circuit electrode and the second circuit electrode face each other. The first circuit electrode and the second circuit electrode disposed opposite each other are heated and pressurized by interposing the circuit connecting material of the present invention, and the first circuit electrode and the second circuit electrode disposed in opposite directions are electrically connected to each other. A circuit connection structure is formed.
構成如此之電路連接構造體的電路構件係可舉例如半導體晶片、電阻體晶片、電容器晶片等之晶片零件、印刷基板等之基板等。於此等之電路構件係一般設有多數(視情況亦可為單數)電路電極,使電路構件之至少1組設於 其等之電路構件的電路電極之至少一部分對向配置,使對向配置之電路電極間介入本發明之電路連接材料,加熱加壓而對向配置之電路電極間電性連接而構成電路連接構造體。The circuit member constituting such a circuit connection structure may be, for example, a wafer component such as a semiconductor wafer, a resistor wafer or a capacitor wafer, or a substrate such as a printed circuit board. The circuit components of these are generally provided with a plurality of (as the case may be singular) circuit electrodes, so that at least one set of circuit components is provided. At least a part of the circuit electrodes of the circuit members are arranged to face each other, and the circuit connecting material of the present invention is interposed between the circuit electrodes arranged in the opposite direction, and the circuit connecting members are electrically connected to each other by heating and pressing to form a circuit connecting structure. body.
藉由使電路構件之至少一組進行加熱加壓,俾對向配置之電路電極間係藉直接接觸或介入異方導電性接著劑(電路連接材料)的導電粒子而電性連接。By heating and pressurizing at least one of the circuit members, the circuit electrodes disposed in opposite directions are electrically connected by direct contact or intervening of conductive particles of an anisotropic conductive adhesive (circuit connecting material).
本發明之電路連接材料係連接時電路連接材料會熔融流動,得到相對向之電路電極的連接,硬化而保持連接者,電路連接材料之流動性為重要的因子。When the circuit connecting material of the present invention is connected, the circuit connecting material melts and flows to obtain a connection with respect to the circuit electrode, and hardens to maintain the connector, and the fluidity of the circuit connecting material is an important factor.
於厚0.7mm、15mm×15mm之玻璃板上,挾住厚35μm、5mm×5mm之電路連接材料,以170℃、2MPa、10秒之條件進行加熱加壓時,使用初期之面積(A)與加熱加壓後之面積(B)所示之流動性(B/A)之值宜為1.3~3.0,更宜為1.5~2.5。此值未達1.3時,流動性差,有無法得到良好之連接的傾向,超過3.0時,易產生氣泡,有信賴性差之傾向。On a glass plate having a thickness of 0.7 mm and 15 mm × 15 mm, the circuit connecting material having a thickness of 35 μm and 5 mm × 5 mm is sandwiched, and when it is heated and pressurized at 170 ° C, 2 MPa, and 10 seconds, the initial area (A) is used. The fluidity (B/A) indicated by the area (B) after heating and pressurization is preferably from 1.3 to 3.0, more preferably from 1.5 to 2.5. When the value is less than 1.3, the fluidity is poor, and there is a tendency that a good connection cannot be obtained. When the value exceeds 3.0, bubbles are likely to occur, and the reliability tends to be poor.
本發明之電路連接材料在硬化後之40℃的彈性率宜為100~3000MPa,更宜為500~2000MPa。The elastic modulus of the circuit connecting material of the present invention at 40 ° C after hardening is preferably from 100 to 3,000 MPa, more preferably from 500 to 2,000 MPa.
又,本發明之電路電極的連接方法係使具有以熱或光所產生之硬化性的電路連接材料,形成於表面為選自金、銀、錫及鉑族之金屬的一者之電路電極上之後,使另一者之電路電極對位,進行加熱、加壓而連接。Further, the connection method of the circuit electrode of the present invention is such that a circuit connecting material having a hardening property by heat or light is formed on a circuit electrode whose surface is selected from a metal of a gold, silver, tin, and platinum group. Thereafter, the other circuit electrodes are aligned, and heated and pressurized to be connected.
