TWI840624B - Conductive adhesive, electromagnetic wave shielding film and conductive bonding film - Google Patents
Conductive adhesive, electromagnetic wave shielding film and conductive bonding film Download PDFInfo
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- TWI840624B TWI840624B TW109136157A TW109136157A TWI840624B TW I840624 B TWI840624 B TW I840624B TW 109136157 A TW109136157 A TW 109136157A TW 109136157 A TW109136157 A TW 109136157A TW I840624 B TWI840624 B TW I840624B
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- Prior art keywords
- conductive adhesive
- conductive
- inorganic particles
- insulating inorganic
- electromagnetic wave
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- 239000000853 adhesive Substances 0.000 title claims abstract description 91
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 91
- 239000010954 inorganic particle Substances 0.000 claims abstract description 73
- 239000011231 conductive filler Substances 0.000 claims abstract description 58
- 239000011148 porous material Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims description 75
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 47
- 239000010410 layer Substances 0.000 claims description 40
- 239000012790 adhesive layer Substances 0.000 claims description 33
- 238000010030 laminating Methods 0.000 claims description 4
- 239000011342 resin composition Substances 0.000 description 25
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 7
- 239000004734 Polyphenylene sulfide Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 235000010724 Wisteria floribunda Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000001788 irregular Effects 0.000 description 6
- 239000011859 microparticle Substances 0.000 description 6
- 229920000069 polyphenylene sulfide Polymers 0.000 description 6
- 206010040844 Skin exfoliation Diseases 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910002041 SYLYSIA SY370 Inorganic materials 0.000 description 1
- 229910002043 SYLYSIA SY380 Inorganic materials 0.000 description 1
- 229910002051 SYLYSIA SY530 Inorganic materials 0.000 description 1
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- OYQYHJRSHHYEIG-UHFFFAOYSA-N ethyl carbamate;urea Chemical compound NC(N)=O.CCOC(N)=O OYQYHJRSHHYEIG-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005678 polyethylene based resin Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005673 polypropylene based resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/025—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles 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
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- 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
-
- 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
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- 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
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
本發明之課題係提供一種導電性接著劑，其縱使在嚴酷的環境下使用，亦可獲得充分的連接穩定性。 一種導電性接著劑，特徵在於：具有樹脂、導電性填料及絕緣性無機粒子，且前述絕緣性無機粒子具有細孔。The subject of the present invention is to provide a conductive adhesive which can obtain sufficient connection stability even when used in a harsh environment. A conductive adhesive is characterized by having a resin, a conductive filler and insulating inorganic particles, and the insulating inorganic particles have pores.
Description
本發明係關於導電性接著劑、電磁波屏蔽膜及導電性接合膜。The present invention relates to a conductive adhesive, an electromagnetic wave shielding film and a conductive bonding film.
在小型化、高功能化急速進展之行動電話、視訊照相機、筆記型電腦等電子設備中，撓性印刷配線板經常被使用來建立複雜機構中的電路。進而，利用其優異之可撓性，還能被使用於印表機打印頭等可動部與控制部之連接上。於此等電子設備中，需要採取電磁波屏蔽對策，即使是在裝置內使用的撓性印刷配線板，亦逐漸開始使用已實施電磁波屏蔽對策的撓性印刷配線板(以下亦記載為「屏蔽印刷配線板」)。In electronic devices such as mobile phones, video cameras, and laptops, which are rapidly progressing in miniaturization and high functionality, flexible printed wiring boards are often used to build circuits in complex mechanisms. Furthermore, due to its excellent flexibility, it can also be used to connect movable parts such as printer print heads with control parts. In such electronic devices, electromagnetic wave shielding measures need to be taken, and even for flexible printed wiring boards used in devices, flexible printed wiring boards that have implemented electromagnetic wave shielding measures (hereinafter also referred to as "shielded printed wiring boards") are gradually being used.
一般的屏蔽印刷配線板通常由印刷配線板及電磁波屏蔽膜構成，該印刷配線板係於基材膜上依序設置印刷電路(包含接地電路)與絕緣膜而成，該電磁波屏蔽膜係由導電性接著劑層、積層於導電性接著劑層之屏蔽層及積層於屏蔽層之絕緣層構成。A general shielded printed wiring board is usually composed of a printed wiring board and an electromagnetic wave shielding film. The printed wiring board is formed by sequentially arranging a printed circuit (including a grounding circuit) and an insulating film on a base film, and the electromagnetic wave shielding film is composed of a conductive adhesive layer, a shielding layer laminated on the conductive adhesive layer, and an insulating layer laminated on the shielding layer.
由於是將設於印刷配線板之接地電路與電磁波屏蔽膜之屏蔽層經由導電性接著劑層中之導電性填料電性穩定地連接，故要求導電性填料與接地電路及屏蔽層的接觸穩定性。Since the ground circuit provided on the printed wiring board and the shielding layer of the electromagnetic wave shielding film are electrically and stably connected via the conductive filler in the conductive adhesive layer, the contact stability between the conductive filler and the ground circuit and the shielding layer is required.
關於上述的電磁波屏蔽膜，於專利文獻1中揭示有一種電磁波屏蔽片，特徵在於：其具備絕緣層與導電層，前述導電層包含導電性微粒子、熱硬化性樹脂及氧化矽粒子，且相對於熱硬化性樹脂100重量份，包含3~95重量份的前述氧化矽粒子。 先行技術文獻 專利文獻Regarding the above-mentioned electromagnetic wave shielding film, Patent Document 1 discloses an electromagnetic wave shielding sheet characterized in that: it has an insulating layer and a conductive layer, the conductive layer comprises conductive microparticles, a thermosetting resin and silicon oxide particles, and contains 3 to 95 parts by weight of the silicon oxide particles relative to 100 parts by weight of the thermosetting resin. Prior Art Documents Patent Documents
[專利文獻1]日本特開2015-53412號公報[Patent Document 1] Japanese Patent Application Publication No. 2015-53412
發明概要 發明欲解決之課題 近年來，屏蔽印刷配線板亦被使用於車載零件。 由於車載零件要在承受激烈的溫度變化或振動的嚴酷環境下使用，故要求更高的可靠性(電性連接穩定性)。 為了使導電性填料與接地電路及屏蔽層之接觸穩定，考慮用增加導電性接著劑層中之導電性填料的量來使接觸數增加之方法。然而，縱然使導電性接著劑層中之導電性填料的量增加，亦無法獲得在嚴酷環境下使用時的充分的連接穩定性。Summary of the invention Problems to be solved by the invention In recent years, shielded printed wiring boards have also been used in automotive parts. Since automotive parts are used in harsh environments that are subject to drastic temperature changes or vibrations, higher reliability (electrical connection stability) is required. In order to stabilize the contact between the conductive filler and the ground circuit and the shielding layer, a method of increasing the amount of conductive filler in the conductive adhesive layer to increase the number of contacts is considered. However, even if the amount of conductive filler in the conductive adhesive layer is increased, sufficient connection stability cannot be obtained when used in harsh environments.
