TW202104497A - Isotropically electroconductive pressure-sensitive adhesive sheet - Google Patents

Isotropically electroconductive pressure-sensitive adhesive sheet Download PDF

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TW202104497A
TW202104497A TW109118097A TW109118097A TW202104497A TW 202104497 A TW202104497 A TW 202104497A TW 109118097 A TW109118097 A TW 109118097A TW 109118097 A TW109118097 A TW 109118097A TW 202104497 A TW202104497 A TW 202104497A
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adhesive sheet
conductive adhesive
acrylic resin
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meth
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TW109118097A
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TWI788670B (en
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山本祥久
渡邊正博
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日商拓自達電線股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Conductive Materials (AREA)

Abstract

Provided is an electroconductive pressure-sensitive adhesive sheet which can be easily adhered to adherends to have high adhesive force, has excellent electrical-connection stability, and changes little in resistivity through a heat cycle test. The isotropically electroconductive pressure-sensitive adhesive sheet of the present invention is formed from a pressure-sensitive adhesive which comprises an acrylic resin having a glass transition temperature of 0 DEG C or lower, an isocyanate-based hardener, and dendritic electroconductive particles, wherein the contents of the isocyanate-based hardener and the dendritic electroconductive particles are 0.05-5.0 parts by mass and 120-240 parts by mass, respectively, per 100 parts by mass of the acrylic resin. The ratio of the thickness of the pressure-sensitive adhesive sheet to the median diameter D50 of the dendritic electroconductive particles, (pressure-sensitive-adhesive sheet thickness)/D50, is 1.3-5.0.

Description

各向同性導電性黏著片Isotropic conductive adhesive sheet

本發明係關於各向同性導電性黏著片。更詳細地說，本發明係關於用於印刷配線板之各向同性導電性黏著片。The present invention relates to an isotropic conductive adhesive sheet. In more detail, the present invention relates to an isotropic conductive adhesive sheet for printed wiring boards.

背景技術 於印刷配線板中，經常使用導電性接著劑。例如，接著於印刷配線板進行使用之電磁波屏蔽膜(以下有時簡稱為「屏蔽膜」)，具有金屬箔等屏蔽層與設置於該屏蔽層表面之導電性接著片。導電性接著片係例如將導電性接著劑片狀地塗覆於屏蔽層表面而形成，將屏蔽層接著於印刷配線板表面之同時，使印刷配線板之接地圖案與屏蔽層導通。Background technique In printed wiring boards, conductive adhesives are often used. For example, an electromagnetic wave shielding film (hereinafter sometimes referred to as a "shielding film") to be subsequently used on a printed wiring board has a shielding layer such as a metal foil and a conductive adhesive sheet provided on the surface of the shielding layer. The conductive adhesive sheet is formed by, for example, coating a conductive adhesive on the surface of the shielding layer in a sheet form. The shielding layer is adhered to the surface of the printed wiring board and at the same time the grounding pattern of the printed wiring board and the shielding layer are connected.

上述導電性接著片係要求與設置於印刷配線板表面之絕緣膜(覆蓋膜)牢固地密著，且於屏蔽膜所設置之開口部中確保與外部接地良好的導通。The above-mentioned conductive adhesive sheet is required to be firmly adhered to the insulating film (covering film) provided on the surface of the printed wiring board, and to ensure good conduction with the external ground in the opening provided in the shielding film.

關於具有導電性接著片之屏蔽膜，例如已知有專利文獻1及2所揭示者。上述屏蔽膜係以露出導電性接著片之表面貼著於印刷配線板表面、具體為印刷配線板表面所設置之覆蓋膜表面之方式進行貼合後使用。此等導電性接著片通常於高溫、高壓條件下進行熱壓接，而接著及積層於印刷配線板。 先行技術文獻 專利文獻Regarding a shielding film having a conductive adhesive sheet, for example, those disclosed in Patent Documents 1 and 2 are known. The above-mentioned shielding film is used after being pasted so that the surface of the conductive adhesive sheet is exposed to the surface of the printed wiring board, specifically the surface of the cover film provided on the surface of the printed wiring board. These conductive adhesive sheets are usually thermally compressed under high temperature and high pressure conditions, and then laminated on the printed wiring board. Advanced technical literature Patent literature

[專利文獻1]日本特開2015-110769號公報 [專利文獻2]日本專利2012-28334號公報[Patent Document 1] Japanese Patent Application Publication No. 2015-110769 [Patent Document 2] Japanese Patent No. 2012-28334

發明概要 發明欲解決之課題 近年來，有追求不於高溫、高壓條件下而是可於較寬大條件下接著於印刷配線板之導電性黏著片的傾向。然而，先前的各向異性導電性黏著片以較寬大條件接著於印刷配線板時，有如下問題：與外部接地之電性連接不穩定、熱循環試驗後之電阻值變化變大。為了提高電性連接之穩定性，增加先前的各向異性導電性黏著片中的導電性粒子的調配量而製成各向同性導電性黏著片時，則與印刷配線板之密著力就會變差。Summary of the invention The problem to be solved by the invention In recent years, there is a tendency to pursue a conductive adhesive sheet that can be adhered to a printed wiring board under a wide range of conditions, not under high temperature and high pressure conditions. However, when the previous anisotropic conductive adhesive sheet is attached to a printed wiring board under a wide range of conditions, there are problems as follows: the electrical connection to the external ground is unstable, and the resistance value change after the thermal cycle test becomes large. In order to improve the stability of electrical connection, increase the amount of conductive particles in the previous anisotropic conductive adhesive sheet to make an isotropic conductive adhesive sheet, the adhesion force to the printed wiring board will change difference.

本發明係鑑於上述而完成者，本發明之目的在於提供一種導電性黏著片，其可以簡單地以高密著力接著於被接著體，且電性連接穩定性優異、熱循環試驗後之電阻值變化較小。The present invention was completed in view of the above. The object of the present invention is to provide a conductive adhesive sheet that can be easily adhered to the adherend with high adhesion, has excellent electrical connection stability, and changes in resistance after thermal cycle tests. Smaller.

用以解決課題之手段 本發明人等為達成上述目的，專心致力於研究，結果發現：由含有特定的丙烯酸系樹脂、特定量的異氰酸酯系硬化劑及特定量的樹枝狀導電性粒子的黏著劑形成、且黏著片厚度與樹枝狀導電性粒子之中值粒徑D50之比在特定範圍內之各向同性導電性黏著片，可以簡單地以高密著力接著於被接著體，且電性連接穩定性優異、熱循環試驗後之電阻值變化較小。本發明係基於上述發現而完成者。Means to solve the problem In order to achieve the above-mentioned object, the inventors devoted themselves to research and found that it is formed by an adhesive containing a specific acrylic resin, a specific amount of an isocyanate curing agent, and a specific amount of dendritic conductive particles, and the thickness of the adhesive sheet The isotropic conductive adhesive sheet with the ratio of the median diameter D50 of the dendritic conductive particles within a specific range can be easily adhered to the adherend with high density, and the electrical connection stability is excellent, and the thermal cycle test After that, the resistance value changes less. The present invention was completed based on the above findings.

即，本發明提供一種各向同性導電性黏著片，其由黏著劑形成，該黏著劑含有玻璃轉移溫度為0℃以下之丙烯酸系樹脂、異氰酸酯系硬化劑及樹枝狀導電性粒子，且相對於上述丙烯酸系樹脂100質量份，上述異氰酸酯系硬化劑之含量為0.05~5.0質量份、上述樹枝狀導電性粒子之含量為120~240質量份；並且，黏著片厚度與上述樹枝狀導電性粒子之中值粒徑D50之比[黏著片厚度/D50]為1.3~5.0。That is, the present invention provides an isotropic conductive adhesive sheet, which is formed of an adhesive containing an acrylic resin having a glass transition temperature of 0°C or less, an isocyanate curing agent, and dendritic conductive particles, and relative to 100 parts by mass of the acrylic resin, 0.05 to 5.0 parts by mass of the isocyanate curing agent, and 120 to 240 parts by mass of the dendritic conductive particles; and the thickness of the adhesive sheet is more than that of the dendritic conductive particles. The ratio of median particle diameter D50 [adhesive sheet thickness/D50] is 1.3~5.0.

上述樹枝狀導電性粒子之D50宜為6~15μm。The D50 of the dendritic conductive particles is preferably 6 to 15 μm.

上述各向同性導電性黏著片之厚度宜為1~100μm。The thickness of the above-mentioned isotropic conductive adhesive sheet is preferably 1-100μm.

上述丙烯酸系樹脂之酸值宜為5mgKOH/g以下。The acid value of the above-mentioned acrylic resin is preferably 5 mgKOH/g or less.

上述丙烯酸系樹脂之重量平均分子量宜為10萬~100萬。The weight average molecular weight of the above-mentioned acrylic resin is preferably 100,000 to 1 million.

上述丙烯酸系樹脂之玻璃轉移溫度宜為-50℃以上。The glass transition temperature of the above-mentioned acrylic resin is preferably -50°C or higher.

