CN116003858A - Filler-containing film - Google Patents
Filler-containing film Download PDFInfo
- Publication number
- CN116003858A CN116003858A CN202211291848.5A CN202211291848A CN116003858A CN 116003858 A CN116003858 A CN 116003858A CN 202211291848 A CN202211291848 A CN 202211291848A CN 116003858 A CN116003858 A CN 116003858A
- Authority
- CN
- China
- Prior art keywords
- filler
- resin layer
- containing film
- layer
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000945 filler Substances 0.000 title claims abstract description 684
- 229920005989 resin Polymers 0.000 claims abstract description 509
- 239000011347 resin Substances 0.000 claims abstract description 509
- 239000002245 particle Substances 0.000 claims abstract description 278
- 239000006185 dispersion Substances 0.000 claims abstract description 46
- 238000003825 pressing Methods 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 31
- 238000004519 manufacturing process Methods 0.000 claims description 29
- 239000003505 polymerization initiator Substances 0.000 claims description 13
- 238000012546 transfer Methods 0.000 claims description 6
- 230000002950 deficient Effects 0.000 claims description 5
- 238000012719 thermal polymerization Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 2
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- 238000011156 evaluation Methods 0.000 description 44
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- 238000010438 heat treatment Methods 0.000 description 5
- 238000000016 photochemical curing Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
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- 229920000877 Melamine resin Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
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- 238000007689 inspection Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
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- 229920001721 polyimide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000010023 transfer printing Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 239000007848 Bronsted acid Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Chemical class 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-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
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229910021523 barium zirconate Inorganic materials 0.000 description 1
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002115 bismuth titanate Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 230000009969 flowable effect Effects 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
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000005011 phenolic resin Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- 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
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
- H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/831—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus
- H01L2224/83101—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus as prepeg comprising a layer connector, e.g. provided in an insulating plate member
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Non-Insulated Conductors (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Conductive Materials (AREA)
Abstract
And a filler-containing film having a filler dispersed in the resin layer, wherein the filler flow due to unnecessary flow of the resin layer is suppressed when the filler-containing film is pressure-bonded to an article. The filler-containing film 10A has: a filler dispersion layer 3 in which a filler 1 is dispersed in the resin layer 2. The surface of the resin layer 2 near the filler l has depressions 2b, 2c with respect to the tangential plane of the resin layer 2 at the central portion between adjacent fillers l. The ratio (La/D) of the layer thickness La of the resin layer 2 to the particle diameter D of the filler l is preferably 0.6 to 10, and the ratio (Lb/D) of the distance Lb of the deepest portion of the filler l from the tangential plane at the central portion between adjacent fillers l on the surface of the resin layer 2 where the recesses 2b, 2c are formed to the particle diameter D of the filler is preferably 60% to 105%.
Description
The present application is a divisional application of patent application with original filing date of 2017, 8, 31, application number of 201780052909.3 (international application number of PCT/JP 2017/051799) and the name of "filler-containing film".
Technical Field
The present invention relates to a filler-containing film.
Background
Filler-containing films in which a filler is dispersed in a resin layer are used in various applications such as matting films, films for capacitors, optical films, films for labels, antistatic films, anisotropic conductive films, and the like (patent document 1, patent document 2, patent document 3, and patent document 4). In terms of optical characteristics, mechanical characteristics, or electrical characteristics, it is desirable to suppress unnecessary resin flow of a resin that forms a filler-containing film when the filler-containing film is pressed against an article that is an adherend of the filler-containing film, thereby suppressing the occurrence of segregation of filler. In particular, when a filler-containing film is formed as an anisotropic conductive film for mounting electronic components such as IC chips, if the conductive particles are dispersed in an insulating resin layer at a high density so as to be able to cope with a high mounting density of the electronic components, the conductive particles dispersed at a high density are unnecessarily moved by resin flow during mounting of the electronic components, and are thus present in a biased state between terminals, which is a factor of occurrence of short circuits.