其次,使用圖面而說明本發明之電路連接構造體的製 造方法的適當之一形態。圖5係模式地表示本發明之電路連接構造體的製造方法之步驟截面圖。圖5(a)係連接電路構件間之前的電路構件之截面圖,圖5(b)係連接電路構件間之時的電路連接構造體之截面圖,圖5(c)係連接電路構件間之電路連接構造體之截面圖。Next, the system of the circuit connection structure of the present invention will be described using the drawings. One of the appropriate forms of the method. Fig. 5 is a cross-sectional view showing the steps of a method of manufacturing the circuit connecting structure of the present invention. Fig. 5 (a) is a cross-sectional view of the circuit member before connecting the circuit members, Fig. 5 (b) is a cross-sectional view of the circuit connection structure when connecting the circuit members, and Fig. 5 (c) is a connection between the circuit members A cross-sectional view of the circuit connection structure.
首先,如圖5(a)所示,在設於LCD面板73上之電路電極72上,載置使電路連接材料成形為薄膜狀而成之薄膜狀的電路連接材料(異方導電性黏著薄膜)50。First, as shown in FIG. 5(a), a circuit-connected circuit connecting material (isotropic conductive adhesive film) in which a circuit connecting material is formed into a film shape is placed on a circuit electrode 72 provided on an LCD panel 73. ) 50.
繼而,如圖5(b)所示,一邊進行對位,一邊使設有電路電極76之電路基板75以電路電極72與電路電極76相互對向之方式載置於薄膜狀之電路連接材料50上,使薄膜狀之電路連接材料50介於電路電極72與電路電極76之間。又,電路電極72及76係於深度方向具有複數電極並排之構造(未圖示)。又,設有電路電極76之電路基板75係可舉例如COF等。Then, as shown in FIG. 5(b), the circuit board 75 provided with the circuit electrode 76 is placed on the film-like circuit connecting material 50 such that the circuit electrode 72 and the circuit electrode 76 face each other while being aligned. The film-like circuit connecting material 50 is interposed between the circuit electrode 72 and the circuit electrode 76. Further, the circuit electrodes 72 and 76 have a structure in which a plurality of electrodes are arranged side by side in the depth direction (not shown). Further, the circuit board 75 provided with the circuit electrode 76 is, for example, COF or the like.
薄膜狀之電路連接材料50係薄膜狀,故很容易處理。因此,可使此薄膜狀之電路連接材料50容易地介入電路電極72與電路電極76之間,可使LCD面板73與電路基板75之連接作業容易進行。The film-like circuit connecting material 50 is a film-like material, so it is easy to handle. Therefore, the film-like circuit connecting material 50 can be easily interposed between the circuit electrode 72 and the circuit electrode 76, and the connection work between the LCD panel 73 and the circuit board 75 can be easily performed.
其次,一邊加熱,一邊隔著LCD面板73與電路基板75,將薄膜狀之電路連接材料50朝圖5(b)之箭頭A的方向加壓而進行硬化處理。藉此而如圖5(c)所示般,可藉由電路連接材料50之硬化物所構成之電路連接部60得到連接電路構件間之電路連接構造體70。硬化處理 之方法係依所使用之接著劑成分而可採用加熱及光照射之一者或兩者。藉加壓薄膜狀之電路連接材料50而進行硬化處理,電路連接材料50會流動,硬化,使電路電極72與電路電極76電性連接,且機械性固定。Then, while heating, the film-like circuit connecting material 50 is pressed in the direction of the arrow A of FIG. 5(b) via the LCD panel 73 and the circuit board 75, and is hardened. Thereby, as shown in FIG. 5(c), the circuit connection structure 70 between the circuit members can be obtained by the circuit connection portion 60 composed of the cured material of the circuit connection material 50. Hardening treatment The method may be one or both of heating and light irradiation depending on the adhesive composition used. The circuit connecting material 50 is subjected to a hardening treatment by pressing the film-like connecting material 50, and the circuit connecting material 50 flows and hardens, and the circuit electrode 72 is electrically connected to the circuit electrode 76, and is mechanically fixed.
以下,藉實施例更詳細地說明本發明,但,本發明係不受此等之實施例限制。In the following, the invention will be described in more detail by way of examples, but the invention is not limited by the examples.