上述各向同性導電性黏著片宜在溫度20℃、壓力1kg/10mm之條件下貼著於聚醯亞胺膜時對聚醯亞胺膜之180°剝離接著力為4N/20mm以上。The above-mentioned isotropic conductive adhesive sheet is preferably attached to the polyimide film at a temperature of 20°C and a pressure of 1kg/10mm. The 180° peeling adhesive force to the polyimide film should be 4N/20mm or more.

發明效果 根據本發明之各向同性導電性黏著片，可以簡單地以高密著力接著於被接著體，且電性連接穩定性優異、熱循環試驗後之電阻值變化較小。因此，可簡單地製造具備本發明之各向同性導電性黏著片之屏蔽印刷配線板，該屏蔽印刷配線板與外部接地之連接穩定性優異。Invention effect According to the isotropic conductive adhesive sheet of the present invention, the adherend can be easily adhered to the adherend with high density, and the electrical connection stability is excellent, and the resistance value change after the thermal cycle test is small. Therefore, the shield printed wiring board provided with the isotropic conductive adhesive sheet of the present invention can be easily manufactured, and the connection stability of the shield printed wiring board to the external ground is excellent.

用以實施發明之形態 [各向同性導電性黏著片] 本發明之各向同性導電性黏著片係由至少包含玻璃轉移溫度為0℃以下之丙烯酸系樹脂、異氰酸酯系硬化劑及樹枝狀導電性粒子的黏著劑(黏著劑組成物)形成。The form used to implement the invention [Isotropic conductive adhesive sheet] The isotropic conductive adhesive sheet of the present invention is formed of an adhesive (adhesive composition) containing at least an acrylic resin having a glass transition temperature of 0°C or less, an isocyanate curing agent, and dendritic conductive particles.

本發明之各向同性導電性黏著片，其黏著片厚度與樹枝狀導電性粒子之D50之比[黏著片厚度/D50]為1.3~5.0、宜為1.4~4.0、較佳為1.5~4.0、更佳為2.5~4.0。藉由上述比為1.3以上，可簡單地接著於被接著體，且對被接著體之密著性更良好。藉由上述比為5.0以下，電性連接穩定性優異。又，藉由上述比於上述範圍內，熱循環試驗後之電阻值變化較小。In the isotropic conductive adhesive sheet of the present invention, the ratio of the thickness of the adhesive sheet to the D50 of the dendritic conductive particles [adhesive sheet thickness/D50] is 1.3 to 5.0, preferably 1.4 to 4.0, preferably 1.5 to 4.0, More preferably, it is 2.5~4.0. With the above ratio of 1.3 or more, it can be easily adhered to the adherend, and the adhesion to the adherend is better. When the above ratio is 5.0 or less, the electrical connection stability is excellent. In addition, by the above ratio being within the above range, the resistance value change after the thermal cycle test is small.

(丙烯酸系樹脂) 用以形成本發明之各向同性導電性黏著片的黏著劑(黏著劑組成物)，包含玻璃轉移溫度為0℃以下的丙烯酸系樹脂。上述丙烯酸系樹脂可僅使用一種、亦可使用二種以上。(Acrylic resin) The adhesive (adhesive composition) used to form the isotropic conductive adhesive sheet of the present invention includes an acrylic resin having a glass transition temperature of 0°C or less. Only one type of the above-mentioned acrylic resin may be used, or two or more types may be used.

上述丙烯酸系樹脂之玻璃轉移溫度(Tg)為0℃以下、宜為-5℃以下、較佳為-10℃以下。又，上述玻璃轉移溫度宜為-50℃以上、較佳為-30℃以上。上述玻璃轉移溫度係利用示差掃描熱量分析求出。若玻璃轉移溫度超過0℃，在較低壓力及溫度條件下貼著於被接著體時，與被接著體之密著強度及連接電阻值變低。The glass transition temperature (Tg) of the acrylic resin is 0°C or lower, preferably -5°C or lower, and preferably -10°C or lower. In addition, the above-mentioned glass transition temperature is preferably -50°C or higher, more preferably -30°C or higher. The above-mentioned glass transition temperature is obtained by differential scanning calorimetry. If the glass transition temperature exceeds 0°C, when it is attached to the adherend under relatively low pressure and temperature conditions, the adhesion strength and connection resistance value with the adherend will decrease.

上述丙烯酸系樹脂之酸值並無特別限定，但宜為5mgKOH/g以下、較佳為3mgKOH/g以下、更佳為1mgKOH/g以下。上述酸值，例如大於0mgKOH/g。若上述酸值為5mgKOH/g以下，因硬化劑所致之丙烯酸系樹脂的硬化就不會進行過度，故可簡單地接著於被接著體，對被接著體之密著性變得更良好，且電性連接穩定性更優異，熱循環試驗後之電阻值變化變更小。The acid value of the acrylic resin is not particularly limited, but it is preferably 5 mgKOH/g or less, preferably 3 mgKOH/g or less, and more preferably 1 mgKOH/g or less. The aforementioned acid value is, for example, greater than 0 mgKOH/g. If the above acid value is 5 mgKOH/g or less, the curing of the acrylic resin due to the curing agent will not proceed excessively, so it can be easily adhered to the adherend, and the adhesion to the adherend becomes better. And the electrical connection stability is more excellent, and the resistance value change after the thermal cycle test is small.

上述丙烯酸系樹脂之重量平均分子量並無特別限定，但宜為10萬~100萬、較佳為20萬~60萬。若上述重量平均分子量於上述範圍內，對被接著體之密著性變得更良好，且電性連接穩定性更優異，熱循環試驗後之電阻值變化變更小。上述重量平均分子量可利用凝膠滲透層析法(GPC)使用聚苯乙烯作為標準物質進行測定。The weight average molecular weight of the acrylic resin is not particularly limited, but is preferably 100,000 to 1 million, and more preferably 200,000 to 600,000. If the weight average molecular weight is within the above range, the adhesion to the adherend becomes better, the electrical connection stability is more excellent, and the change in the resistance value after the thermal cycle test is small. The above-mentioned weight average molecular weight can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

上述丙烯酸系樹脂宜具有能與異氰酸酯反應之官能基、較佳具有羥基。藉此，上述丙烯酸系樹脂因異氰酸酯系硬化劑而來的硬化性會提高、對被接著體之密著性變得更良好，且電性連接穩定性更優異，熱循環試驗後之電阻值變化變更小。上述具有羥基之丙烯酸系樹脂，例如可藉由使用後述的含羥基(甲基)丙烯酸酯作為單體成分來製作。The aforementioned acrylic resin preferably has a functional group capable of reacting with isocyanate, and preferably has a hydroxyl group. As a result, the acrylic resin has improved curability due to the isocyanate curing agent, better adhesion to the adherend, and better electrical connection stability, and the resistance value changes after the thermal cycle test The change is small. The acrylic resin having a hydroxyl group can be produced, for example, by using the hydroxyl-containing (meth)acrylate described later as a monomer component.

上述丙烯酸系樹脂係以(甲基)丙烯酸酯化合物作為必要的單體成分所構成的聚合物、即至少具有來自(甲基)丙烯酸酯化合物之結構單元的聚合物(或共聚物)。又，於本說明書中所謂「(甲基)丙烯酸酯」係指丙烯酸酯及/或甲基丙烯酸酯。然後，所謂「(甲基)丙烯酸酯化合物」係表示具有丙烯醯基及/或甲基丙烯醯基之化合物。關於「(甲基)丙烯醯基」亦相同。上述(甲基)丙烯酸酯化合物可僅使用一種，亦可使用二種以上。The acrylic resin is a polymer composed of a (meth)acrylate compound as an essential monomer component, that is, a polymer (or copolymer) having at least a structural unit derived from the (meth)acrylate compound. In addition, the term "(meth)acrylate" in this specification means acrylate and/or methacrylate. In addition, the term "(meth)acrylate compound" means a compound having an acrylic group and/or a methacrylic group. The same applies to "(meth)acryloyl". Only one type of the (meth)acrylate compound may be used, or two or more types may be used.

上述丙烯酸系樹脂，在構成丙烯酸系樹脂之單體成分總量(100質量%)中來自(甲基)丙烯酸酯化合物的結構單元的含有比率，並無特別限定，例如為50質量%以上(50~100質量%)、宜為60質量%以上(60~100質量%)、較佳為90質量%以上、更佳為95質量%以上。The above-mentioned acrylic resin has no particular limitation on the content ratio of the structural unit derived from the (meth)acrylate compound in the total amount (100% by mass) of the monomer components constituting the acrylic resin. For example, it is 50% by mass or more (50% by mass). ~100% by mass), preferably 60% by mass or more (60-100% by mass), preferably 90% by mass or more, more preferably 95% by mass or more.