In order to reduce short-circuiting and improve the operability when temporarily pressing the anisotropic conductive film against the substrate, an anisotropic conductive film has been proposed in which a photocurable resin layer in which conductive particles are embedded in a single layer and an insulating adhesive layer are laminated (patent document 5). As a method for using the anisotropic conductive film, temporary pressure bonding is performed in a state where the photocurable resin is uncured and has tackiness, then the photocurable resin layer is cured by light to fix the conductive particles, and then the substrate and the electronic component are subjected to main pressure bonding.
In order to achieve the same object as in patent document 5, there has been proposed an anisotropic conductive film having a three-layer structure in which a first connection layer is sandwiched between a second connection layer and a third connection layer, which are mainly made of an insulating resin (patent documents 6 and 7). Specifically, in the anisotropic conductive film of patent document 6, the first connection layer has a structure in which conductive particles are arranged in a single layer along the plane direction of the second connection layer side of the insulating resin layer, and the insulating resin layer thickness in the central region between adjacent conductive particles is thinner than the insulating resin layer thickness in the vicinity of the conductive particles. On the other hand, the anisotropic conductive film of patent document 7 has a structure in which the boundary between the first connection layer and the third connection layer is undulating, the first connection layer has a structure in which conductive particles are arranged in a single layer along the planar direction on the third connection layer side of the insulating resin layer, and the insulating resin layer thickness in the central region between adjacent conductive particles is thinner than the insulating resin layer thickness in the vicinity of the conductive particles.
Prior art literature
Patent literature
Patent document 5 Japanese patent laid-open publication No. 2003-64224
Patent document 6 Japanese patent application laid-open No. 2014-060150
Patent document 7, japanese patent application laid-open No. 2014-060151.
Disclosure of Invention
Problems to be solved by the invention
However, the anisotropic conductive film described in patent document 5 has the following problems: the conductive particles are easily moved during temporary pressure bonding of the anisotropic conductive connection, and precise arrangement of the conductive particles before the anisotropic conductive connection cannot be maintained after the anisotropic conductive connection, or the distance between the conductive particles cannot be sufficiently spaced. Further, when the photocurable resin layer is cured after the anisotropic conductive film is temporarily pressed against the substrate and the photocurable resin layer in which the conductive particles are embedded is bonded to the electronic component, there is a problem that it is difficult to catch the conductive particles at the end portions of the bumps of the electronic component, or there is a problem that excessive force is required for pressing the conductive particles, and the conductive particles may not be sufficiently pressed. Patent document 5 also fails to sufficiently study the exposure of the conductive particles from the photocurable resin layer for the purpose of improving the press-in of the conductive particles.
Therefore, it is considered that, instead of the photocurable resin layer, the conductive particles are dispersed in the insulating resin layer having a high viscosity at a heating temperature at the time of anisotropic conductive connection, so that fluidity of the conductive particles at the time of anisotropic conductive connection is suppressed and workability at the time of bonding the anisotropic conductive film to the electronic component is improved. However, even if the conductive particles are temporarily and precisely arranged in such an insulating resin layer, if the resin layer flows during anisotropic conductive connection, the conductive particles flow simultaneously, and therefore it is difficult to sufficiently improve the trapping property of the conductive particles or reduce short circuits, to maintain the initial precise arrangement of the conductive particles after anisotropic conductive connection, and to maintain the conductive particles in a state of being spaced apart from each other.
In addition, in the case of the three-layer anisotropic conductive films described in patent documents 6 and 7, although there is no problem in the anisotropic conductive connection characteristics at the base points, the three-layer anisotropic conductive film is intended to reduce the number of manufacturing steps from the viewpoint of manufacturing costs. Further, in the vicinity of the conductive particles on one surface of the first connection layer, the entire first connection layer or a part thereof largely bulges along the outer shape of the conductive particles, and the insulating resin layer itself forming the first connection layer is uneven, and the conductive particles are held in the bulged portion, so that there is a possibility that restrictions in design for holding the conductive particles and improving the capturing property of the terminal increase.