使重量平均分子量800之聚己內酯二醇400質量份、2-羥基丙基丙烯酸酯131質量份、作為觸媒之二丁基錫二月桂酸酯0.5質量份、及、作為聚合抑制劑之氫醌單甲基醚1.0質量份一邊進行攪拌,一邊加熱至50℃而混合。400 parts by mass of polycaprolactone diol having a weight average molecular weight of 800, 131 parts by mass of 2-hydroxypropyl acrylate, 0.5 parts by mass of dibutyltin dilaurate as a catalyst, and hydroquinone as a polymerization inhibitor 1.0 part by mass of monomethyl ether was mixed while heating to 50 ° C while stirring.
然後,滴下異佛爾酮二異氰酸酯222質量份,進一步一邊進行攪拌一邊昇溫至80℃而進行胺基甲酸酯反應。確認異氰酸酯基之反應率成為99%以上之後,降低溫度,得到自由基聚合性物質之胺基甲酸酯丙烯酸酯。Then, 222 parts by mass of isophorone diisocyanate was dropped, and the mixture was heated to 80 ° C while stirring to carry out a carbamate reaction. After confirming that the reaction rate of the isocyanate group was 99% or more, the temperature was lowered to obtain a urethane acrylate of a radical polymerizable substance.
以對酞酸/丙二醇/4,4’-二苯基甲烷二異氰酸酯的莫耳 比成為1.0/1.3/0.25之方式的量,使用作為二羧酸之對酞酸、作為二醇之丙二醇、作為異氰酸酯之4,4’-二苯基甲烷二異氰酸酯,以如下之順序調製聚酯胺基甲酸酯樹脂。Mole with citric acid/propylene glycol/4,4'-diphenylmethane diisocyanate The amount is adjusted to 1.0/1.3/0.25, and the polyester is used as a dicarboxylic acid, a propylene glycol as a diol, a 4,4'-diphenylmethane diisocyanate as an isocyanate, and a polyester is prepared in the following order. A urethane resin.
使藉二羧酸與二醇之反應所得到的聚酯多元醇溶解於甲乙酮之溶液投入於具備攪拌機、溫度計、冷凝器及真空產生裝置與氮氣導入管之附燒杯之不銹鋼製高壓鍋中。然後,投入異氰酸酯特定量,相對於聚酯多元醇100質量份而投入二丁基錫月桂酸酯0.02質量份作為觸媒,在75℃下反應10小時後,冷卻40℃。進一步,加入六氫化吡啶而反應30分以進行鏈延長後,再以三乙胺中和。The solution in which the polyester polyol obtained by the reaction of the dicarboxylic acid and the diol was dissolved in methyl ethyl ketone was placed in a stainless steel pressure cooker equipped with a stirrer, a thermometer, a condenser, and a beaker containing a vacuum generating device and a nitrogen gas introducing tube. Then, a specific amount of isocyanate was charged, and 0.02 parts by mass of dibutyltin laurate was added as a catalyst to 100 parts by mass of the polyester polyol, and the mixture was reacted at 75 ° C for 10 hours, and then cooled at 40 ° C. Further, hexahydropyridine was added and reacted for 30 minutes to carry out chain extension, followed by neutralization with triethylamine.
若使上述反應後之溶液滴下於純水中,溶劑及觸媒會溶解於水,同時作為酯胺基甲酸酯化合物之聚酯胺基甲酸酯樹脂會析出。所析出之聚酯胺基甲酸酯樹脂以真空乾燥機乾燥,得到聚酯胺基甲酸酯樹脂。When the solution after the above reaction is dropped into pure water, the solvent and the catalyst are dissolved in water, and the polyester urethane resin as the ester urethane compound is precipitated. The precipitated polyester urethane resin was dried in a vacuum dryer to obtain a polyester urethane resin.
所得到之聚酯胺基甲酸酯樹脂的重量分子量藉凝膠浸透色層分析而測定後,為30000。The weight molecular weight of the obtained polyester urethane resin was measured by a gel-soaked color layer analysis and found to be 30,000.