本發明係為解決上述問題而完成者，本發明之目的係提供一種導電性接著劑，其縱使在嚴酷的環境下使用，亦可獲得充分的連接穩定性。 用以解決課題之手段This invention is completed to solve the above-mentioned problem. The purpose of this invention is to provide a conductive adhesive that can obtain sufficient connection stability even when used in a harsh environment. Means for solving the problem
即，本發明之導電性接著劑之特徵在於：具有樹脂、導電性填料及絕緣性無機粒子，且上述絕緣性無機粒子具有細孔。That is, the conductive adhesive of the present invention is characterized in that it comprises a resin, a conductive filler and insulating inorganic particles, and the insulating inorganic particles have pores.
本發明之導電性接著劑係呈層狀配置於印刷配線板與電子零件或屏蔽膜等接著對象物之間(以下，亦將配置後之導電性接著劑記載為「導電性接著劑層」)。然後，印刷配線板與該接著對象物經由導電性接著劑中所含的導電性填料而電性連接。 若該導電性填料因為溫度變化或振動等而由固定位置偏離，恐致印刷配線板、導電性填料與接著對象物失去接觸，從而連接穩定性下降。 本發明之導電性接著劑中所含之絕緣性無機粒子可在導電性填料欲從固定位置偏離時，妨礙導電性填料之移動。其結果，可防止連接穩定性降低。 進而，本發明之導電性接著劑因為絕緣性無機粒子具有細孔，故連接穩定性更加提高。 推測其原因如下。 絕緣性無機粒子因為具有細孔，故每一粒子的表面積增大，且絕緣性無機粒子與導電性填料或樹脂之摩擦阻力變高。 因此，可有效率地防止導電性填料從固定位置移動。其結果，推測連接穩定性會更加提高。The conductive adhesive of the present invention is arranged in layers between a printed wiring board and an object to be bonded, such as an electronic component or a shielding film (hereinafter, the conductive adhesive after arrangement is also recorded as a "conductive adhesive layer"). Then, the printed wiring board and the object to be bonded are electrically connected through the conductive filler contained in the conductive adhesive. If the conductive filler deviates from a fixed position due to temperature changes or vibrations, the printed wiring board, the conductive filler and the object to be bonded may lose contact, thereby reducing the stability of the connection. The insulating inorganic particles contained in the conductive adhesive of the present invention can hinder the movement of the conductive filler when the conductive filler wants to deviate from the fixed position. As a result, the connection stability can be prevented from being reduced. Furthermore, the conductive adhesive of the present invention has further improved connection stability because the insulating inorganic particles have fine pores. The reason is estimated as follows. Since the insulating inorganic particles have fine pores, the surface area of each particle increases, and the friction resistance between the insulating inorganic particles and the conductive filler or resin increases. Therefore, the conductive filler can be effectively prevented from moving from a fixed position. As a result, it is estimated that the connection stability will be further improved.
於本發明之導電性接著劑中，上述絕緣性無機粒子宜為氧化矽粒子。 若絕緣性無機粒子為氧化矽粒子，則連接穩定性會更加提高。 又，氧化矽粒子亦作為填充材料而起作用。In the conductive adhesive of the present invention, the insulating inorganic particles are preferably silicon oxide particles. If the insulating inorganic particles are silicon oxide particles, the connection stability will be further improved. In addition, the silicon oxide particles also act as a filler.
於本發明之導電性接著劑中，上述絕緣性無機粒子之細孔容積宜為0.44~1.80mL/g。 若細孔容積在上述範圍，可進一步防止導電性填料之移動，可防止連接穩定性降低。 若細孔容積小於0.44mL/g，連接穩定性容易降低。 具有大於1.80mL/g之細孔容積的絕緣性無機粒子，其變得難以分散於導電性接著劑中，且難以製造絕緣性無機粒子。In the conductive adhesive of the present invention, the pore volume of the insulating inorganic particles is preferably 0.44~1.80mL/g. If the pore volume is within the above range, the migration of the conductive filler can be further prevented, and the connection stability can be prevented from being reduced. If the pore volume is less than 0.44mL/g, the connection stability is easily reduced. Insulating inorganic particles with a pore volume greater than 1.80mL/g become difficult to disperse in the conductive adhesive, and it is difficult to produce insulating inorganic particles.
於本發明之導電性接著劑中，上述絕緣性無機粒子之粒徑(D50 )宜為1.0~9.0μm。 若絕緣性無機粒子之粒徑(D50 )小於1.0μm，就不易獲得防止導電性填料移動的效果。 若絕緣性無機粒子之粒徑(D50 )大於9.0μm，則連接穩定性容易降低。In the conductive adhesive of the present invention, the particle size (D 50 ) of the insulating inorganic particles is preferably 1.0 to 9.0 μm. If the particle size (D 50 ) of the insulating inorganic particles is less than 1.0 μm, it is difficult to obtain the effect of preventing the conductive filler from moving. If the particle size (D 50 ) of the insulating inorganic particles is greater than 9.0 μm, the connection stability is likely to be reduced.
於本發明之導電性接著劑中，上述導電性填料之粒徑(D50 )宜為9~30μm。 若導電性填料之粒徑(D50 )小於9μm，導電性填料容易偏離，連接穩定性容易降低。 若導電性填料之粒徑(D50 )大於30μm，在將導電性接著劑形成層狀而成為導電性接著劑層時，導電性接著劑層變得過厚。In the conductive adhesive of the present invention, the particle size (D 50 ) of the conductive filler is preferably 9 to 30 μm. If the particle size (D 50 ) of the conductive filler is less than 9 μm, the conductive filler is easily separated and the connection stability is easily reduced. If the particle size (D 50 ) of the conductive filler is greater than 30 μm, when the conductive adhesive is formed into a conductive adhesive layer, the conductive adhesive layer becomes too thick.
於本發明之導電性接著劑中，上述絕緣性無機粒子之粒徑(D50 )宜小於上述導電性填料之粒徑(D50 )。 此時，因為可於導電性填料之間填充多數個絕緣性無機粒子，故可進一步防止導電性填料之移動，可防止連接穩定性降低。In the conductive adhesive of the present invention, the particle size (D 50 ) of the insulating inorganic particles is preferably smaller than the particle size (D 50 ) of the conductive filler. In this case, since a plurality of insulating inorganic particles can be filled between the conductive fillers, the migration of the conductive fillers can be further prevented, and the reduction of the connection stability can be prevented.
於本發明之導電性接著劑中，若將上述導電性接著劑所包含之上述樹脂的重量設為100重量份，上述導電性接著劑宜包含上述絕緣性無機粒子1~30重量份。 若絕緣性無機粒子之含量小於1重量份，就不易獲得因為包含絕緣性無機粒子而防止連接穩定性降低的效果。 若絕緣性無機粒子之含量大於30重量份，因為絕緣性無機粒子過多，故導電性填料不易與接著對象物接觸。其結果，連接穩定性容易降低。 又，因為樹脂之比率變少，故導電性接著劑之柔軟性及密著強度降低。In the conductive adhesive of the present invention, if the weight of the resin contained in the conductive adhesive is set to 100 parts by weight, the conductive adhesive preferably contains 1 to 30 parts by weight of the insulating inorganic particles. If the content of the insulating inorganic particles is less than 1 part by weight, it is difficult to obtain the effect of preventing the connection stability from being reduced due to the inclusion of the insulating inorganic particles. If the content of the insulating inorganic particles is greater than 30 parts by weight, the conductive filler is not easy to contact the object to be bonded because the insulating inorganic particles are too many. As a result, the connection stability is easily reduced. In addition, because the ratio of the resin is reduced, the softness and adhesion strength of the conductive adhesive are reduced.