關於上述(甲基)丙烯酸酯化合物，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十二烷酯等具有直鏈或支鏈狀烷基的(甲基)丙烯酸烷基酯；(甲基)丙烯酸；丙烯酸羧乙酯等含羧基之(甲基)丙烯酸酯；(甲基)丙烯酸2-羥甲酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸6-羥己酯、二乙二醇單(甲基)丙烯酸酯、二丙二醇單(甲基)丙烯酸酯等含羥基之(甲基)丙烯酸酯；(甲基)丙烯酸環己酯等(甲基)丙烯酸環烷基酯；N-羥甲基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺等(甲基)丙烯醯胺衍生物；(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯、(甲基)丙烯酸二丙胺基乙酯、(甲基)丙烯酸二甲胺基丙酯、(甲基)丙烯酸二丙胺基丙酯等(甲基)丙烯酸二烷胺基烷基酯等。Regarding the above-mentioned (meth)acrylate compounds, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate ) Butyl acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, hexyl (meth)acrylate, isoamyl (meth)acrylate , Octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, etc. Alkyl (meth)acrylate with chain or branched alkyl; (meth)acrylic acid; carboxyethyl acrylate and other carboxyl-containing (meth)acrylates; 2-hydroxymethyl (meth)acrylate, ( 2-hydroxyethyl meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, diethylene glycol mono(methyl) (Meth)acrylic acid esters containing hydroxyl groups such as acrylate and dipropylene glycol mono(meth)acrylate; cyclohexyl (meth)acrylate and other cycloalkyl (meth)acrylates; N-methylol( Meth)acrylamide, N-butoxymethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide (Meth)acrylamide derivatives such as amines; dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dipropylaminoethyl (meth)acrylate, (methyl) ) Dialkylaminoalkyl (meth)acrylates such as dimethylaminopropyl acrylate, dipropylaminopropyl (meth)acrylate and the like.

又，關於上述(甲基)丙烯酸酯化合物，亦可列舉：新戊二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯等多官能(甲基)丙烯酸酯。進而，亦可列舉：2-羥基-3-丙烯醯氧基丙基(甲基)丙烯酸酯、苯基環氧丙基醚(甲基)丙烯酸酯六亞甲基二異氰酸酯胺基甲酸酯預聚物、雙酚A二環氧丙基醚丙烯酸加成物等。Moreover, regarding the above-mentioned (meth)acrylate compound, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra( Multifunctional (meth)acrylates such as meth)acrylate, ethylene glycol di(meth)acrylate, and diethylene glycol di(meth)acrylate. Furthermore, it can also be listed: 2-hydroxy-3-acryloyloxypropyl (meth)acrylate, phenylglycidyl ether (meth)acrylate hexamethylene diisocyanate urethane pre Polymers, bisphenol A diglycidyl ether acrylic acid adducts, etc.

上述丙烯酸系樹脂亦可具有來自(甲基)丙烯酸化合物以外之單體成分的結構單元。關於上述單體成分，並無特別限定，例如可列舉：巴豆酸、衣康酸、富馬酸、馬來酸等含羧基之聚合性不飽和化合物或其酸酐；苯乙烯、乙烯基甲苯、α-甲基苯乙烯等苯乙烯系化合物；乙酸乙烯酯、丙酸乙烯酯等乙烯酯類；氯乙烯等鹵化乙烯；甲基乙烯基醚等乙烯基醚類；(甲基)丙烯腈等含氰基之乙烯基化合物；乙烯、丙烯等α-烯烴等。The acrylic resin may have a structural unit derived from a monomer component other than the (meth)acrylic compound. There are no particular limitations on the above-mentioned monomer components, and examples include: crotonic acid, itaconic acid, fumaric acid, maleic acid and other carboxyl group-containing polymerizable unsaturated compounds or their anhydrides; styrene, vinyl toluene, α -Styrenic compounds such as methyl styrene; vinyl esters such as vinyl acetate and vinyl propionate; halogenated vinyl such as vinyl chloride; vinyl ethers such as methyl vinyl ether; (meth)acrylonitrile and other cyanide-containing compounds Base vinyl compounds; α-olefins such as ethylene and propylene.

上述丙烯酸系樹脂之含有比率並無特別限定，但宜相對於上述黏著劑中之固體成分總量100質量%為20~60質量%、較佳為30~50質量%、更佳為35~45質量%。若上述含有比率為20質量%以上，對被接著體之密著性變得更加良好。若上述含有比率為60質量%以下，則導電性粒子之比率相對較多、電穩定性更優異。The content ratio of the acrylic resin is not particularly limited, but it is preferably 20-60% by mass, preferably 30-50% by mass, more preferably 35-45 relative to the total solid content 100% by mass in the adhesive. quality%. If the above-mentioned content ratio is 20% by mass or more, the adhesion to the adherend becomes more favorable. If the said content ratio is 60 mass% or less, the ratio of electroconductive particle will be relatively large, and electrical stability will be more excellent.

(異氰酸酯系硬化劑) 上述異氰酸酯系硬化劑為分子內具有2個以上異氰酸酯基的化合物，用以促進上述丙烯酸系樹脂的硬化。上述異氰酸酯系硬化劑可僅使用一種，亦可使用二種以上。(Isocyanate hardener) The isocyanate-based curing agent is a compound having two or more isocyanate groups in the molecule, and is used to promote the curing of the acrylic resin. Only one kind of the above-mentioned isocyanate-based curing agent may be used, or two or more kinds may be used.

關於上述異氰酸酯系硬化劑，例如可列舉：1,2-伸乙基二異氰酸酯、1,4-伸丁基二異氰酸酯、1,6-六亞甲基二異氰酸酯等低級脂肪族聚異氰酸酯；伸環戊基二異氰酸酯、伸環己基二異氰酸酯、異佛爾酮二異氰酸酯、氫化甲苯二異氰酸酯、氫化二甲苯二異氰酸酯等脂環族聚異氰酸酯；2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、4,4’-二苯甲烷二異氰酸酯、伸茬基二異氰酸酯等芳香族聚異氰酸酯等。Regarding the isocyanate-based curing agent, for example, lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; ring extension Alicyclic polyisocyanates such as amyl diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate; 2,4-toluene diisocyanate, 2,6-toluene diisocyanate , 4,4'-diphenylmethane diisocyanate, diisocyanate and other aromatic polyisocyanates.

上述異氰酸酯系硬化劑之含量相對於上述丙烯酸系樹脂100質量份為0.05~5.0質量份、宜為0.1~4.0質量份、較佳為1.0~3.5質量份。藉由上述含量為0.05質量份以上，可防止熱循環試驗時之黏著片溶解，且熱循環試驗後之電阻值變化變小。藉由上述含量為5.0質量份以下，可抑制因硬化劑所致之丙烯酸系樹脂的過度硬化，且對被接著體之密著性變得良好。The content of the isocyanate-based hardener is 0.05 to 5.0 parts by mass, preferably 0.1 to 4.0 parts by mass, and more preferably 1.0 to 3.5 parts by mass relative to 100 parts by mass of the acrylic resin. With the above content being 0.05 parts by mass or more, the dissolution of the adhesive sheet during the thermal cycle test can be prevented, and the resistance value change after the thermal cycle test is reduced. When the content is 5.0 parts by mass or less, excessive curing of the acrylic resin due to the curing agent can be suppressed, and the adhesion to the adherend can be improved.

(導電性粒子) 本發明之各向同性導電性黏著片包含樹枝狀(枝晶形狀(dendrite))的導電性粒子。藉由使用樹枝狀導電性粒子，能獲得可簡單地以高密著力接著於被接著體、且電性連接穩定性優異、熱循環試驗後之電阻值變化較小的導電性黏著片。上述樹枝狀導電性粒子可僅使用一種，亦可使用二種以上。(Conductive particles) The isotropic conductive adhesive sheet of the present invention contains dendritic (dendrite) conductive particles. By using dendritic conductive particles, it is possible to obtain a conductive adhesive sheet that can be easily adhered to the adherend with high adhesion, has excellent electrical connection stability, and has a small change in resistance value after a thermal cycle test. As for the said dendritic electroconductive particle, only 1 type may be used and 2 or more types may be used.

關於上述樹枝狀導電性粒子，例如可列舉：金屬粒子、金屬被覆樹脂粒子、碳填料等。Examples of the dendritic conductive particles include metal particles, metal-coated resin particles, and carbon fillers.

關於構成上述金屬粒子及上述金屬被覆樹脂粒子之被覆部的金屬，例如可列舉：金、銀、銅、鎳、鋅等。上述金屬可僅使用一種，亦可使用二種以上。Regarding the metal constituting the coating portion of the metal particles and the metal-coated resin particles, for example, gold, silver, copper, nickel, zinc, etc. may be mentioned. Only one kind of the above-mentioned metals may be used, or two or more kinds may be used.