使上述聚酯胺基甲酸酯樹脂溶解於甲乙酮成為20質量%。上述聚酯胺基甲酸酯樹脂之甲乙酮溶液使用塗佈裝置而塗佈於厚度80μm之單面經表面處理之PET薄膜,藉由70℃、10分鐘之熱風乾燥,製作厚度為35μm之樹脂薄膜。有關此樹脂薄膜,使用廣域動態黏彈性測定裝置,以抗拉荷重5 gf、頻率10 Hz之條件測定彈性率的溫度依存性。在所得到之彈性率-溫度曲線中,從使玻璃轉移區域之前後各別的基線延長之直線,朝縱軸方向位於等距離 之直線、與玻璃轉移區域之階段狀變化部分的曲線交差之點的溫度(中間點玻璃轉移溫度)作為聚酯胺基甲酸酯樹脂之玻璃轉移區域而求出之後,為105℃。The polyester urethane resin was dissolved in methyl ethyl ketone to 20% by mass. The methyl ethyl ketone solution of the above polyester urethane resin was applied to a single-faced surface-treated PET film having a thickness of 80 μm using a coating device, and dried at 70 ° C for 10 minutes to prepare a resin film having a thickness of 35 μm. . With respect to this resin film, the temperature dependence of the modulus of elasticity was measured under the conditions of a tensile load of 5 gf and a frequency of 10 Hz using a wide-area dynamic viscoelasticity measuring apparatus. In the obtained elastic modulus-temperature curve, the straight line extending from the front and the rear of the glass transition region is equidistant toward the longitudinal axis. The temperature at the point where the straight line and the curve of the stepwise change portion of the glass transition region intersect (the intermediate point glass transition temperature) was determined as the glass transition region of the polyester urethane resin, and was 105 °C.
準備一種於由成為核之聚苯乙烯所構成之粒子的表面,設有厚0.2μm之鎳層,並於此鎳層之外側設有厚0.04μm之金層的平均粒徑4μm的導電粒子。另外,準備由苯乙烯-(甲基)丙烯酸酯共聚物所構成之絕緣性粒子。使用Hybridizer,使上述導電粒子之表面以上述絕緣性粒子被覆,準備第一導電粒子a。此第一導電粒子a的D2 /D1 為1/12,被覆率為50%。A surface of a particle composed of polystyrene which is a core was prepared, and a nickel layer having a thickness of 0.2 μm was provided, and on the outer side of the nickel layer, conductive particles having an average particle diameter of 4 μm of a gold layer having a thickness of 0.04 μm were provided. Further, insulating particles composed of a styrene-(meth)acrylate copolymer were prepared. The surface of the above-mentioned conductive particles was coated with the above-mentioned insulating particles using a Hybridizer, and the first conductive particles a were prepared. The first conductive particle a had a D 2 /D 1 of 1/12 and a coverage ratio of 50%.
準備一種於由成為核之聚苯乙烯所構成之粒子的表面,設有厚0.2μm之鎳層,並於此鎳層之外側設有Ni突起之平均粒徑4μm的第二導電粒子a。此第二導電粒子a之Ni的維克斯(Vicker’s)硬度為350 Hv,突起之高度為120nm,突起間距離為420nm。A surface of a particle composed of polystyrene which is a core was prepared, and a nickel layer having a thickness of 0.2 μm was provided, and a second conductive particle a having an average particle diameter of 4 μm of Ni protrusion was provided on the outer side of the nickel layer. The Vic of the second conductive particles a has a Vicker's hardness of 350 Hv, a height of the protrusions of 120 nm, and a distance between the protrusions of 420 nm.