In contrast, the present invention aims to: in a filler-containing film in which a filler such as conductive particles is dispersed in a resin layer, even if a three-layer structure is not necessary, even if the entire or a part of the resin layer in the vicinity of the filler holding the filler is not greatly raised from the outer shape of the filler, the flow of the filler due to unnecessary flow of the resin layer is suppressed at the time of press-bonding of the filler-containing film to an article, and in particular, when the filler-containing film is formed as an anisotropic conductive film, the unnecessary flow of conductive particles is suppressed at the time of thermocompression bonding of the anisotropic conductive film to an electronic component, the trapping of conductive particles at a terminal is improved, and short circuits are reduced.
Means for solving the problems
The present inventors have found the following findings regarding a filler-containing film having a filler dispersion layer in which a filler such as conductive particles is dispersed in a resin layer, regarding the relationship between the surface shape near the filler of the resin layer and the viscosity of the resin layer. That is, in the anisotropic conductive film described in patent document 5, the surface of the insulating resin layer (i.e., the photocurable resin layer) itself on the side where the conductive particles are embedded is flattened, and in contrast to this, (i) when the filler such as the conductive particles is exposed from the resin layer, if the surface of the resin layer around the filler is recessed with respect to the tangential plane of the resin layer at the central portion between adjacent fillers, the surface of the resin layer becomes partially defective due to the recess, and when the filler-containing film is bonded to an article by pressure bonding the filler-containing film to the article, unnecessary insulating resin that may interfere with the bonding of the filler to the article can be reduced; in addition, (ii) when the filler is embedded in the resin layer without being exposed from the resin layer, if undulation, which is considered as a trace of embedding the filler in the resin layer, is formed on the surface of the resin layer directly above the filler, the amount of resin in the concave portion of the undulation becomes small, and the filler is easily pushed in through the article when the filler-containing film is pressed against the article; (iii) Therefore, if 2 articles are pressed against each other via the filler-containing film, it is found that the filler held by the articles facing each other is well connected to the articles, in other words, the filler trapping property of the articles or the uniformity of the arrangement state of the filler held by the articles before and after the press-contact is improved, and further, the inspection of the article containing the filler film and the confirmation of the use surface are facilitated. It was also found that such a recess in the resin layer can be formed by adjusting the viscosity of the resin layer into which the filler is to be pressed in, in the case where the filler dispersion layer is formed by pressing the filler into the resin layer.
The present invention is based on the above-described findings, and provides a filler-containing film having a filler-dispersed layer in which a filler is dispersed in a resin layer,
wherein the surface of the resin layer near the filler has a recess with respect to the tangential plane of the resin layer at the central portion between adjacent fillers; in particular, a film is provided in which, in the recess, the surface of the resin layer around the filler is defective with respect to the tangential plane, or the resin amount of the resin layer directly above the filler is reduced as compared with when the surface of the resin layer directly above the filler is located in the tangential plane.
The present invention also provides a method for producing a filler-containing film, comprising a step of forming a filler-dispersed layer in which a filler is dispersed in a resin layer,
the filler dispersion layer forming step includes: a step of holding a filler on the surface of the resin layer, and a step of pressing the filler held on the surface of the resin layer into the resin layer;
in the step of holding the filler on the surface of the resin layer, the filler is held on the surface of the resin layer in a state in which the filler is dispersed,
in the step of pressing the filler into the resin layer, the viscosity, pressing speed, or temperature of the resin layer at the time of pressing the filler is adjusted so that the surface of the resin layer near the filler is recessed with respect to the tangential plane of the resin layer at the central portion between adjacent fillers; in particular, a method of making a filler-containing film is provided to form: as the recess, the surface of the resin layer around the filler is defective with respect to the tangential plane, or the resin amount of the resin layer directly above the filler is reduced as compared with when the surface of the resin layer directly above the filler is located on the tangential plane.