關於上述金屬粒子，具體上例如可列舉：銅粒子、銀粒子、鎳粒子、銀被覆銅粒子、金被覆銅粒子、銀被覆鎳粒子、金被覆鎳粒子、銀被覆合金粒子等。關於上述銀被覆合金粒子，可舉例如：利用銀被覆包含銅之合金粒子(例如由銅、鎳及鋅之合金構成之銅合金粒子)的銀被覆銅合金粒子等。上述金屬粒子可藉由電解法、霧化法或還原法等製作。Specific examples of the metal particles include copper particles, silver particles, nickel particles, silver-coated copper particles, gold-coated copper particles, silver-coated nickel particles, gold-coated nickel particles, and silver-coated alloy particles. The aforementioned silver-coated alloy particles include, for example, silver-coated copper alloy particles in which alloy particles containing copper (for example, copper alloy particles composed of an alloy of copper, nickel, and zinc) are coated with silver. The above-mentioned metal particles can be produced by an electrolysis method, an atomization method, a reduction method, or the like.

關於上述金屬粒子，其中較佳為銀粒子、銀被覆銅粒子、銀被覆銅合金粒子。由導電性優異、可抑制金屬粒子之氧化及凝集且可降低金屬粒子成本之觀點，尤宜為銀被覆銅粒子、銀被覆銅合金粒子。Among the above-mentioned metal particles, preferred are silver particles, silver-coated copper particles, and silver-coated copper alloy particles. From the viewpoint of excellent electrical conductivity, suppression of oxidation and aggregation of metal particles, and reduction of the cost of metal particles, silver-coated copper particles and silver-coated copper alloy particles are particularly suitable.

上述樹枝狀導電性粒子之中值粒徑(D50)並無特別限定，但宜為6~15μm、較佳為7~10μm。若上述D50為6μm以上，對被接著體之密著性變得更加良好。若上述D50為15μm以下，則熱循環試驗後之電阻值變化變更小。上述D50係指利用雷射繞射-散射法求得的粒度分布中於累計值50%的粒徑。The median diameter (D50) of the dendritic conductive particles is not particularly limited, but is preferably 6 to 15 μm, more preferably 7 to 10 μm. If the above-mentioned D50 is 6 μm or more, the adhesion to the adherend becomes better. If the above D50 is 15 μm or less, the change in resistance value after the thermal cycle test is small. The above D50 refers to the particle size that is 50% of the cumulative value in the particle size distribution obtained by the laser diffraction-scattering method.

上述樹枝狀導電性粒子之含量係相對於上述丙烯酸系樹脂100質量份為120~240質量份、宜為130~200質量份、較佳為140~180質量份。藉由上述含量為120質量份以上，電性連接穩定性優異且熱循環試驗後之電阻值變化較小。藉由上述含量為240質量份以下，可簡單地接著於被接著體，且對被接著體之密著性變得良好。The content of the dendritic conductive particles is 120 to 240 parts by mass relative to 100 parts by mass of the acrylic resin, preferably 130 to 200 parts by mass, and more preferably 140 to 180 parts by mass. With the above content being 120 parts by mass or more, the electrical connection stability is excellent and the resistance value change after the thermal cycle test is small. When the aforementioned content is 240 parts by mass or less, it can be easily adhered to the adherend, and the adhesion to the adherend becomes good.

於無損本發明效果之範圍內，本發明之各向同性導電性黏著片及用以形成其之黏著劑亦可含有上述各成分以外的其他成分。關於上述其他成分，可舉公知乃至慣用的接著片中所含的成分。關於上述其他成分，例如可列舉：阻燃劑、塑化劑、消泡劑、黏度調整劑、抗氧化劑、稀釋劑、防沉劑、填充劑、著色劑、調平劑、偶合劑、賦黏樹脂等。上述其他成分可僅使用一種，亦可使用二種以上。再者，相對於上述黏著劑中之固體成分總量100質量%，上述丙烯酸系樹脂、上述異氰酸酯系硬化劑及上述樹枝狀導電性粒子合計之含有比率宜為80質量%以上、較佳為90質量%以上、更佳為95質量%以上、尤宜為98質量%以上。Within the range that does not impair the effects of the present invention, the isotropic conductive adhesive sheet of the present invention and the adhesive used to form it may also contain other components other than the above-mentioned components. Regarding the above-mentioned other components, known or commonly used components contained in the adhesive sheet can be cited. Regarding the above-mentioned other components, for example, flame retardants, plasticizers, defoamers, viscosity modifiers, antioxidants, diluents, anti-settling agents, fillers, colorants, leveling agents, coupling agents, and tackifiers are listed. Resin etc. Only one kind of the above-mentioned other components may be used, or two or more kinds may be used. Furthermore, the total content of the acrylic resin, the isocyanate curing agent, and the dendritic conductive particles is preferably 80% by mass or more, preferably 90% by mass, relative to 100% by mass of the total solid content in the adhesive. Mass% or more, more preferably 95 mass% or more, particularly preferably 98 mass% or more.

本發明之各向同性導電性黏著片之厚度可根據用途適當選擇，但宜為1~100μm、較佳為5~50μm、更佳為10~40μm、尤宜為10~30μm。若上述厚度為1μm以上，可簡單地接著於被接著體，且對被接著體之密著性變得更良好。若上述厚度為100μm以下，則電性連接穩定性變得更良好。又，將本發明之各向同性導電性黏著片用於黏接膜(例如補強板或外部接地與印刷配線板的導電性黏接膜)時，例如為10~70μm、宜為30~65μm。The thickness of the isotropic conductive adhesive sheet of the present invention can be appropriately selected according to the application, but is preferably 1-100 μm, preferably 5-50 μm, more preferably 10-40 μm, and particularly preferably 10-30 μm. If the above-mentioned thickness is 1 μm or more, it can be easily adhered to the adherend, and the adhesion to the adherend becomes better. If the thickness is 100 μm or less, the electrical connection stability becomes better. In addition, when the isotropic conductive adhesive sheet of the present invention is used for an adhesive film (for example, a reinforcing plate or a conductive adhesive film for external grounding and a printed wiring board), the thickness is, for example, 10 to 70 μm, preferably 30 to 65 μm.

本發明之各向同性導電性黏著片在溫度20℃、壓力1kg/10mm之條件下貼著於聚醯亞胺膜時對聚醯亞胺膜之180°剝離接著力並無特別限定，宜為4N/20mm以上、較佳為5N/20mm以上。若上述剝離接著力為4N/20mm以上，可簡單地接著於被接著體，且對被接著體之密著性變得更良好。且藉此，電性連接穩定性更優異且熱循環試驗後之電阻值變化亦變得更小。上述180°剝離接著力係於常溫下以拉伸速度300mm/分之條件測定的值。When the isotropic conductive adhesive sheet of the present invention is attached to a polyimide film under the conditions of a temperature of 20°C and a pressure of 1kg/10mm, there is no particular limitation on the 180° peel adhesion force of the polyimide film, and it is preferably 4N/20mm or more, preferably 5N/20mm or more. If the peeling adhesive force is 4N/20mm or more, it can be easily adhered to the adherend, and the adhesion to the adherend becomes better. And by this, the electrical connection stability is more excellent and the resistance value change after the thermal cycle test becomes smaller. The above-mentioned 180° peeling adhesive force is a value measured under the condition of a stretching speed of 300 mm/min at room temperature.

本發明之各向同性導電性黏著片的利用以下導電性試驗求得的電阻值(初始電阻值)並無特別限定，但宜為1000mΩ以下、較佳為100mΩ以下、更佳為20mΩ以下。若上述電阻值為1000mΩ以下，外部接地與各向同性導電性黏著片之於通孔中的導通性變得良好。 ＜導電性試驗＞ 將二個寬度10mm×長度30mm之電極以間隔成為100mm之方式配置於厚度25μm之聚醯亞胺膜上，並將貼合有屏蔽基材(厚度12μm之PET膜/厚度0.1μm之銀蒸鍍膜)的銀蒸鍍膜面與各向同性導電性黏著片的積層體的各向同性導電性黏著片面，於壓力1kg/10mm之條件下以連接二個電極間之方式進行貼合，再使用4端子法測試儀測定二個電極間的電阻值。The resistance value (initial resistance value) obtained by the following conductivity test of the isotropic conductive adhesive sheet of the present invention is not particularly limited, but is preferably 1000 mΩ or less, preferably 100 mΩ or less, and more preferably 20 mΩ or less. If the above-mentioned resistance value is 1000mΩ or less, the electrical conductivity of the external grounding and isotropic conductive adhesive sheet in the through hole becomes good. ＜Conductivity test＞ Two electrodes with a width of 10mm x a length of 30mm are arranged on a polyimide film with a thickness of 25μm at an interval of 100mm, and a shielding substrate (PET film with a thickness of 12μm/a silver vapor-deposited film with a thickness of 0.1μm is attached. ) The silver vapor-deposited film surface and the isotropic conductive adhesive sheet surface of the laminated body of the isotropic conductive adhesive sheet are bonded by connecting two electrodes under the condition of a pressure of 1kg/10mm, and then 4 terminals are used The method tester measures the resistance between the two electrodes.