使作為自由基聚合性物質之上述胺基甲酸酯丙烯酸酯30質量份及三聚異氰酸酯型丙烯酸酯(製品名:M-325,東亞合成公司製)20質量份、2-甲基丙烯醯氧乙基酸磷 酸酯(製品名:P-2M、共榮社化學社製)1質量份、作為游離自由基產生劑之過氧化苯甲醯基(製品名:Nyper BMT-K40、日本油脂公司製)3質量份、以及上述聚酯胺基甲酸酯樹脂的20質量%甲乙酮溶液60質量份(固形分:12質量份)進行混合,攪拌而作為接著劑成分。30 parts by mass of the above urethane acrylate as a radically polymerizable substance and 20 parts by mass of a trimeric isocyanate type acrylate (product name: M-325, manufactured by Toagosei Co., Ltd.), 2-methylpropene oxime Phosphate 1 part by mass of an acid ester (product name: P-2M, manufactured by Kyoeisha Chemical Co., Ltd.), and a benzoyl peroxide group (product name: Nyper BMT-K40, manufactured by Nippon Oil & Fats Co., Ltd.) as a free radical generator 60 parts by mass of a 20% by mass methyl ethyl ketone solution of the above polyester urethane resin (solid content: 12 parts by mass) was mixed and stirred to obtain an adhesive component.
使上述第一導電粒子a及上述第二導電粒子a調配分散於接著劑成分,得到塗佈用之分散液。第一導電粒子a及第二導電粒子a之調配量係以塗佈用之分散液的固形分全量作為基準,任一者均成為1.5體積%之量。The first conductive particles a and the second conductive particles a are prepared and dispersed in an adhesive component to obtain a dispersion for coating. The blending amount of the first conductive particles a and the second conductive particles a is 1.5% by volume based on the total solid content of the dispersion liquid for coating.
使所得到之分散液使用塗佈裝置而塗佈於厚度50μm之單面經表面處理之PET薄膜,藉由進行70℃、10分鐘之熱風乾燥,形成厚度為16μm之接著劑層(異方導電性接著劑層)(寬度15cm、長度70m)。將所得到之接著劑層與PET薄膜的層合體裁切成1.5mm寬,於內徑40mm及外徑48mm之塑膠製軋的側面(1.7mm寬)使黏著薄膜面作為內側而捲成50m,得到膠帶狀之電路連接材料。The obtained dispersion liquid was applied to a single-faced surface-treated PET film having a thickness of 50 μm using a coating device, and dried at 70 ° C for 10 minutes to form an adhesive layer having a thickness of 16 μm (isoelectric conduction). Adhesive layer) (width 15 cm, length 70 m). The obtained laminate of the adhesive layer and the PET film was cut into a width of 1.5 mm, and the side of the plastic rolling (1.7 mm width) having an inner diameter of 40 mm and an outer diameter of 48 mm was wound into a 50 m side as an inner side of the adhesive film surface. A tape-like circuit connecting material is obtained.
使第一導電粒子a及第二導電粒子a之調配量如表1所示般改變以外,其餘係與實施例1同樣做法,得到實施例2~3之膠帶狀的電路連接材料。The tape-like circuit connecting materials of Examples 2 to 3 were obtained in the same manner as in Example 1 except that the amounts of the first conductive particles a and the second conductive particles a were changed as shown in Table 1.
準備一種於由成為核之聚苯乙烯所構成之粒子的表面,設有厚0.09μm之鎳層,並於此鎳層之外側設有厚0.03μm之金層的平均粒徑3μm之導電粒子。另外,準備由苯乙烯-(甲基)丙烯酸酯共聚物所構成之絕緣性粒子。使用Hybridizer,使上述導電粒子之表面以上述絕緣性粒子被覆,準備第一導電粒子b。此第一導電粒子b的D2 /D1 為1/15,被覆率為55%。A surface of a particle composed of polystyrene which is a core was prepared, and a nickel layer having a thickness of 0.09 μm was provided, and on the outer side of the nickel layer, conductive particles having an average particle diameter of 3 μm of a gold layer having a thickness of 0.03 μm were provided. Further, insulating particles composed of a styrene-(meth)acrylate copolymer were prepared. The surface of the conductive particles is coated with the insulating particles using a Hybridizer to prepare the first conductive particles b. The first conductive particles b had a D 2 /D 1 of 1/15 and a coverage ratio of 55%.
準備一種於由成為核之聚苯乙烯所構成之粒子的表面,設有厚0.1μm之鎳層,並於此鎳層之外側設有Ni突起之平均粒徑3μm的第二導電粒子b。此第二導電粒子b之Ni的維克斯(Vicker’s)硬度為350 Hv,突起之高度為100nm,突起間距離為200nm。A surface of a particle composed of polystyrene which is a core is prepared, and a nickel layer having a thickness of 0.1 μm is provided, and a second conductive particle b having an average particle diameter of 3 μm of Ni protrusion is provided on the outer side of the nickel layer. The Vic of the second conductive particles b has a Vicker's hardness of 350 Hv, a height of the protrusions of 100 nm, and a distance between the protrusions of 200 nm.