本發明之電磁波屏蔽膜，特徵在於：其係積層絕緣層及導電性接著劑層而成者，上述導電性接著劑層係由上述本發明導電性接著劑構成。The electromagnetic wave shielding film of the present invention is characterized in that it is formed by laminating an insulating layer and a conductive adhesive layer, and the conductive adhesive layer is composed of the conductive adhesive of the present invention.
如上所述，若使用本發明之導電性接著劑，可防止連接穩定性降低。 因此，若將使用了本發明之導電性接著劑的本發明之電磁波屏蔽膜黏貼於印刷配線板而形成屏蔽印刷配線板時，縱使於嚴酷的環境下使用該屏蔽印刷配線板，亦可防止印刷配線板之接地電路與電磁波屏蔽膜之屏蔽層的連接穩定性降低。As described above, if the conductive adhesive of the present invention is used, the connection stability can be prevented from being reduced. Therefore, when the electromagnetic wave shielding film of the present invention using the conductive adhesive of the present invention is adhered to a printed wiring board to form a shielded printed wiring board, even if the shielded printed wiring board is used in a harsh environment, the connection stability between the ground circuit of the printed wiring board and the shielding layer of the electromagnetic wave shielding film can be prevented from being reduced.
於本發明之電磁波屏蔽膜中，上述導電性接著劑層之厚度宜為5~50μm。 若導電性接著劑層之厚度在上述範圍內，則連接穩定性更加提高。In the electromagnetic wave shielding film of the present invention, the thickness of the conductive adhesive layer is preferably 5 to 50 μm. If the thickness of the conductive adhesive layer is within the above range, the connection stability is further improved.
本發明之導電性接合膜，特徵在於：包含上述本發明之導電性接著劑。 本發明之導電性接合膜因為包含上述本發明之導電性接著劑，故可提高經由本發明之導電性接合膜形成的電性連接的連接穩定性。 發明效果The conductive bonding film of the present invention is characterized in that it contains the conductive adhesive of the present invention. Since the conductive bonding film of the present invention contains the conductive adhesive of the present invention, the connection stability of the electrical connection formed by the conductive bonding film of the present invention can be improved. Effect of the invention
於本發明之導電性接著劑中，因為絕緣性無機粒子具有細孔，故連接穩定性更加提高。In the conductive adhesive of the present invention, since the insulating inorganic particles have fine pores, the connection stability is further improved.
用以實施發明之形態 以下，就本發明之導電性接著劑具體地進行說明。然而，本發明不限定於以下實施形態，可於不變更本發明主旨之範圍內進行適當變更並應用。Forms for implementing the invention The following specifically describes the conductive adhesive of the present invention. However, the present invention is not limited to the following implementation forms, and can be appropriately modified and applied within the scope of the present invention.
本發明之導電性接著劑，特徵在於：具有樹脂、導電性填料及絕緣性無機粒子，且上述絕緣性無機粒子具有細孔。The conductive adhesive of the present invention is characterized in that it comprises a resin, a conductive filler and insulating inorganic particles, and the insulating inorganic particles have pores.
本發明之導電性接著劑係呈層狀配置於印刷配線板與電子零件或屏蔽膜等接著對象物之間。然後，印刷配線板與該接著對象物經由導電性接著劑中所含的導電性填料電性連接。 若該導電性填料因為溫度變化或振動等而由固定位置偏離，恐致印刷配線板、導電性填料與接著對象物失去接觸，從而連接穩定性下降。 本發明之導電性接著劑中所含之絕緣性無機粒子可在導電性填料欲從固定位置偏離時，妨礙導電性填料之移動。其結果，可防止連接穩定性降低。 進而，本發明之導電性接著劑因為絕緣性無機粒子具有細孔，故連接穩定性更加提高。 推測其原因如下。 絕緣性無機粒子因為具有細孔，故每一粒子的表面積增大，且絕緣性無機粒子與導電性填料或樹脂之摩擦阻力變高。 因此，可有效率地防止導電性填料從固定位置移動。其結果，推測連接穩定性會更加提高。The conductive adhesive of the present invention is arranged in layers between a printed wiring board and an object to be bonded, such as an electronic component or a shielding film. Then, the printed wiring board and the object to be bonded are electrically connected via the conductive filler contained in the conductive adhesive. If the conductive filler deviates from a fixed position due to temperature changes or vibrations, the printed wiring board, the conductive filler and the object to be bonded may lose contact, thereby reducing the stability of the connection. The insulating inorganic particles contained in the conductive adhesive of the present invention can hinder the movement of the conductive filler when the conductive filler wants to deviate from the fixed position. As a result, the connection stability can be prevented from being reduced. Furthermore, the conductive adhesive of the present invention has further improved connection stability because the insulating inorganic particles have fine pores. The reason is estimated as follows. Since the insulating inorganic particles have fine pores, the surface area of each particle increases, and the friction resistance between the insulating inorganic particles and the conductive filler or resin increases. Therefore, the conductive filler can be effectively prevented from moving from a fixed position. As a result, it is estimated that the connection stability will be further improved.
以下，就本發明之導電性接著劑之各構成進行說明。The following describes the various components of the conductive adhesive of the present invention.
(絕緣性無機粒子) 於本發明之導電性接著劑中，絕緣性無機粒子只要具有細孔，可為任何種類。 關於具有細孔之絕緣性無機粒子，可列舉：氧化矽粒子、滑石粒子、雲母粒子、氧化鋁粒子等。 此等之中，較佳為氧化矽粒子。 若絕緣性無機粒子為氧化矽粒子，則連接穩定性會更加提高。 又，氧化矽粒子亦作為填充材料而起作用。(Insulating inorganic particles) In the conductive adhesive of the present invention, the insulating inorganic particles may be of any type as long as they have pores. As for the insulating inorganic particles having pores, silicon oxide particles, talc particles, mica particles, aluminum oxide particles, etc. can be listed. Among these, silicon oxide particles are preferred. If the insulating inorganic particles are silicon oxide particles, the connection stability will be further improved. In addition, silicon oxide particles also act as a filler.
於本發明之導電性接著劑中，絕緣性無機粒子之細孔容積宜為0.44~1.80mL/g、較佳為0.80~1.60mL/g。 若細孔容積在上述範圍，可進一步防止導電性填料之移動，可防止連接穩定性降低。 若細孔容積小於0.44mL/g，則連接穩定性容易降低。 具有大於1.80mL/g之細孔容積的絕緣性無機粒子，其變得難以分散於導電性接著劑中，且難以製造絕緣性無機粒子。In the conductive adhesive of the present invention, the pore volume of the insulating inorganic particles is preferably 0.44 to 1.80 mL/g, preferably 0.80 to 1.60 mL/g. If the pore volume is within the above range, the migration of the conductive filler can be further prevented, and the connection stability can be prevented from being reduced. If the pore volume is less than 0.44 mL/g, the connection stability is easily reduced. Insulating inorganic particles with a pore volume greater than 1.80 mL/g become difficult to disperse in the conductive adhesive, and it is difficult to produce insulating inorganic particles.