Effects of the invention
The filler-containing film of the present invention has a filler dispersion layer in which a filler is dispersed in a resin layer. In the filler dispersion layer, the surface of the resin layer near the filler has a recess with respect to the tangential plane of the resin layer at the central portion between adjacent fillers. That is, when the filler is exposed from the resin layer, the surface of the resin layer around the exposed filler has a recess, and the resin layer in the recess is in a state of being defective with respect to the tangential plane, so that the resin amount is reduced. In addition, when the filler is embedded in the resin layer without being exposed from the resin layer, the surface of the resin layer directly above the filler has a recess, and the amount of resin in the recess portion is reduced with respect to the tangential plane.
Therefore, if the resin layer around the filler exposed from the resin layer has a dent, the resin flow is reduced when the filler-containing film is pressed against the article due to the reduced amount of resin in the dent portion, and the filler is liable to press against the article. In addition, when 2 articles are pressure-bonded via a filler-containing film, it is difficult for the resin to form an obstacle to sandwiching the filler and to collapse the filler into a flat shape. In addition, to the extent that the amount of resin around the filler is reduced due to the dishing, the resin flow associated with making the filler unnecessarily flow is reduced. Therefore, the filler trapping property of the article is improved, and in particular, when the filler-containing film is an anisotropic conductive film, the trapping property of the conductive particles at the terminals is improved, and thus the conduction reliability is improved.
In addition, if the resin layer directly above the filler buried in the resin layer has a recess, the pressing force from the article is easily applied to the filler when the filler-containing film is pressed against the article. In addition, to the extent that the amount of resin directly above the filler is reduced due to the dishing, the resin flow associated with making the filler unnecessarily flow is reduced. Therefore, even in this case, the filler trapping property of the article is improved, and in particular, in the case where the filler-containing film is configured as an anisotropic conductive film, even in the case where conductive particles as the filler are dispersed in an insulating resin layer, the trapping property of the conductive particles at the terminals is improved, and thus the conduction reliability is improved.
Thus, according to the filler-containing film of the present invention, the trapping property of the filler is improved, and the filler on the article is not easily flowable, whereby the arrangement of the filler can be precisely controlled. Therefore, when the filler-containing film is an anisotropic conductive film, the arrangement of the conductive particles can be precisely controlled with respect to the terminals, and thus, the conductive film can be used for connection of electronic components having a terminal width of 6 μm to 50 μm and a fine pitch of 6 μm to 50 μm between terminals, for example. When the size of the conductive particles is smaller than 3 μm (for example, 2.5 to 2.8 μm), the electronic component can be connected without generating a short circuit if the effective connection terminal width (the width of the overlapping portion in a plan view among the pair of terminals facing each other at the time of connection) is 3 μm or more and the shortest inter-terminal distance is 3 μm or more.
Further, since the arrangement of the conductive particles can be precisely controlled, when electronic components having standard pitches are connected, the arrangement region of the conductive particles and the arrangement of the region in which the number density of the conductive particles is changed can be made to correspond to the arrangement of terminals of various electronic components.
In the filler-containing film of the present invention, if the resin layer directly above the filler buried in the resin layer has a recess, the position of the filler is clearly defined by visual observation of the filler-containing film, and therefore, product inspection is easily performed by visual appearance, and the front and back of the film surface are easily recognized. Therefore, when the filler-containing film is pressure-bonded to the article, it is easy to confirm the use surface of the "which film surface of the filler-containing film is bonded to the article". The same advantages are obtained in the case of the manufacture of filler-containing films.
Further, according to the filler-containing film of the present invention, it is not necessarily required to photo-cure the resin layer in order to fix the arrangement of the filler, and therefore, the resin layer may have tackiness when the filler-containing film is pressure-bonded to an article. Therefore, in the case of performing the main compression bonding after temporarily compressing the filler-containing film and the article, the operability at the time of the temporary compression bonding is improved, and in the case of performing the main compression bonding of the article after the temporary compression bonding, the operability is also improved.
On the other hand, according to the production method of the present invention, the viscosity, press-in speed, or temperature of the resin layer when the filler is embedded in the resin layer is adjusted to form the above-described recess in the resin layer. Therefore, the filler-containing film of the present invention exhibiting the above-described effects can be easily produced.