除使用第一導電粒子b及第二導電粒子b取代第一導電粒子a及第二導電粒子a,並使其等之調配量為表1所示之量以外,其餘係與實施例1同樣做法,得到實施例4~6之膠帶狀的電路連接材料。The first conductive particle b and the second conductive particle b were used in place of the first conductive particle a and the second conductive particle a, and the amount of the first conductive particle a and the second conductive particle a was the same as in the first embodiment except for the amount shown in Table 1. A tape-like circuit connecting material of Examples 4 to 6 was obtained.
準備一種於由成為核之聚苯乙烯所構成之粒子的表面 ,設有厚0.2μm之鎳層,並於此鎳層之外側設有厚0.04μm之金層,平均粒徑4μm的被覆Au之導電粒子。此被覆Au之導電粒子的Au之維克斯(Vicker’s)硬度為150 Hv。Preparing a surface for particles composed of polystyrene that becomes a core A nickel layer having a thickness of 0.2 μm was provided, and a gold layer having a thickness of 0.04 μm and an Au-coated conductive particle having an average particle diameter of 4 μm were provided on the outer side of the nickel layer. The Vic's hardness of the Au-coated conductive particles was 150 Hv.
除以同表所示之調配量使用表2所示之導電粒子以外,其餘係與實施例1同樣做法,得到比較例1~7之膠帶狀的電路連接材料。The tape-like circuit connecting materials of Comparative Examples 1 to 7 were obtained in the same manner as in Example 1 except that the conductive particles shown in Table 2 were used in the same amounts as shown in the same table.
又,表1及2中,個數比係意指第一導電粒子與第二導電粒子之個數比(第一導電粒子之個數/第二導電粒子之個數)。又,使用被覆Au之導電粒子取代第二導電粒子時,個數比係意指第一導電粒子與被覆Au之導電粒子之個數比(第一導電粒子之個數/被覆Au之導電粒子之個數)。Further, in Tables 1 and 2, the number ratio means the ratio of the number of the first conductive particles to the second conductive particles (the number of the first conductive particles / the number of the second conductive particles). Further, when the second conductive particles are replaced with the conductive particles coated with Au, the number ratio means the ratio of the number of the first conductive particles to the conductive particles coated with Au (the number of the first conductive particles / the conductive particles coated with Au) Number).
就電路構件而言,係準備厚0.7mm之塗佈ITO玻璃基板(15~20 Ω/□、全面電極)、及厚0.7mm之Cr/IZO[Al(2000埃)+Cr(500埃)+IZO(1000埃)、全面電極]塗佈玻璃基板的2種類之電路構件。For the circuit components, a coated ITO glass substrate (15-20 Ω/□, full-electrode) with a thickness of 0.7 mm and Cr/IZO [Al (2000 angstrom) + Cr (500 angstroms) +) with a thickness of 0.7 mm are prepared. IZO (1000 angstroms), full-electrode] Two types of circuit components coated with a glass substrate.
分別對於塗佈ITO的玻璃基板、及、塗佈Cr/IZO之玻璃基板,於上述實施例及比較例所得到之電路連接材料(寬1.5mm及長3cm),使接著劑層側朝向基板,以70℃、1 MPa加熱加壓2秒鐘而進行層合,剝離PET薄膜而使接著劑層轉印於基板。The circuit connecting material (1.5 mm in width and 3 cm in length) obtained in the above examples and comparative examples was applied to the ITO-coated glass substrate and the Cr/IZO-coated glass substrate, and the adhesive layer side was directed toward the substrate. The laminate was heat-pressed at 70 ° C and 1 MPa for 2 seconds, and the PET film was peeled off to transfer the adhesive layer to the substrate.