於本發明之導電性接著劑中，絕緣性無機粒子之比表面積宜為10~700m2 /g、較佳為280~500m2 /g。 比表面積在上述範圍時，表示絕緣性無機粒子中之細孔較多，得以認為可更進一步防止導電性填料之移動，可防止連接穩定性降低。In the conductive adhesive of the present invention, the specific surface area of the insulating inorganic particles is preferably 10-700 m 2 /g, more preferably 280-500 m 2 /g. When the specific surface area is within the above range, it means that the insulating inorganic particles have more pores, which is considered to further prevent the migration of the conductive filler and prevent the connection stability from being reduced.
再者，絕緣性無機粒子之細孔容積及比表面積可使用元素分析裝置：Vari EL III(Elementar公司製)藉由氮吸附法進行測定。The pore volume and specific surface area of the insulating inorganic particles can be measured by a nitrogen adsorption method using an elemental analyzer: Vari EL III (manufactured by Elementar).
於本發明之導電性接著劑中，絕緣性無機粒子之粒徑(D50 )宜為1.0~9.0μm、較佳為2.0~7.0μm、更佳為2.5~7.0μm。 若絕緣性無機粒子之粒徑(D50 )小於1.0μm，就不易獲得防止導電性填料移動的效果。 若絕緣性無機粒子之粒徑(D50 )大於9.0μm，則連接穩定性容易降低。In the conductive adhesive of the present invention, the particle size (D 50 ) of the insulating inorganic particles is preferably 1.0 to 9.0 μm, more preferably 2.0 to 7.0 μm, and more preferably 2.5 to 7.0 μm. If the particle size (D 50 ) of the insulating inorganic particles is less than 1.0 μm, it is difficult to obtain the effect of preventing the conductive filler from moving. If the particle size (D 50 ) of the insulating inorganic particles is greater than 9.0 μm, the connection stability is likely to be reduced.
再者，絕緣性無機粒子之粒徑(D50 )可藉由雷射繞射式粒徑分布測定裝置或流動式粒子像分析裝置等已知方法進行測定。 又，後述的導電性填料的平均粒徑(D50 )之測定方法亦相同。The particle size (D 50 ) of the insulating inorganic particles can be measured by a known method such as a laser diffraction particle size distribution measuring device or a flow particle image analyzer. The method for measuring the average particle size (D 50 ) of the conductive filler described below is also the same.
於本發明之導電性接著劑中，絕緣性無機粒子之粒徑(D50 )宜小於導電性填料之粒徑(D50 )。 此時，因為可於導電性填料之間填充多數個絕緣性無機粒子，故可進一步防止導電性填料之移動，可防止連接穩定性降低。In the conductive adhesive of the present invention, the particle size (D 50 ) of the insulating inorganic particles is preferably smaller than the particle size (D 50 ) of the conductive filler. In this case, since a plurality of insulating inorganic particles can be filled between the conductive fillers, the migration of the conductive fillers can be further prevented, and the decrease in connection stability can be prevented.
於本發明之導電性接著劑中，若將導電性接著劑所包含之上述樹脂的重量設為100重量份，上述導電性接著劑宜包含絕緣性無機粒子1~30重量份、較佳為包含5~20重量份、更佳為包含5~10重量份。 若絕緣性無機粒子之含量小於1重量份，就不易獲得因為包含絕緣性無機粒子而防止連接穩定性降低的效果。 若絕緣性無機粒子之含量大於30重量份，因為絕緣性無機粒子過多，故導電性填料不易與接著對象物接觸。其結果，連接穩定性容易降低。 又，因為樹脂之比率變少，故導電性接著劑之柔軟性及密著強度會降低。In the conductive adhesive of the present invention, if the weight of the resin contained in the conductive adhesive is set to 100 parts by weight, the conductive adhesive preferably contains 1 to 30 parts by weight of insulating inorganic particles, preferably 5 to 20 parts by weight, and more preferably 5 to 10 parts by weight. If the content of the insulating inorganic particles is less than 1 part by weight, it is difficult to obtain the effect of preventing the connection stability from being reduced due to the inclusion of the insulating inorganic particles. If the content of the insulating inorganic particles is greater than 30 parts by weight, the conductive filler is not easy to contact the object to be bonded because the insulating inorganic particles are too much. As a result, the connection stability is easily reduced. Also, as the resin ratio decreases, the softness and adhesion strength of the conductive adhesive will decrease.
就本發明之導電性接著劑而言，於絕緣性無機粒子之細孔容積為0.8mL/g以上之情況下，在將導電性接著劑所含樹脂之重量設為100重量份時的絕緣性無機粒子之含量設為Y、將絕緣性無機粒子之粒徑(D50 )設為X時，宜滿足以下之式(1)~(3)。滿足式(1)~(3)時，連接穩定性會提高且導電性接著劑之接著性會提高。 5＜Y＜30 (1) 2.7＜X＜9.0 (2) Y＜-2.2X+36.6 (3)In the case of the conductive adhesive of the present invention, when the pore volume of the insulating inorganic particles is 0.8 mL/g or more, the content of the insulating inorganic particles when the weight of the resin contained in the conductive adhesive is set to 100 parts by weight is set to Y, and the particle size (D 50 ) of the insulating inorganic particles is set to X, it is preferable to satisfy the following formulas (1) to (3). When the formulas (1) to (3) are satisfied, the connection stability is improved and the adhesiveness of the conductive adhesive is improved. 5＜Y＜30 (1) 2.7＜X＜9.0 (2) Y＜-2.2X+36.6 (3)
(導電性填料) 於本發明之導電性接著劑中，關於導電性填料並無特別限定，可為金屬微粒子、奈米碳管、碳纖維、金屬纖維等。 此等之中，較佳為金屬微粒子。 又，關於金屬微粒子並無特別限定，可為銀粉、銅粉、鎳粉、焊粉、鋁粉、於銅粉上鍍銀之銀包銅粉、以金屬被覆高分子微粒子或玻璃珠等之微粒子等。 此等之中，由經濟性之觀點而言，宜為可低價取得之銅粉或銀包銅粉。(Conductive filler) In the conductive adhesive of the present invention, there is no particular limitation on the conductive filler, and it can be metal microparticles, carbon nanotubes, carbon fibers, metal fibers, etc. Among these, metal microparticles are preferred. In addition, there is no particular limitation on the metal microparticles, and it can be silver powder, copper powder, nickel powder, solder powder, aluminum powder, silver-coated copper powder with silver plated on copper powder, and microparticles of polymer microparticles or glass beads coated with metal, etc. Among these, from the viewpoint of economy, copper powder or silver-coated copper powder that can be obtained at a low price is preferred.