Drawings
Fig. 1A is a plan view showing the arrangement of conductive particles of an anisotropic conductive film 10A as an embodiment of one embodiment of a filler-containing film of the present invention.
Fig. 1B is a cross-sectional view of an anisotropic conductive film 10A as an embodiment of a filler-containing film of the present invention.
Fig. 2 is a cross-sectional view of an anisotropic conductive film 10B as an embodiment of a filler-containing film of the present invention.
Fig. 3A is a cross-sectional view of an anisotropic conductive film 10C as an embodiment of one embodiment of a filler-containing film of the present invention.
Fig. 3B is a cross-sectional view of an anisotropic conductive film 10C' as an embodiment of a filler-containing film of the present invention.
Fig. 4 is a cross-sectional view of an anisotropic conductive film 10D as an embodiment of a filler-containing film of the present invention.
Fig. 5 is a cross-sectional view of an anisotropic conductive film 10E as an embodiment of a filler-containing film of the present invention.
Fig. 6 is a cross-sectional view of an anisotropic conductive film 10F as an embodiment of a filler-containing film of the present invention.
Fig. 7 is a cross-sectional view of an anisotropic conductive film 10G as an embodiment of a filler-containing film of the present invention.
FIG. 8 is a cross-sectional view of an anisotropic conductive film 10X which is a comparative example of the filler-containing film of the present invention.
Fig. 9 is a cross-sectional view of an anisotropic conductive film 10Y which is a comparative example of the filler-containing film of the present invention.
Fig. 10 is a cross-sectional view of an anisotropic conductive film 10H as an embodiment of a filler-containing film of the present invention.
Fig. 11 is a cross-sectional view of an anisotropic conductive film 10I as an embodiment of a filler-containing film of the present invention.
Fig. 12A is a photograph of a cross section of an anisotropic conductive film as an example of an embodiment of a filler-containing film of the present invention.
Fig. 12B is a photograph of a cross section of an anisotropic conductive film as an example of an embodiment of a filler-containing film of the present invention.
FIG. 12C is a photograph of a cross section of an anisotropic conductive film which is a comparative example of a filler-containing film of the present invention.
Fig. 13A is a photograph of the upper surface of an anisotropic conductive film as an example of an embodiment of a filler-containing film of the present invention.
Fig. 13B is a photograph of the upper surface of an anisotropic conductive film as an example of an embodiment of a filler-containing film of the present invention.
Fig. 14 is a diagram showing particle positions of anisotropic conductive films of examples and comparative examples, wherein a: examples 1, b: examples 2, c: examples 3, d: examples 4, e: examples 5, f: example 6, g: example 7,h: example 8,i: example 9,j: examples 10, k: examples 11, l: examples 12, m: example 13, n: examples 14, o: example 15, p: comparative examples 1, q: comparative examples 2, r: example 3.
Detailed Description
An example of the filler-containing film of the present invention will be described in detail below with reference to the drawings. In the drawings, the same reference numerals denote the same or equivalent components.
< integral Structure of Filler-containing film >
Fig. 1A is a plan view illustrating the configuration of a filler-containing film 10A according to an embodiment of the present invention, and fig. 1B is an X-X sectional view thereof. The filler-containing film 10A is used as an anisotropic conductive film, and conductive particles as the filler 1 are dispersed in the insulating resin layer 2.
In the present invention, the filler-containing film 10A such as an anisotropic conductive film may be in the form of a long film having a length of 5m or more, or may be a wound body wound around a winding core.
The filler-containing film 10A is constituted by a filler dispersion layer 3, and the filler 1 is regularly dispersed in the filler dispersion layer 3 in a state of being exposed on one surface of the resin layer 2. The fillers 1 are not in contact with each other in a plan view of the film, and the fillers 1 are regularly dispersed so as not to overlap with each other in the film thickness direction, thereby forming a single filler layer in which the positions of the fillers 1 in the film thickness direction are aligned.