然後,使線寬25μm、節距50μm、厚8μm之鍍錫的銅電路600條形成於聚醯亞胺薄膜上之可撓性電路板(FPC),所轉印之接著劑層上於電路側朝向接著劑層而放置,以24℃、0.5MPa加壓1秒鐘而暫固定。Then, 600 tin-plated copper circuits having a line width of 25 μm, a pitch of 50 μm, and a thickness of 8 μm were formed on a flexible printed circuit board (FPC) on a polyimide film, and the transferred adhesive layer was on the circuit side. It was placed toward the adhesive layer, and was temporarily fixed by pressurizing at 24 ° C and 0.5 MPa for 1 second.
藉接著劑層暫固定此FPC之玻璃基板設置於本壓黏裝置,以厚200μm之聚矽氧橡膠作為緩衝材,從FPC側 ,藉熱密封而以170℃、3MPa加熱加壓6秒鐘,俾涵蓋寬1.5mm進行連接。藉此,得到電路連接構造體。The glass substrate temporarily fixed to the FPC by the adhesive layer is disposed on the pressure bonding device, and the polyethylene oxide rubber having a thickness of 200 μm is used as a buffer material from the FPC side. It is heated and pressurized at 170 ° C and 3 MPa for 6 seconds by heat sealing, and the 俾 covers a width of 1.5 mm for connection. Thereby, a circuit connection structure is obtained.
有關所得到之電路連接構造體,藉Multimeter(裝置名:TR6845、Advantest公司製)測定FPC之電路電極、與對於該電路電極之塗佈ITO的玻璃基板或塗佈Cr/IZO之玻璃基板的電路電極之間的連接電阻。連接電阻係測定對向之電路電極間的電阻值40點,以其等之平均值而求出。將所得到之結果表示於表3~4。The circuit connection structure obtained by the Multimeter (device name: TR6845, manufactured by Advantest Co., Ltd.) was used to measure the circuit electrode of the FPC, the glass substrate coated with ITO for the circuit electrode, or the circuit coated with the Cr/IZO glass substrate. The connection resistance between the electrodes. The connection resistance was measured by measuring the resistance value between the opposing circuit electrodes by 40 points, and the average value thereof was obtained. The results obtained are shown in Tables 3 to 4.
使厚38μm之聚醯亞胺薄膜、線寬50μm、線距寬50μm、厚度1000埃之ITO電極以50μm節距所形成之玻璃基板介由於上述實施例及比較例所得到之電路連接材料(寬1.5mm及長3cm)而壓接。此時,於玻璃邊緣部產生導電粒子之凝集。圖6係表示於形成ITO電極之玻璃基板的邊緣部產生導電粒子之凝集時的外觀之連接體照片。圖6係從玻璃基板側照相連接體之照片,可確認形成ITO電極15之玻璃基板的邊緣部17產生導電粒子之凝集16。又,圖中之18係於基板外之樹脂流動部。繼而,如圖6所示般,於玻璃基板的邊緣部17產生導電粒子之凝集16時,在絕緣性低之電路連接材料中係於鄰接之ITO電極15間產生短路而得到連接電阻。A glass substrate formed by using a polyimide film having a thickness of 38 μm, a line width of 50 μm, a line width of 50 μm, and a thickness of 1000 Å at a pitch of 50 μm was obtained by the above-described examples and comparative examples (width). 1.5mm and 3cm long) and crimped. At this time, aggregation of conductive particles occurs at the edge portion of the glass. Fig. 6 is a photograph showing the appearance of the appearance when the conductive particles are aggregated at the edge portion of the glass substrate on which the ITO electrode is formed. Fig. 6 is a photograph of the photographic connector from the glass substrate side, and it was confirmed that the edge portion 17 of the glass substrate on which the ITO electrode 15 was formed was caused to aggregate 16 of the conductive particles. Further, 18 in the figure is a resin flow portion outside the substrate. Then, as shown in FIG. 6, when the aggregate 16 of the conductive particles is generated in the edge portion 17 of the glass substrate, a short circuit is formed between the adjacent ITO electrodes 15 in the circuit connecting material having low insulating properties, and the connection resistance is obtained.