於本發明之導電性接著劑中，導電性填料之形狀並無特別限定，可從球狀、扁平狀、鱗片狀、枝晶狀、棒狀、纖維狀等中適當選擇。In the conductive adhesive of the present invention, the shape of the conductive filler is not particularly limited, and can be appropriately selected from spherical, flat, scaly, dendrite, rod, fiber, etc.
於本發明之導電性接著劑中，若將導電性接著劑所包含之樹脂的重量設為100重量份，導電性接著劑宜包含導電性填料1~100重量份、較佳為包含5~70重量份、更佳為包含20~40重量份。 若導電性填料之含量小於1重量份，因為對導電性接著劑賦予導電性之導電性填料的量變少，故導電性接著劑整體之導電性降低。 若導電性填料之含量大於100重量份，因為樹脂之比率變少，故導電性接著劑之柔軟性及密著強度降低。In the conductive adhesive of the present invention, if the weight of the resin contained in the conductive adhesive is set to 100 parts by weight, the conductive adhesive preferably contains 1 to 100 parts by weight of a conductive filler, preferably 5 to 70 parts by weight, and more preferably 20 to 40 parts by weight. If the content of the conductive filler is less than 1 part by weight, the amount of the conductive filler that imparts conductivity to the conductive adhesive is reduced, so the conductivity of the conductive adhesive as a whole is reduced. If the content of the conductive filler is greater than 100 parts by weight, the softness and adhesion strength of the conductive adhesive are reduced because the ratio of the resin is reduced.
於本發明之導電性接著劑中，導電性填料之粒徑(D50 )宜為9~30μm、較佳為12~20μm。 若導電性填料之粒徑(D50 )小於9μm，導電性填料容易偏離，連接穩定性容易降低。 若導電性填料之粒徑(D50 )大於30μm，在將導電性接著劑形成層狀而成為導電性接著劑層時，導電性接著劑層變得過厚。In the conductive adhesive of the present invention, the particle size (D 50 ) of the conductive filler is preferably 9 to 30 μm, more preferably 12 to 20 μm. If the particle size (D 50 ) of the conductive filler is less than 9 μm, the conductive filler is easily separated and the connection stability is easily reduced. If the particle size (D 50 ) of the conductive filler is greater than 30 μm, when the conductive adhesive is formed into a conductive adhesive layer, the conductive adhesive layer becomes too thick.
(樹脂) 於本發明之導電性接著劑中，樹脂並無特別限定，但可列舉：苯乙烯系樹脂組成物、乙酸乙烯酯系樹脂組成物、聚酯系樹脂組成物、聚乙烯系樹脂組成物、聚丙烯系樹脂組成物、醯亞胺系樹脂組成物、醯胺系樹脂組成物、丙烯酸系樹脂組成物等熱塑性樹脂組成物；或酚系樹脂組成物、環氧系樹脂組成物、胺基甲酸酯系樹脂組成物、三聚氰胺系樹脂組成物、醇酸系樹脂組成物等熱硬化性樹脂組成物等。(Resin) In the conductive adhesive of the present invention, the resin is not particularly limited, but can be exemplified by: thermoplastic resin compositions such as styrene resin compositions, vinyl acetate resin compositions, polyester resin compositions, polyethylene resin compositions, polypropylene resin compositions, imide resin compositions, amide resin compositions, and acrylic resin compositions; or thermosetting resin compositions such as phenol resin compositions, epoxy resin compositions, urethane resin compositions, melamine resin compositions, and alkyd resin compositions.
於本發明之導電性接著劑中，樹脂於頻率1GHz、23℃下之相對介電常數宜為1~5、較佳為2~4。 樹脂於頻率1GHz、23℃下之介電損耗正切宜為0.0001~0.03、較佳為0.001~0.002。 若為此範圍，於將本發明之導電性接著劑用於電子設備時，可使傳送特性提高。In the conductive adhesive of the present invention, the relative dielectric constant of the resin at a frequency of 1 GHz and 23°C is preferably 1 to 5, preferably 2 to 4. The dielectric loss tangent of the resin at a frequency of 1 GHz and 23°C is preferably 0.0001 to 0.03, preferably 0.001 to 0.002. If it is within this range, when the conductive adhesive of the present invention is used in electronic equipment, the transmission characteristics can be improved.
(其他構成) 除了樹脂、導電性填料及絕緣性無機粒子以外，本發明之導電性接著劑亦可視需要包含硬化促進劑、賦黏劑、抗氧化劑、顏料、染料、塑化劑、紫外線吸收劑、消泡劑、調平劑、填充劑、阻燃劑、黏度調節劑、抗結塊劑等。(Other components) In addition to resin, conductive filler and insulating inorganic particles, the conductive adhesive of the present invention may also include a curing accelerator, a tackifier, an antioxidant, a pigment, a dye, a plasticizer, an ultraviolet absorber, a defoaming agent, a leveling agent, a filler, a flame retardant, a viscosity regulator, an anti-caking agent, etc. as needed.
本發明之導電接著劑亦可為各向異性導電性接著劑。 導電接著劑之各向異性可藉由調整導電性填料之含量及大小而獲得。The conductive adhesive of the present invention can also be an anisotropic conductive adhesive. The anisotropy of the conductive adhesive can be obtained by adjusting the content and size of the conductive filler.
接著，就本發明之導電性接著劑之使用方法進行說明。Next, the method of using the conductive adhesive of the present invention is described.
本發明之導電性接著劑可用於電磁波屏蔽膜。 再者，使用了本發明之導電性接著劑的電磁波屏蔽膜亦為本發明之一態樣。The conductive adhesive of the present invention can be used for electromagnetic wave shielding film. Furthermore, an electromagnetic wave shielding film using the conductive adhesive of the present invention is also an aspect of the present invention.
針對上述電磁波屏蔽膜，使用圖式進行說明。 圖1係示意性顯示本發明之電磁波屏蔽膜之一例的剖面圖。 圖2係示意性顯示本發明之電磁波屏蔽膜之另一例的剖面圖。The electromagnetic wave shielding film is described using drawings. FIG. 1 is a cross-sectional view schematically showing an example of the electromagnetic wave shielding film of the present invention. FIG. 2 is a cross-sectional view schematically showing another example of the electromagnetic wave shielding film of the present invention.
圖1所示之電磁波屏蔽膜1係依序積層絕緣層10及導電性接著劑層20而成之電磁波屏蔽膜。 導電性接著劑層20由上述本發明之導電性接著劑構成。 於上述電磁波屏蔽膜1中，導電性接著劑層20作為屏蔽層而起作用。The electromagnetic wave shielding film 1 shown in FIG1 is an electromagnetic wave shielding film formed by sequentially laminating an insulating layer 10 and a conductive adhesive layer 20. The conductive adhesive layer 20 is composed of the conductive adhesive of the present invention. In the electromagnetic wave shielding film 1, the conductive adhesive layer 20 functions as a shielding layer.