本發明之各向同性導電性黏著片之下述熱循環試驗後所測定的電阻值(熱循環試驗後電阻值)相對於上述初始電阻值的變化率(熱循環試驗後電阻值變化率)，並無特別限定，但宜為40%以下、較佳為30%以下、更佳為25%以下。若上述電阻值之變化率為40%以下，即使於熱循環試驗後，外部接地與各向同性導電性黏著片之於通孔中的導通性亦變得良好。再者，上述熱循環試驗後電阻值變化率由下式求出。又，上述熱循環試驗後電阻值可使用熱循環試驗後之各向同性導電性黏著片，藉由上述導電性試驗所記載的方法進行測定。 熱循環試驗後電阻值變化率(%)={(熱循環試驗後電阻值(Ω)/初始電阻值(Ω))-1}×100 ＜熱循環試驗＞ 於溫度條件設為低溫側-40℃、高溫側85℃、各溫度保持時間30分鐘、升溫速度5℃/分、降溫速度5℃/分且200次循環之條件下，就上述屏蔽基材與各向同性導電性黏著片之積層體進行試驗。The change rate of the resistance value (resistance value after thermal cycle test) measured after the following thermal cycle test of the isotropic conductive adhesive sheet of the present invention with respect to the above-mentioned initial resistance value (resistance value change rate after thermal cycle test), It is not particularly limited, but it is preferably 40% or less, preferably 30% or less, and more preferably 25% or less. If the above-mentioned change rate of the resistance value is 40% or less, even after the thermal cycle test, the conductivity of the external ground and the isotropic conductive adhesive sheet in the through hole becomes good. In addition, the resistance value change rate after the above-mentioned thermal cycle test is obtained by the following formula. In addition, the resistance value after the thermal cycle test can be measured by the method described in the electrical conductivity test using the isotropic conductive adhesive sheet after the thermal cycle test. Change rate of resistance value after thermal cycle test (%)={(resistance value after thermal cycle test (Ω)/initial resistance value (Ω))-1}×100 ＜Thermal cycle test＞ Under the condition that the temperature conditions are set to -40°C on the low temperature side, 85°C on the high temperature side, each temperature holding time of 30 minutes, heating rate 5°C/min, cooling rate 5°C/min, and 200 cycles, the above-mentioned shielding substrate and The laminated body of the isotropic conductive adhesive sheet was tested.

本發明之各向同性導電性接著片可藉由公知乃至慣用之製造方法來製造。例如可將上述黏著劑塗佈(塗覆)於分離膜等暫時基材或基材上，視需要利用加熱等去溶媒及/或使一部分硬化而形成。上述加熱例如於25~100℃下進行1~48小時左右。The isotropic conductive adhesive sheet of the present invention can be manufactured by a well-known or even customary manufacturing method. For example, the adhesive can be formed by coating (coating) the above-mentioned adhesive on a temporary base material or base material such as a separation film, and removing the solvent by heating or the like and/or hardening a part of it as necessary. The heating is performed at 25 to 100°C for about 1 to 48 hours, for example.

上述黏著劑亦可進一步包含溶劑(溶媒)。關於上述溶劑，例如可列舉：甲苯、丙酮、甲乙酮、甲醇、乙醇、丙醇及二甲基甲醯胺等。黏著劑之固體成分濃度可根據欲形成之各向同性導電性黏著片之厚度等而適當設定。The above-mentioned adhesive may further include a solvent (solvent). Examples of the above-mentioned solvent include toluene, acetone, methyl ethyl ketone, methanol, ethanol, propanol, and dimethylformamide. The solid content concentration of the adhesive can be appropriately set according to the thickness of the isotropic conductive adhesive sheet to be formed.

於塗佈上述黏著劑時，亦可使用公知之塗佈法。例如可使用：凹版輥塗佈機、逆輥塗佈機、接觸輥塗佈機、模嘴塗佈機浸漬輥塗佈機、棒塗佈機、刮刀塗佈機、噴霧塗佈機、缺角輪塗佈機、直接塗佈機、狹縫式模具塗佈機等塗佈機。When applying the above-mentioned adhesive, a well-known coating method can also be used. For example, you can use: gravure roll coater, reverse roll coater, contact roll coater, die nozzle coater, dip roll coater, bar coater, knife coater, spray coater, cut corner Coating machines such as wheel coaters, direct coaters, and slot die coaters.

再者，本發明之各向同性導電性黏著片亦可為經B階段化的黏著片(B階段狀態的黏著片)，其係利用加熱使上述丙烯酸系樹脂及異氰酸酯系硬化劑之一部分反應而獲得。Furthermore, the isotropic conductive adhesive sheet of the present invention may also be a B-staged adhesive sheet (adhesive sheet in the B-stage state), which is obtained by partially reacting the acrylic resin and isocyanate-based hardener by heating. obtain.

本發明之各向同性導電性黏著片宜為印刷配線板用途，尤宜為可撓性印刷配線板(FPC)用途。本發明之各向同性導電性黏著片可以簡單地以高密著力接著於被接著體，且電性連接穩定性優異、熱循環試驗後之電阻值變化較小。因此，本發明之各向同性導電性黏著片可適合用作印刷配線板用(尤其FPC用)電磁波屏蔽膜、導電性黏接膜。The isotropic conductive adhesive sheet of the present invention is preferably used for printed wiring boards, and particularly preferably used for flexible printed wiring boards (FPC). The isotropic conductive adhesive sheet of the present invention can be easily adhered to the adherend with high density, has excellent electrical connection stability, and has a small resistance value change after the thermal cycle test. Therefore, the isotropic conductive adhesive sheet of the present invention can be suitably used as an electromagnetic wave shielding film and a conductive adhesive film for printed wiring boards (especially for FPC).

有時將具有本發明之各向同性導電性黏著片之電磁波屏蔽膜稱為「本發明之電磁波屏蔽膜」。本發明之電磁波屏蔽膜宜具備包含本發明之各向同性導電性黏著片及金屬箔的電磁波屏蔽層、與設置於該電磁波屏蔽層之一面的絕緣層。具體而言，本發明之電磁波屏蔽膜例如宜依序具有絕緣層(保護層)、金屬層及本發明之各向同性導電性黏著片。由使電磁波屏蔽性能更良好之觀點，本發明之各向同性導電性黏著片宜積層於金屬層而使用。The electromagnetic wave shielding film having the isotropic conductive adhesive sheet of the present invention is sometimes referred to as the "electromagnetic wave shielding film of the present invention". The electromagnetic wave shielding film of the present invention preferably includes an electromagnetic wave shielding layer including the isotropic conductive adhesive sheet and metal foil of the present invention, and an insulating layer provided on one surface of the electromagnetic wave shielding layer. Specifically, the electromagnetic wave shielding film of the present invention preferably has, for example, an insulating layer (protective layer), a metal layer, and the isotropic conductive adhesive sheet of the present invention in this order. From the viewpoint of making the electromagnetic wave shielding performance better, the isotropic conductive adhesive sheet of the present invention is preferably used by being laminated on a metal layer.

關於構成上述金屬層之金屬，例如可列舉：金、銀、銅、鋁、鎳、錫、鈀、鉻、鈦、鋅或此等之合金等。其中，由使電磁波屏蔽性能更優異之觀點，較佳為銅層、銀層，由經濟性之觀點，較佳為銅。Regarding the metal constituting the above-mentioned metal layer, for example, gold, silver, copper, aluminum, nickel, tin, palladium, chromium, titanium, zinc, and alloys thereof can be cited. Among them, from the viewpoint of making the electromagnetic wave shielding performance more excellent, the copper layer and the silver layer are preferred, and from the viewpoint of economy, copper is preferred.

[印刷配線板] 有時將使用本發明之各向同性導電性黏著片之印刷配線板稱為「本發明之印刷配線板」。[Printed Wiring Board] The printed wiring board using the isotropic conductive adhesive sheet of the present invention is sometimes referred to as the "printed wiring board of the present invention".

圖1係顯示使用本發明之各向同性導電性黏著片之屏蔽印刷配線板之一實施形態。圖1所示之屏蔽印刷配線板X具備：印刷配線板1、積層於印刷配線板1上之電磁波屏蔽積層體2、以其一部分填充於設置在電磁波屏蔽積層體2之通孔24內之方式設置於電磁波屏蔽積層體2上之導電性接著劑層31、及利用導電性接著劑層31接著之補強板32。補強板32可更換為外部接地構件。Fig. 1 shows an embodiment of a shielded printed wiring board using the isotropic conductive adhesive sheet of the present invention. The shielded printed wiring board X shown in FIG. 1 includes: a printed wiring board 1, an electromagnetic wave shielding laminate 2 laminated on the printed wiring board 1, a method in which a part of it is filled in a through hole 24 provided in the electromagnetic wave shielding laminate 2 The conductive adhesive layer 31 provided on the electromagnetic wave shielding laminate 2 and the reinforcing plate 32 bonded by the conductive adhesive layer 31. The reinforcing plate 32 can be replaced with an external ground member.

電磁波屏蔽積層體2亦可為由本發明之電磁波屏蔽膜形成者。即，於電磁波屏蔽積層體2中，導電性接著劑層21可為本發明之各向同性導電性黏著片、亦可為由本發明之各向同性導電性黏著片形成者(例如利用熱壓接而形成者)。The electromagnetic wave shielding laminate 2 may be formed of the electromagnetic wave shielding film of the present invention. That is, in the electromagnetic wave shielding laminate 2, the conductive adhesive layer 21 may be the isotropic conductive adhesive sheet of the present invention, or may be formed of the isotropic conductive adhesive sheet of the present invention (for example, by thermal compression bonding). And the former).