其後,藉Multimeter(裝置名:TR6845、Advantest公司製)測定鄰接之ITO電極間的電阻值。電阻值係測定鄰接之ITO電極間的電阻值20點,記錄可得到1×1010 Ω以下之連接電阻的點(產生短路之電極)之數目,藉其,評估絕緣性。所得到之結果表示於表3~4中。Thereafter, the resistance value between the adjacent ITO electrodes was measured by Multimeter (device name: TR6845, manufactured by Advantest Co., Ltd.). The resistance value was measured by measuring the resistance value between adjacent ITO electrodes by 20 points, and the number of points (electrodes generating short-circuiting) at which a connection resistance of 1 × 10 10 Ω or less was obtained was recorded, and the insulation property was evaluated. The results obtained are shown in Tables 3 to 4.
如以上說明般,若依本發明,相較於習知之電路連接材料,可提供一種很難產生電路間之短路,即使使用IZO電極等之高電阻電極時,亦可得到良好的連接電阻,且連接信賴性優異之電路連接材料及電路連接構造體。As described above, according to the present invention, it is difficult to cause a short circuit between circuits as compared with the conventional circuit connecting material, and even when a high-resistance electrode such as an IZO electrode is used, a good connection resistance can be obtained, and A circuit connection material and a circuit connection structure excellent in reliability are connected.
1‧‧‧核粒子1‧‧‧nuclear particles
1a‧‧‧基材粒子1a‧‧‧Substrate particles
1b‧‧‧導電層1b‧‧‧ Conductive layer
2A‧‧‧絕緣性粒子2A‧‧‧Insulating particles
2B‧‧‧絕緣性層2B‧‧‧Insulating layer
10、10A、10B‧‧‧第一導電粒子10, 10A, 10B‧‧‧ first conductive particles
14‧‧‧突起部14‧‧‧Protruding
20、20A、20B‧‧‧第二導電粒子20, 20A, 20B‧‧‧ second conductive particles
21‧‧‧核體21‧‧‧ nuclear body
21a‧‧‧中核部21a‧‧‧Nuclear Department
21b‧‧‧突起部21b‧‧‧Protruding
22‧‧‧金屬層22‧‧‧metal layer
50‧‧‧薄膜狀之電路連接材料50‧‧‧film-like circuit connecting materials
51‧‧‧接著劑成分51‧‧‧Adhesive ingredients
60‧‧‧電路連接部60‧‧‧Circuit Connection
70‧‧‧電路連接構造體70‧‧‧Circuit connection structure
72、76‧‧‧電路電極72, 76‧‧‧ circuit electrodes
73‧‧‧LCD面板73‧‧‧LCD panel
74‧‧‧液晶顯示部74‧‧‧LCD display
75‧‧‧電路基板75‧‧‧ circuit board
圖1係表示第一導電粒子之適當的一形態的模式截面圖。Fig. 1 is a schematic cross-sectional view showing a suitable form of the first conductive particles.
圖2係表示第一導電粒子之另一適當的一形態之模式截面圖。Fig. 2 is a schematic cross-sectional view showing another suitable form of the first conductive particles.
圖3係表示第二導電粒子之適當的一形態之模式截面圖。Fig. 3 is a schematic cross-sectional view showing a suitable form of the second conductive particles.
圖4係表示本發明之電路連接材料之一實施形態的模式截面圖。Fig. 4 is a schematic cross-sectional view showing an embodiment of a circuit connecting material of the present invention.
圖5係模式性表示本發明之電路連接構造體的製造方法之步驟截面圖。Fig. 5 is a cross-sectional view schematically showing the steps of a method of manufacturing the circuit connecting structure of the present invention.
圖6係表示於形成ITO電極之玻璃基板的邊緣部產生導電粒子之凝集時的外觀之連接體照片。Fig. 6 is a photograph showing the appearance of the appearance when the conductive particles are aggregated at the edge portion of the glass substrate on which the ITO electrode is formed.
10‧‧‧第一導電粒子10‧‧‧First conductive particles
20‧‧‧第二導電粒子20‧‧‧Second conductive particles
50‧‧‧薄膜狀之電路連接材料50‧‧‧film-like circuit connecting materials
51‧‧‧接著劑成分51‧‧‧Adhesive ingredients
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