圖2所示之電磁波屏蔽膜2係依序積層絕緣層10、金屬層30及導電性接著劑層20而成之電磁波屏蔽膜。 導電性接著劑層20由上述本發明之導電性接著劑構成。 於上述電磁波屏蔽膜2中，金屬層30作為屏蔽層而起作用。又，導電性接著劑層20可具有各向同性導電性、抑或具有各向異性導電性。The electromagnetic wave shielding film 2 shown in FIG2 is an electromagnetic wave shielding film formed by sequentially laminating an insulating layer 10, a metal layer 30, and a conductive adhesive layer 20. The conductive adhesive layer 20 is composed of the conductive adhesive of the present invention. In the electromagnetic wave shielding film 2, the metal layer 30 functions as a shielding layer. In addition, the conductive adhesive layer 20 may have isotropic conductivity or anisotropic conductivity.
於電磁波屏蔽膜1及電磁波屏蔽膜2中，因為導電性接著劑層20由上述本發明之導電性接著劑構成，故可防止連接穩定性降低。 因此，若將使用了本發明之導電性接著劑的電磁波屏蔽膜1或電磁波屏蔽膜2黏貼於印刷配線板而形成屏蔽印刷配線板時，縱使於嚴酷的環境下使用該屏蔽印刷配線板，亦可防止印刷配線板之接地電路與電磁波屏蔽膜之屏蔽層的連接穩定性降低。In the electromagnetic wave shielding film 1 and the electromagnetic wave shielding film 2, since the conductive adhesive layer 20 is composed of the conductive adhesive of the present invention, it is possible to prevent the connection stability from being reduced. Therefore, when the electromagnetic wave shielding film 1 or the electromagnetic wave shielding film 2 using the conductive adhesive of the present invention is adhered to a printed wiring board to form a shielded printed wiring board, even if the shielded printed wiring board is used in a harsh environment, it is possible to prevent the connection stability between the ground circuit of the printed wiring board and the shielding layer of the electromagnetic wave shielding film from being reduced.
於電磁波屏蔽膜1及電磁波屏蔽膜2中，導電性接著劑層20之厚度並無特別限定，但宜為5~50μm、較佳為10~40μm。 若導電性接著劑層之厚度在上述範圍內，則連接穩定性更加提高。In the electromagnetic wave shielding film 1 and the electromagnetic wave shielding film 2, the thickness of the conductive adhesive layer 20 is not particularly limited, but is preferably 5 to 50 μm, and more preferably 10 to 40 μm. If the thickness of the conductive adhesive layer is within the above range, the connection stability is further improved.
於電磁波屏蔽膜1及電磁波屏蔽膜2中，絕緣層10並無特別限定，但宜由熱塑性樹脂組成物、熱硬化性樹脂組成物、活性能量線硬化性組成物等構成。In the electromagnetic wave shielding film 1 and the electromagnetic wave shielding film 2, the insulating layer 10 is not particularly limited, but is preferably composed of a thermoplastic resin composition, a thermosetting resin composition, an active energy ray-curable composition, or the like.
關於上述熱塑性樹脂組成物並無特別限定，可列舉：苯乙烯系樹脂組成物、乙酸乙烯酯系樹脂組成物、聚酯系樹脂組成物、聚乙烯系樹脂組成物、聚丙烯系樹脂組成物、醯亞胺系樹脂組成物及丙烯酸系樹脂組成物等。The thermoplastic resin composition is not particularly limited, and examples thereof include styrene-based resin compositions, vinyl acetate-based resin compositions, polyester-based resin compositions, polyethylene-based resin compositions, polypropylene-based resin compositions, imide-based resin compositions, and acrylic-based resin compositions.
關於上述熱硬化性樹脂組成物，並無特別限定，可列舉：選自於由環氧系樹脂組成物、胺基甲酸酯系樹脂組成物、胺基甲酸酯脲系樹脂組成物、苯乙烯系樹脂組成物、酚系樹脂組成物、三聚氰胺系樹脂組成物、丙烯酸系樹脂組成物及醇酸系樹脂組成物所構成群組中之至少1種樹脂組成物。The thermosetting resin composition is not particularly limited, and may be at least one selected from the group consisting of epoxy resin compositions, urethane resin compositions, urethane urea resin compositions, styrene resin compositions, phenol resin compositions, melamine resin compositions, acrylic resin compositions, and alkyd resin compositions.
關於上述活性能量線硬化性組成物，並無特別限定，可舉例如於分子中具有至少2個(甲基)丙烯醯氧基之聚合性化合物等。The active energy ray-curable composition is not particularly limited, and examples thereof include a polymerizable compound having at least two (meth)acryloyloxy groups in a molecule.
絕緣層10之厚度宜為1~12μm。The thickness of the insulating layer 10 is preferably 1-12 μm.
於絕緣層中視需要亦可包含：硬化促進劑、賦黏劑、抗氧化劑、顏料、染料、塑化劑、紫外線吸收劑、消泡劑、調平劑、填充材、阻燃劑、黏度調節劑、抗結塊劑等。The insulating layer may also contain, as needed: a hardening accelerator, a tackifier, an antioxidant, a pigment, a dye, a plasticizer, an ultraviolet absorber, a defoaming agent, a leveling agent, a filler, a flame retardant, a viscosity regulator, an anti-caking agent, etc.
於電磁波屏蔽膜2中，金屬層30並無特別限定，但宜由金、銀、銅、鋁、鎳、錫、鈀、鉻、鈦、鋅等構成。其等之中，較佳為銅。In the electromagnetic wave shielding film 2, the metal layer 30 is not particularly limited, but is preferably made of gold, silver, copper, aluminum, nickel, tin, palladium, chromium, titanium, zinc, etc. Among them, copper is preferred.
金屬層30亦可由上述金屬之合金構成。 又，金屬層30亦可為藉由濺鍍或無電鍍覆、電鍍等方法形成之金屬膜。The metal layer 30 may also be composed of an alloy of the above metals. In addition, the metal layer 30 may also be a metal film formed by sputtering, electroless plating, electroplating, or the like.
金屬層30之厚度，宜為0.01~10μm。 金屬層的厚度小於0.01μm，就不易獲得充分的屏蔽效果。 若金屬層的厚度大於10μm，則難以撓曲。The thickness of the metal layer 30 is preferably 0.01 to 10 μm. If the thickness of the metal layer is less than 0.01 μm, it is difficult to obtain a sufficient shielding effect. If the thickness of the metal layer is greater than 10 μm, it is difficult to bend.
又，本發明之導電性接著劑可用作導電性接合膜。 再者，使用了本發明之導電性接著劑的導電性接合膜亦為本發明之一態樣。Furthermore, the conductive adhesive of the present invention can be used as a conductive bonding film. Furthermore, a conductive bonding film using the conductive adhesive of the present invention is also an aspect of the present invention.
本發明之導電性接合膜可藉由於表面經實施離型處理之基材膜的表面呈層狀配置本發明導電性接著劑來製造。 因為包含上述本發明之導電性接著劑，故可使經由本發明導電性接合膜形成之電性連接的連接穩定性提高。例如，可用於導電性(金屬)補強板對撓性印刷配線基板的安裝。The conductive bonding film of the present invention can be manufactured by disposing the conductive adhesive of the present invention in layers on the surface of a substrate film subjected to a release treatment. Because the conductive adhesive of the present invention is included, the connection stability of the electrical connection formed by the conductive bonding film of the present invention can be improved. For example, it can be used for mounting a conductive (metal) reinforcing plate on a flexible printed wiring board.