印刷配線板1具有：基底構件11、局部地設置於基底構件11之表面之電路圖案13、覆蓋電路圖案13用以絕緣保護之絕緣保護層(覆蓋膜)14、及覆蓋電路圖案13且用以接著電路圖案13及基底構件11與絕緣保護層14之接著劑層12。電路圖案13包含複數個信號電路。The printed wiring board 1 has: a base member 11, a circuit pattern 13 partially provided on the surface of the base member 11, an insulating protective layer (covering film) 14 covering the circuit pattern 13 for insulation protection, and a covering circuit pattern 13 for The circuit pattern 13 and the adhesive layer 12 of the base member 11 and the insulating protective layer 14 are then followed. The circuit pattern 13 includes a plurality of signal circuits.

電磁波屏蔽積層體2係按導電性接著劑層21、金屬箔22、絕緣層23之順序積層於印刷配線板1上、具體為印刷配線板1之絕緣保護層14上。電磁波屏蔽積層體2具有於厚度方向上貫通(即，使印刷配線板1表面露出)之通孔24。藉由具有通孔24，可利用加壓及加熱使用以形成導電性接著劑層31之接著劑流入通孔24內，與導電性接著劑層21電性連接。通孔24之底為印刷配線板1、具體為絕緣保護層14。即，通孔24由絕緣層23側面、由導電性接著劑層21與金屬箔22構成之電磁波屏蔽層側面、及印刷配線板1(尤其是絕緣保護層14)表面所形成。The electromagnetic wave shielding laminate 2 is laminated on the printed wiring board 1, specifically the insulating protective layer 14 of the printed wiring board 1, in the order of the conductive adhesive layer 21, the metal foil 22, and the insulating layer 23. The electromagnetic wave shielding laminate 2 has a through hole 24 penetrating in the thickness direction (that is, exposing the surface of the printed wiring board 1). By having the through hole 24, the adhesive that can be used to form the conductive adhesive layer 31 by pressing and heating flows into the through hole 24 and is electrically connected to the conductive adhesive layer 21. The bottom of the through hole 24 is a printed wiring board 1 and specifically an insulating protective layer 14. That is, the through hole 24 is formed by the side surface of the insulating layer 23, the side surface of the electromagnetic wave shielding layer composed of the conductive adhesive layer 21 and the metal foil 22, and the surface of the printed wiring board 1 (especially the insulating protective layer 14).

導電性接著劑層31係配置於電磁波屏蔽積層體2上，其一部分填充通孔24，於通孔24中與導電性接著劑層21電性連接。補強板32經由導電性接著劑層31而固定於印刷配線板1及電磁波屏蔽積層體2。導電性接著劑層31由導電性黏接膜形成。導電性接著劑層31亦可為由本發明之各向同性導電性黏著片形成者。即，上述導電性黏接膜亦可為本發明之各向同性導電性黏著片。The conductive adhesive layer 31 is disposed on the electromagnetic wave shielding laminate 2, a part of which fills the through hole 24, and is electrically connected to the conductive adhesive layer 21 in the through hole 24. The reinforcing plate 32 is fixed to the printed wiring board 1 and the electromagnetic wave shielding laminate 2 via the conductive adhesive layer 31. The conductive adhesive layer 31 is formed of a conductive adhesive film. The conductive adhesive layer 31 may also be formed of the isotropic conductive adhesive sheet of the present invention. That is, the above-mentioned conductive adhesive film may also be the isotropic conductive adhesive sheet of the present invention.

導電性接著劑層31不與電路圖案接觸。此時，由於形成導電性接著劑層31之接著劑流入通孔的高度較低，故可防止因朝通孔內部之流入不足所造成的氣泡混入。因此，例如可抑制於回焊步驟之界面剝離，可獲得穩定的連接可靠性。The conductive adhesive layer 31 is not in contact with the circuit pattern. At this time, since the height of the adhesive that forms the conductive adhesive layer 31 flowing into the through hole is low, it is possible to prevent air bubbles from being mixed due to insufficient inflow into the through hole. Therefore, for example, the interface peeling during the reflow step can be suppressed, and stable connection reliability can be obtained.

屏蔽印刷配線板X可藉由如下製造方法製造，該製造方法具備：將電磁波屏蔽膜積層於印刷配線板1上之步驟(屏蔽膜積層步驟)；將具備導電性黏接膜的補強板32以電磁波黏接膜與上述電磁波屏蔽膜接觸之方式積層於通孔24之上表面的步驟(補強板積層步驟)；及藉由熱壓接使導電性黏接膜流入通孔24內而由導電性黏接膜形成導電性接著劑層31，使電磁波屏蔽積層體2中的導電性接著劑層21與導電性接著劑層31接觸的步驟(熱壓接步驟)。再者，藉由上述熱壓接，導電性接著劑層31會熱硬化或熔融、冷卻固化而形成導電性接著劑層31，從而自電磁波屏蔽膜形成電磁波屏蔽積層體2。The shielding printed wiring board X can be manufactured by a manufacturing method including: a step of laminating an electromagnetic wave shielding film on the printed wiring board 1 (a shielding film laminating step); and a reinforcing plate 32 with a conductive adhesive film The step of laminating the electromagnetic wave adhesive film on the upper surface of the through hole 24 by contacting the electromagnetic wave shielding film (reinforcement plate layering step); The adhesive film forms the conductive adhesive layer 31 and brings the conductive adhesive layer 21 and the conductive adhesive layer 31 in the electromagnetic wave shielding laminate 2 into contact (thermocompression bonding step). Furthermore, by the above-mentioned thermal compression bonding, the conductive adhesive layer 31 is thermally cured or melted, and cooled and solidified to form the conductive adhesive layer 31, thereby forming the electromagnetic wave shielding laminate 2 from the electromagnetic wave shielding film.

於上述屏蔽膜積層步驟中，以絕緣保護層14與導電性接著劑層21接觸之方式將電磁波屏蔽膜積層於印刷配線板1上。又，通孔24可以於電磁波屏蔽膜之積層前或積層後形成。通孔24之形成例如利用雷射加工進行。In the step of laminating the shielding film, the electromagnetic wave shielding film is laminated on the printed wiring board 1 so that the insulating protective layer 14 is in contact with the conductive adhesive layer 21. In addition, the through hole 24 may be formed before or after the layering of the electromagnetic wave shielding film. The formation of the through hole 24 is performed by, for example, laser processing.

具體而言，例如將具有導電性接著劑層之電磁波屏蔽膜以導電性接著劑層面成為印刷配線板1側之方式重疊貼合於絕緣保護層14上。又，亦可視需要將積層有電磁波屏蔽膜之狀態的印刷配線板進行熱壓接，使電磁波屏蔽膜中之導電性接著劑層熱硬化或熔融、冷卻固化。藉此，形成導電性接著劑層21，形成電磁波屏蔽積層體2。使用本發明之電磁波屏蔽膜作為上述電磁波屏蔽膜時，本發明之各向同性導電性黏著片可簡單地以高密著力接著於被接著體、與絕緣保護層14之密著力較高，故可不進行上述熱壓接或者以較弱條件的熱壓接形成電磁波屏蔽積層體2。然後，可形成熱循環試驗後之電阻值變化較小的屏蔽印刷配線板X。Specifically, for example, an electromagnetic wave shielding film having a conductive adhesive layer is laminated on the insulating protective layer 14 so that the conductive adhesive layer becomes the printed wiring board 1 side. In addition, if necessary, the printed wiring board in the state where the electromagnetic wave shielding film is laminated can be thermocompression bonded to thermally harden or melt the conductive adhesive layer in the electromagnetic wave shielding film, and cool and solidify. Thereby, the conductive adhesive layer 21 is formed, and the electromagnetic wave shielding laminated body 2 is formed. When the electromagnetic wave shielding film of the present invention is used as the above electromagnetic wave shielding film, the isotropic conductive adhesive sheet of the present invention can be easily adhered to the adherend with a high density, and the adhesion with the insulating protective layer 14 is high, so it is not necessary. The above-mentioned thermocompression bonding or thermocompression bonding under a weaker condition forms the electromagnetic wave shielding laminated body 2. Then, a shielded printed wiring board X with a small change in resistance value after the thermal cycle test can be formed.

於上述補強板積層步驟中，將導電性黏接膜與補強板32貼合，切割為任意的尺寸後，導電性黏接膜之面配置於絕緣層23之表面以封閉通孔24之開口部。In the step of laminating the reinforcing plate, the conductive adhesive film is attached to the reinforcing plate 32 and cut into any size. The surface of the conductive adhesive film is arranged on the surface of the insulating layer 23 to close the opening of the through hole 24 .

然後，於上述熱壓接步驟中，導電性黏接膜利用加壓及加熱而軟化流動，並藉由加壓時的壓力流入填充於通孔24內。然後，利用之後的冷卻或熱聚合而硬化，藉此形成導電性接著劑層31。如此，導電性黏接膜就會因熱壓接而流動，從而與導電性接著劑層21接觸。使用本發明之各向同性導電性黏著片作為上述導電性黏接膜時，本發明之各向同性導電性黏著片可簡單地以高密著力接著於被接著體、與絕緣保護層14之密著力較高，故可利用較弱條件下的熱壓接形成電性連接穩定性優異、熱循環試驗後之電阻值變化較小的屏蔽印刷配線板X。Then, in the above-mentioned thermocompression bonding step, the conductive adhesive film is softened and flowed by pressurization and heating, and flows and fills the through hole 24 by the pressure during pressurization. Then, it is cured by subsequent cooling or thermal polymerization, thereby forming the conductive adhesive layer 31. In this way, the conductive adhesive film flows due to thermocompression bonding and contacts the conductive adhesive layer 21. When the isotropic conductive adhesive sheet of the present invention is used as the above-mentioned conductive adhesive film, the isotropic conductive adhesive sheet of the present invention can be easily adhered to the adherend and the insulating protective layer 14 with high adhesion. It is higher, so thermal compression bonding under weaker conditions can be used to form a shielded printed wiring board X with excellent electrical connection stability and small resistance value changes after thermal cycle tests.

[實施例] 以下，基於實施例更詳細地說明本發明，但本發明並非僅限定於此等實施例。再者，表1記載的調配量為將丙烯酸系樹脂(純份)設為100質量份時的各成分的相對調配量(純份)，除非另有說明，以「質量份」表示。[Example] Hereinafter, the present invention will be explained in more detail based on examples, but the present invention is not limited to these examples. In addition, the compounding amount described in Table 1 is the relative compounding amount (pure part) of each component when the acrylic resin (pure part) is set to 100 parts by mass, and unless otherwise specified, it is expressed as "parts by mass".

實施例1~5、比較例1~9 以表中所示之調配量，調配混合丙烯酸系樹脂溶液、異氰酸酯系硬化劑及導電性粒子，製備實施例及比較例之各黏著劑組成物(固體成分45質量%)。使用的各成分的細節如後所述。Examples 1 to 5, Comparative Examples 1 to 9 The acrylic resin solution, isocyanate curing agent, and conductive particles were blended and mixed in the blending amounts shown in the table to prepare each adhesive composition (solid content 45% by mass) of Examples and Comparative Examples. The details of each component used will be described later.

使用線棒將黏著劑組成物塗佈於表面經離型劑處理的PET膜(厚度50μm)的表面，於100℃下加熱3分鐘，藉此片化後，於40℃、0.5MPa之壓力下以1m/min速度熱層壓於屏蔽基材(厚度12μm之PET膜/厚度0.1μm之銀蒸鍍膜)之銀蒸鍍膜面側。將熱層壓後之片材於60℃下放置24小時，藉此製成導電性黏著片與屏蔽基材之積層體。Use a wire rod to coat the adhesive composition on the surface of a PET film (thickness 50μm) treated with a release agent, and heat it at 100°C for 3 minutes to form a sheet, and then under a pressure of 40°C and 0.5MPa Thermally laminated on the silver vapor-deposited film side of the shielding substrate (PET film with a thickness of 12 μm/silver vapor-deposited film with a thickness of 0.1 μm) at a speed of 1 m/min. The heat-laminated sheet was placed at 60°C for 24 hours to form a laminate of a conductive adhesive sheet and a shielding substrate.

＜丙烯酸系樹脂＞ 丙烯酸系樹脂A：商品名「Hitaloid 5505」(酸值：小於1mgKOH/g、重量平均分子量：30萬、Tg：-25℃)、日立化成股份有限公司製 丙烯酸系樹脂B：商品名「Hitaloid 5507」(酸值：小於1mgKOH/g、重量平均分子量：50萬、Tg：-15℃)、日立化成股份有限公司製 丙烯酸系樹脂C：商品名「Teisanresin SG708-6」(酸值：9mgKOH/g、重量平均分子量：70萬、Tg：4℃)、Nagasechemtex股份有限公司製 丙烯酸系樹脂D：商品名「AR2412」(酸值：小於1mgKOH/g、重量平均分子量：40萬、Tg：-45℃)、Vigteqnos股份有限公司製 ＜導電性粒子＞ 導電性粒子A：Ag塗層電解枝晶Cu粉(樹枝狀、D50：8μm) 導電性粒子B：Ag塗層電解枝晶Cu粉(樹枝狀、D50：13μm) 導電性粒子C：Ag塗層霧化Cu粉(球狀、D50：5μm) 導電性粒子D：Ag塗層電解Cu粉(馬鈴薯狀、D50：7μm) ＜硬化劑＞ 異氰酸酯系硬化劑：商品名「CORONATE L」、東曹股份有限公司製＜Acrylic resin＞ Acrylic resin A: Trade name "Hitaloid 5505" (acid value: less than 1 mgKOH/g, weight average molecular weight: 300,000, Tg: -25°C), manufactured by Hitachi Chemical Co., Ltd. Acrylic resin B: Trade name "Hitaloid 5507" (acid value: less than 1 mgKOH/g, weight average molecular weight: 500,000, Tg: -15°C), manufactured by Hitachi Chemical Co., Ltd. Acrylic resin C: Trade name "Teisanresin SG708-6" (acid value: 9mgKOH/g, weight average molecular weight: 700,000, Tg: 4°C), manufactured by Nagasechemtex Co., Ltd. Acrylic resin D: trade name "AR2412" (acid value: less than 1 mgKOH/g, weight average molecular weight: 400,000, Tg: -45°C), manufactured by Vigteqnos Co., Ltd. ＜Conductive particles＞ Conductive particles A: Ag-coated electrolytic dendritic Cu powder (dendritic, D50: 8μm) Conductive particle B: Ag-coated electrolytic dendritic Cu powder (dendritic, D50: 13μm) Conductive particles C: Ag coated atomized Cu powder (spherical, D50: 5μm) Conductive particles D: Ag coated electrolytic Cu powder (potato shape, D50: 7μm) ＜Hardening agent＞ Isocyanate-based hardener: brand name "CORONATE L", manufactured by Tosoh Corporation

(評價) 就於實施例及比較例獲得之各導電性黏著片如下所述進行評價。評價結果記載於表中。(Evaluation) The conductive adhesive sheets obtained in the examples and comparative examples were evaluated as follows. The evaluation results are described in the table.

(1)密著性(聚醯亞胺膜) 將於實施例及比較例獲得之積層體裁斷為寬度20mm，於溫度20℃之環境下使用2kg輥，使輥往返一次，將導電性黏著片面貼著於聚醯亞胺膜，製作出試驗片。將上述試驗片於20℃、60%Rh之環境下放置12小時後，利用雙面膠將試驗片的聚醯亞胺膜面固定於補強板(FR-1、厚度2mm)，使用拉伸試驗機(商品名「AGS-50NX」、島津製作所股份有限公司製)實施180°剝離試驗。於180°剝離拉伸速度為300mm/分之條件下測定。(1) Adhesion (polyimide film) The laminates obtained in the Examples and Comparative Examples were cut to a width of 20mm, and a 2kg roller was used in an environment at a temperature of 20°C. The roller was reciprocated once, and the conductive adhesive sheet was pasted on the polyimide film to make a test piece. . After placing the above test piece in an environment of 20°C and 60% Rh for 12 hours, use double-sided tape to fix the polyimide film surface of the test piece to a reinforcing plate (FR-1, thickness 2mm), and use a tensile test A machine (trade name "AGS-50NX", manufactured by Shimadzu Corporation) was subjected to a 180° peel test. Measure under the condition of 180° peeling and stretching speed of 300mm/min.