本發明之導電性接合膜可具有各向同性導電性、抑或具有各向異性導電性。The conductive bonding film of the present invention may have isotropic conductivity or anisotropic conductivity.
本發明之導電性接合膜之厚度宜為10~100μm、較佳為20~70μm。 [實施例]The thickness of the conductive bonding film of the present invention is preferably 10 to 100 μm, preferably 20 to 70 μm. [Example]
以下顯示更具體地說明本發明之實施例，但本發明並非限定於此等實施例。The following are examples that more specifically illustrate the present invention, but the present invention is not limited to these examples.
準備具有表1所示之細孔容積、粒徑(D50 )、比表面積及形狀的氧化矽粒子1~氧化矽粒子10作為絕緣性無機粒子。 再者，各絕緣性無機粒子之製品名、製造商等如下所述。 氧化矽粒子1：製品名：sylysia710(富士SILYSIA化學股份有限公司製) 氧化矽粒子2：製品名：sylysia310P(富士SILYSIA化學股份有限公司製) 氧化矽粒子3：製品名：sylysia530(富士SILYSIA化學股份有限公司製) 氧化矽粒子4：製品名：sylysia280(富士SILYSIA化學股份有限公司製) 氧化矽粒子5：製品名：sylysia370(富士SILYSIA化學股份有限公司製) 氧化矽粒子6：製品名：sylysia380(富士SILYSIA化學股份有限公司製) 氧化矽粒子7：製品名：Y10SM-AM1(Admatechs股份有限公司製) 氧化矽粒子8：製品名：SC1050-MLM(Admatechs股份有限公司製) 氧化矽粒子9：製品名：FB-3SDC(DENKA股份有限公司製) 氧化矽粒子10：製品名：FB-7SDC(DENKA股份有限公司製)As insulating inorganic particles, silicon oxide particles 1 to 10 having the pore volume, particle size (D 50 ), specific surface area and shape shown in Table 1 were prepared. The product name, manufacturer, etc. of each insulating inorganic particle are as follows. Silicon oxide particle 1: Product name: Sylysia710 (manufactured by Fuji Silysia Chemical Co., Ltd.) Silicon oxide particle 2: Product name: Sylysia310P (manufactured by Fuji Silysia Chemical Co., Ltd.) Silicon oxide particle 3: Product name: Sylysia530 (manufactured by Fuji Silysia Chemical Co., Ltd.) Silicon oxide particle 4: Product name: Sylysia280 (manufactured by Fuji Silysia Chemical Co., Ltd.) Silicon oxide particle 5: Product name: Sylysia370 (manufactured by Fuji Silysia Chemical Co., Ltd.) Silicon oxide particle 6: Product name: Sylysia380 (manufactured by Fuji Silysia Chemical Co., Ltd.) Silicon oxide particle 7: Product name: Y10SM-AM1 (manufactured by Admatechs Co., Ltd.) Silicon oxide particle 8: Product name: SC1050-MLM (manufactured by Admatechs Co., Ltd.) Silicon oxide particles 9: Product name: FB-3SDC (manufactured by DENKA Co., Ltd.) Silicon oxide particles 10: Product name: FB-7SDC (manufactured by DENKA Co., Ltd.)
[表1]
(電阻值試驗) 將100重量份的作為樹脂之熱塑性聚酯樹脂、25重量份的作為導電性填料之銀包銅粉(D50 =12μm)、5重量份的作為絕緣性無機粒子之氧化矽粒子1進行混練，製作導電性接著劑。(Electrical resistance test) 100 parts by weight of a thermoplastic polyester resin as a resin, 25 parts by weight of silver-coated copper powder (D 50 = 12 μm) as a conductive filler, and 5 parts by weight of silicon oxide particles 1 as insulating inorganic particles were mixed to prepare a conductive adhesive.
接著，準備於單面實施過剝離處理之聚對苯二甲酸乙二酯膜作為轉印膜。 然後，於轉印膜之剝離處理面塗佈環氧樹脂，使用電烤箱於100℃下加熱2分鐘，製作厚度5μm之絕緣層。 之後，藉由無電鍍覆於絕緣層上形成2μm銅層。該銅層成為屏蔽層。 然後，於銅層上塗佈準備好的導電性接著劑，使用電烤箱於100℃下加熱2分鐘，製作厚度20μm的導電性接著劑層。 藉由上述步驟而製作電磁波屏蔽膜。Next, a polyethylene terephthalate film subjected to a peeling treatment on one side is prepared as a transfer film. Then, epoxy resin is applied to the peeling treatment surface of the transfer film, and an electric oven is used to heat it at 100°C for 2 minutes to produce an insulating layer with a thickness of 5μm. After that, a 2μm copper layer is formed on the insulating layer by electroless plating. The copper layer becomes a shielding layer. Then, a prepared conductive adhesive is applied to the copper layer, and an electric oven is used to heat it at 100°C for 2 minutes to produce a conductive adhesive layer with a thickness of 20μm. An electromagnetic wave shielding film is produced by the above steps.
其次，使用圖式說明電阻值試驗之方法。 圖3A及圖3B係顯示電阻值試驗之方法的示意圖。 首先，如圖3A所示，準備橫150mm、縱25mm之聚苯硫醚膜(圖3A中，以符號「51」表示)與橫15mm、縱25mm、厚度35μm之鍍錫銅箔膠帶(3M公司製1345)(圖3A中，以符號「52」表示)，於聚苯硫醚膜51之兩端，在距離端部15mm的位置將鍍錫銅箔膠帶52與聚苯硫醚膜51黏合，製作電阻值基板50。 接著，如圖3B所示，將電磁波屏蔽膜2切斷成橫140mm、縱20mm，並以電磁波屏蔽膜2之導電性接著劑層20與電阻值基板50之鍍錫銅箔膠帶52相對向之方式進行疊合。然後，使用加壓機於120℃、0.5MPa之條件下進行加熱加壓5秒鐘，使鍍錫銅箔膠帶52與電磁波屏蔽膜2之間導通，而製作電磁波屏蔽基板60。 將電磁波屏蔽基板60於-40℃之環境下放置500小時後，測定導電性接著劑層20之電阻值(厚度方向之電阻值)。其結果為42mΩ。Next, the method of the resistance value test is described using diagrams. Figures 3A and 3B are schematic diagrams showing the method of the resistance value test. First, as shown in Figure 3A, a polyphenylene sulfide film with a width of 150 mm and a length of 25 mm (indicated by symbol "51" in Figure 3A) and a tinned copper foil tape (1345 manufactured by 3M Company) with a width of 15 mm and a length of 25 mm and a thickness of 35 μm (indicated by symbol "52" in Figure 3A) are prepared. The tinned copper foil tape 52 is bonded to the polyphenylene sulfide film 51 at both ends of the polyphenylene sulfide film 51 at a position 15 mm away from the end to produce a resistance value substrate 50. Next, as shown in FIG3B , the electromagnetic wave shielding film 2 is cut into 140 mm in width and 20 mm in length, and the conductive adhesive layer 20 of the electromagnetic wave shielding film 2 and the tinned copper foil tape 52 of the resistance value substrate 50 are stacked in a manner opposite to each other. Then, a press is used to heat and pressurize for 5 seconds at 120°C and 0.5 MPa to make the tinned copper foil tape 52 and the electromagnetic wave shielding film 2 conductive, thereby producing an electromagnetic wave shielding substrate 60. After the electromagnetic wave shielding substrate 60 is placed in an environment of -40°C for 500 hours, the resistance value (resistance value in the thickness direction) of the conductive adhesive layer 20 is measured. The result is 42 mΩ.
除了令使用的絕緣性無機粒子的種類與其使用量如表2所示以外，以相同方法製作電磁波屏蔽膜，並測定電阻值。將結果顯示於表2。 又，表2中之數值單位為「mΩ」。又，所謂「0重量份」表示導電性接著劑不含絕緣性無機粒子。Except that the type and amount of insulating inorganic particles used are shown in Table 2, an electromagnetic wave shielding film is prepared in the same manner and the resistance value is measured. The results are shown in Table 2. In addition, the numerical unit in Table 2 is "mΩ". In addition, the so-called "0 parts by weight" means that the conductive adhesive does not contain insulating inorganic particles.
[表2]
(接著性試驗) 使用採用了氧化矽粒子2~氧化矽粒子6之導電性接著劑製作電磁波屏蔽膜，按以下方法進行接著性試驗。 將電磁波屏蔽膜切斷為橫70mm、縱10mm，以120℃、0.5MPa、5秒之條件於電磁波屏蔽膜之接著劑層面加熱加壓厚度50μm之聚苯硫醚膜，製作測定樣品。接著，為了測定接著強度，使用拉伸試驗機AGS-X50N(島津製作所公司製)將該測定樣品以剝離速度50mm/min、剝離角度180°，對導電性接著劑層與聚苯硫醚膜之界面進行剝離，測定剝離強度。 評價基準如下。將結果顯示於表3。 〇：3.5N/10mm以上 無實用上問題 ×：小於3.5N/10mm 有實用上問題(Adhesion test) An electromagnetic wave shielding film was prepared using a conductive adhesive using silicon oxide particles 2 to 6, and the adhesion test was performed as follows. The electromagnetic wave shielding film was cut into 70 mm in width and 10 mm in length, and a polyphenylene sulfide film with a thickness of 50 μm was heated and pressed on the adhesive layer of the electromagnetic wave shielding film at 120°C, 0.5 MPa, and 5 seconds to prepare a test sample. Then, in order to measure the adhesion strength, the test sample was peeled at a peeling speed of 50 mm/min and a peeling angle of 180° using a tensile tester AGS-X50N (manufactured by Shimadzu Corporation) to peel the interface between the conductive adhesive layer and the polyphenylene sulfide film, and the peeling strength was measured. The evaluation criteria are as follows. The results are shown in Table 3. 0: 3.5N/10mm or more, no practical problems ×: less than 3.5N/10mm, practical problems
[表3]
如表2所示可知，具有樹脂、導電性填料及絕緣性無機粒子且上述絕緣性無機粒子具有細孔的本發明之導電性接著劑，縱使長時間曝露於嚴酷的環境下，仍顯示較高的可靠性。As shown in Table 2, the conductive adhesive of the present invention, which has a resin, a conductive filler and insulating inorganic particles, and the insulating inorganic particles have fine pores, still shows high reliability even when exposed to a harsh environment for a long time.
1,2:電磁波屏蔽膜 10:絕緣層 20:導電性接著劑層 30:金屬層 50:電阻值基板 51:聚苯硫醚膜 52:鍍錫銅箔膠帶 60:電磁波屏蔽基板1,2: Electromagnetic wave shielding film 10: Insulation layer 20: Conductive adhesive layer 30: Metal layer 50: Resistance value substrate 51: Polyphenylene sulfide film 52: Tinned copper foil tape 60: Electromagnetic wave shielding substrate
圖1係示意性顯示本發明之電磁波屏蔽膜之一例的剖面圖。 圖2係示意性顯示本發明之電磁波屏蔽膜之另一例的剖面圖。 圖3A係顯示電阻值試驗之方法的示意圖。 圖3B係顯示電阻值試驗之方法的示意圖。FIG. 1 is a cross-sectional view schematically showing an example of the electromagnetic wave shielding film of the present invention. FIG. 2 is a cross-sectional view schematically showing another example of the electromagnetic wave shielding film of the present invention. FIG. 3A is a schematic view showing a method of a resistance value test. FIG. 3B is a schematic view showing a method of a resistance value test.
1:電磁波屏蔽膜 1:Electromagnetic wave shielding film
10:絕緣層 10: Insulating layer
20:導電性接著劑層 20: Conductive adhesive layer
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04209687A (en) * | 1990-12-04 | 1992-07-31 | Toshiba Chem Corp | Conductive paste |
| JP2004339325A (en) * | 2003-05-14 | 2004-12-02 | Matsushita Electric Ind Co Ltd | Electrically-conducting adhesive and electronic component mounted body using the same |
| JP2005136144A (en) * | 2003-10-30 | 2005-05-26 | Kyocera Corp | Solid-state imaging apparatus |
| JP2014195067A (en) * | 2013-02-27 | 2014-10-09 | ｎ−ｔｅｃｈ株式会社 | Electromagnetic wave shield paint |
| TW201812795A (en) * | 2016-09-09 | 2018-04-01 | 拓自達電線股份有限公司 | Conductive adhesive composition |
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| JP5444699B2 (en) | 2008-11-28 | 2014-03-19 | 富士通株式会社 | Conductive particles for anisotropic conductive adhesive, anisotropic conductive adhesive, method for producing conductive particles for anisotropic conductive adhesive, semiconductor device |
| JP6255816B2 (en) | 2013-09-09 | 2018-01-10 | 東洋インキＳｃホールディングス株式会社 | Electromagnetic shielding sheet and printed wiring board |
| JP7003540B2 (en) | 2017-09-28 | 2022-02-10 | Dic株式会社 | Compositions and cured products |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04209687A (en) * | 1990-12-04 | 1992-07-31 | Toshiba Chem Corp | Conductive paste |
| JP2004339325A (en) * | 2003-05-14 | 2004-12-02 | Matsushita Electric Ind Co Ltd | Electrically-conducting adhesive and electronic component mounted body using the same |
| JP2005136144A (en) * | 2003-10-30 | 2005-05-26 | Kyocera Corp | Solid-state imaging apparatus |
| JP2014195067A (en) * | 2013-02-27 | 2014-10-09 | ｎ−ｔｅｃｈ株式会社 | Electromagnetic wave shield paint |
| TW201812795A (en) * | 2016-09-09 | 2018-04-01 | 拓自達電線股份有限公司 | Conductive adhesive composition |
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| TW202132510A (en) | 2021-09-01 |
| CN115038768A (en) | 2022-09-09 |
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