(2)連接電阻值測定 將二個寬度10mm×長度30mm之電極以間隔成為100mm之方式配置於厚度25μm之聚醯亞胺膜上。然後，將於實施例及比較例獲得之積層體沖裁成寬度10mm×長度130mm，以2kg輥往返一次來將導電性黏著片面以連接電極間之方式貼合於電極之配置面。貼合導電性黏著片後，使用4端子法測試儀(商品名「RM3542」、日置電機股份有限公司製)測定2個電極間的電阻值。再者，電阻值之測定係分別於熱循環試驗前及熱循環試驗後進行，將前者設為初始電阻值、將後者設為熱循環試驗後電阻值，由下式求出熱循環試驗後電阻值變化率。上述熱循環試驗係於溫度條件設為低溫側-40℃、高溫側85℃、各溫度保持時間30分鐘、升溫速度5℃/分、降溫速度5℃/分，就上述積層體進行200次循環。 熱循環試驗後電阻值變化率(%)={(熱循環試驗後電阻值(Ω)/初始電阻值(Ω))-1}×100(2) Measurement of connection resistance Two electrodes with a width of 10 mm and a length of 30 mm are arranged on a polyimide film with a thickness of 25 μm at a distance of 100 mm. Then, the laminates obtained in the Examples and Comparative Examples were punched into a width of 10 mm × a length of 130 mm, and a 2 kg roll was used to reciprocate once to bond the conductive adhesive sheet surface to the electrode arrangement surface in a manner to connect the electrodes. After bonding the conductive adhesive sheet, the resistance value between the two electrodes was measured using a 4-terminal method tester (trade name "RM3542", manufactured by Hioki Electric Co., Ltd.). Furthermore, the resistance value is measured before the thermal cycle test and after the thermal cycle test. The former is set as the initial resistance value and the latter is set as the resistance value after the thermal cycle test. The resistance after the thermal cycle test is obtained from the following formula Value change rate. The above-mentioned thermal cycle test was performed under the temperature conditions of -40°C on the low temperature side, 85°C on the high temperature side, each temperature holding time of 30 minutes, the temperature rising rate of 5°C/min, and the cooling rate of 5°C/min. The laminate was subjected to 200 cycles . Change rate of resistance value after thermal cycle test (%)={(resistance value after thermal cycle test (Ω)/initial resistance value (Ω))-1}×100

[表1]

Figure 02_image001
[Table 1]
Figure 02_image001

本發明之各向同性導電性黏著片(實施例)在較弱壓力及溫度條件下貼著於聚醯亞胺膜時其對於聚醯亞胺膜之密著性較高、初始之連接電阻值較低、熱循環試驗後之電阻值變化亦較小。另一方面，[黏著片厚度/D50]較低時(比較例1)，在較弱壓力及溫度條件下貼著時對聚醯亞胺膜之密著性差。導電性粒子之含量較少時(比較例2、4、5)，熱循環試驗後之電阻值變化較大。導電性粒子之含量較多時(比較例3)，在較弱壓力及溫度條件下貼著時對聚醯亞胺膜之密著性差。使用球狀粒子作為導電性粒子時(比較例6)，熱循環試驗後之電阻值變化較大。使用馬鈴薯狀粒子作為導電性粒子時(比較例7)，初始之連接電阻值較高、熱循環試驗後之電阻值變化亦較大。使用Tg較高者作為丙烯酸系樹脂時(比較例8)，在較弱壓力及溫度條件下貼著時對聚醯亞胺膜之密著性差，熱循環試驗後之電阻值變化亦較大。When the isotropic conductive adhesive sheet of the present invention (embodiment) is attached to the polyimide film under weaker pressure and temperature conditions, its adhesion to the polyimide film is relatively high, and the initial connection resistance value Lower, the resistance value change after the thermal cycle test is also smaller. On the other hand, when [Adhesive Sheet Thickness/D50] is low (Comparative Example 1), the adhesion to the polyimide film is poor when it is stuck under weak pressure and temperature conditions. When the content of conductive particles is small (Comparative Examples 2, 4, and 5), the resistance value after the thermal cycle test changes greatly. When the content of conductive particles is large (Comparative Example 3), the adhesion to the polyimide film is poor when pasted under weak pressure and temperature conditions. When spherical particles were used as the conductive particles (Comparative Example 6), the resistance value after the thermal cycle test changed significantly. When potato-like particles are used as conductive particles (Comparative Example 7), the initial connection resistance value is high, and the resistance value change after the thermal cycle test is also large. When an acrylic resin with a higher Tg is used (Comparative Example 8), the adhesion to the polyimide film is poor when attached under weaker pressure and temperature conditions, and the resistance value changes after the thermal cycle test is also greater.

又，使用球狀粒子作為導電性粒子時，即使使用Tg特別低者作為丙烯酸系樹脂，雖然在較弱壓力及溫度條件下貼著時對聚醯亞胺膜之密著性為良好，但熱循環試驗後之電阻值變化依然較大(比較例9)。由比較例6及9之結果可知，於使用球狀粒子作為導電性粒子時，雖然改變丙烯酸系樹脂種類可提高對於聚醯亞胺膜之黏著力，但熱循環試驗後之電阻值變化雖得以減輕卻難以保持在容許範圍內。In addition, when spherical particles are used as conductive particles, even if an acrylic resin with a particularly low Tg is used, the adhesion to the polyimide film is good when stuck under weak pressure and temperature conditions, but heat The resistance value change after the cycle test is still large (Comparative Example 9). From the results of Comparative Examples 6 and 9, it can be seen that when spherical particles are used as conductive particles, although the type of acrylic resin can be changed to improve the adhesion to the polyimide film, the resistance value change after the thermal cycle test can be improved. Mitigation is difficult to keep within the allowable range.

X:屏蔽印刷配線板 1:印刷配線板 11:基底構件 12:接著劑層 13:電路圖案 14:絕緣保護層(覆蓋膜) 2:電磁波屏蔽積層體 21:導電性接著劑層 22:金屬箔 23:絕緣層 24:通孔 31:導電性接著劑層 32:補強板X: shielded printed wiring board 1: Printed wiring board 11: base member 12: Adhesive layer 13: circuit pattern 14: Insulation protective layer (covering film) 2: Electromagnetic wave shielding laminated body 21: Conductive adhesive layer 22: Metal foil 23: Insulation layer 24: Through hole 31: Conductive adhesive layer 32: Reinforcement board

圖1係顯示使用本發明各向同性導電性黏著片之屏蔽印刷配線板之一實施形態的示意剖面圖。Fig. 1 is a schematic cross-sectional view showing an embodiment of a shielded printed wiring board using the isotropic conductive adhesive sheet of the present invention.

X:屏蔽印刷配線板 X: shielded printed wiring board

1:印刷配線板 1: Printed wiring board

11:基底構件 11: base member

12:接著劑層 12: Adhesive layer

13:電路圖案 13: circuit pattern

14:絕緣保護層(保護膜) 14: Insulation protective layer (protective film)

2:電磁波屏蔽積層體 2: Electromagnetic wave shielding laminated body

21:導電性接著劑層 21: Conductive adhesive layer

22:金屬箔 22: Metal foil

23:絕緣層 23: Insulation layer

24:通孔 24: Through hole

31:導電性接著劑層 31: Conductive adhesive layer

32:補強板 32: Reinforcement board

Claims (7)

一種各向同性導電性黏著片，係由黏著劑形成，該黏著劑含有玻璃轉移溫度為0℃以下之丙烯酸系樹脂、異氰酸酯系硬化劑及樹枝狀導電性粒子，且相對於前述丙烯酸系樹脂100質量份，前述異氰酸酯系硬化劑之含量為0.05~5.0質量份、前述樹枝狀導電性粒子之含量為120~240質量份； 並且，黏著片厚度與前述樹枝狀導電性粒子之中值粒徑D50之比[黏著片厚度/D50]為1.3~5.0。An isotropic conductive adhesive sheet, formed by an adhesive containing acrylic resin with a glass transition temperature of 0°C or less, an isocyanate curing agent, and dendritic conductive particles, and is relative to the aforementioned acrylic resin 100 Parts by mass, the content of the aforementioned isocyanate-based hardener is 0.05-5.0 parts by mass, and the content of the aforementioned dendritic conductive particles is 120-240 parts by mass; In addition, the ratio of the thickness of the adhesive sheet to the median diameter D50 of the aforementioned dendritic conductive particles [adhesive sheet thickness/D50] is 1.3 to 5.0. 如請求項1之各向同性導電性黏著片，其中前述樹枝狀導電性粒子之D50為6~15μm。Such as the isotropic conductive adhesive sheet of claim 1, wherein the D50 of the aforementioned dendritic conductive particles is 6-15μm. 如請求項1或2之各向同性導電性黏著片，其厚度為1~100μm。For example, the isotropic conductive adhesive sheet of claim 1 or 2 has a thickness of 1-100μm. 如請求項1或2之各向同性導電性黏著片，其中前述丙烯酸系樹脂之酸值為5mgKOH/g以下。The isotropic conductive adhesive sheet of claim 1 or 2, wherein the acid value of the aforementioned acrylic resin is 5 mgKOH/g or less. 如請求項1或2之各向同性導電性黏著片，其中前述丙烯酸系樹脂之重量平均分子量為10萬~100萬。The isotropic conductive adhesive sheet of claim 1 or 2, wherein the weight average molecular weight of the aforementioned acrylic resin is 100,000 to 1 million. 如請求項1或2之各向同性導電性黏著片，其中前述丙烯酸系樹脂之玻璃轉移溫度為-50℃以上。The isotropic conductive adhesive sheet of claim 1 or 2, wherein the glass transition temperature of the aforementioned acrylic resin is -50°C or higher. 如請求項1或2之各向同性導電性黏著片，其在溫度20℃、壓力1kg/10mm之條件下貼著於聚醯亞胺膜時對聚醯亞胺膜之180°剝離接著力為4N/20mm以上。Such as the isotropic conductive adhesive sheet of claim 1 or 2, when it is attached to the polyimide film under the conditions of temperature 20℃ and pressure 1kg/10mm, the 180° peeling adhesive force to the polyimide film is Above 4N/20mm.
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