On the surface 2a of the resin layer 2 around each filler 1, a recess 2b is formed with respect to the tangential plane 2p of the resin layer 2 at the central portion between adjacent fillers. As will be described later, in the filler-containing film of the present invention, the surface of the resin layer directly above the filler 1 embedded in the resin layer 2 may be recessed 2c (fig. 4 and 6).
< state of dispersion of filler >
The dispersed state of the filler in the present invention includes a state in which the filler 1 is randomly dispersed and a state in which the filler is regularly arranged and dispersed. In any case, the alignment in the film thickness direction is preferable in terms of capturing stability. Here, the positional alignment of the filler 1 in the film thickness direction means that the filler 1 is not limited to the positional alignment of the filler 1 at a single depth in the film thickness direction, and includes a case where the filler 1 is present at or near the interface between the front and back surfaces of the resin layer 2.
In order to make the optical, mechanical, or electrical characteristics of the filler-containing film uniform, in particular, in the case where the filler-containing film is an anisotropic conductive film, it is preferable that the fillers 1 are arranged regularly in a planar view of the film in terms of suppressing short circuits. The arrangement scheme may be determined according to the article to be press-bonded with the filler-containing film, for example, in the anisotropic conductive film, the arrangement scheme of the conductive particles may be determined according to the layout of the terminals and the bumps, and thus the arrangement scheme of the conductive particles is not particularly limited. For example, the films may be arranged in a square lattice as shown in fig. 1A in a plan view. Examples of the regular arrangement of the fillers include rectangular lattices, diagonal lattices, hexagonal lattices, and triangular lattices. A combination of a plurality of lattices of different shapes is also possible. As an arrangement of the fillers, the particles of the linear arrangement of the fillers at predetermined intervals may be arranged at predetermined intervals. Alternatively, the filler may be provided in a form such that the filler is regularly provided in a predetermined direction of the film.
By arranging the fillers 1 in a regular arrangement such as a lattice shape so as not to contact each other, when the filler-containing film is pressure-bonded to an article, pressure is uniformly applied to each filler 1, and variation in the connection state can be reduced. In addition, by repeatedly causing the gaps of the filler in the longitudinal direction of the film or gradually increasing or decreasing the gaps of the filler in the longitudinal direction of the film, batch management can be performed, and traceability (traceability property) of the filler-containing film and the connection structure using the same can be provided. This is also effective for preventing forgery, falsification, illegal use, and the like of the filler-containing film or the connection structure using the same.
Therefore, in the anisotropic conductive film, the conductive particles are regularly arranged, and thus, when the electronic components are connected through the anisotropic conductive film, the on-resistance unevenness can be reduced. The conductive particles are more preferably aligned in the film thickness direction in order to achieve both the trapping stability and the short circuit suppression.
On the other hand, in the case where the inter-terminal intervals of the electronic components to be connected are wide and short circuits are unlikely to occur, the conductive particles may be randomly dispersed without being regularly arranged.
In the case where the fillers in the filler-containing film are regularly arranged, the lattice axis or the arrangement axis of the arrangement may be parallel to the longitudinal direction of the film or the direction perpendicular to the longitudinal direction, may intersect the longitudinal direction of the film, may be determined according to the article to be connected, and in the case where the filler-containing film is an anisotropic conductive film, may be determined according to the terminal width, the terminal pitch, or the like. For example, in the case of an anisotropic conductive film for fine pitch, as shown in fig. 1A, the lattice axis a of the conductive particles 1 is inclined with respect to the longitudinal direction of the anisotropic conductive film 10A, and the angle θ between the longitudinal direction of the terminal 20 (the short side direction of the film) connected by the anisotropic conductive film 10A and the lattice axis a is preferably 6 ° to 84 °, more preferably 11 ° to 74 °.
The distance between the fillers in the filler-containing film may be determined according to the article to be connected, and in the case where the filler-containing film is an anisotropic conductive film, the inter-particle distance of the conductive particles 1 may be appropriately determined according to the size of the terminals connected by the anisotropic conductive film and the terminal pitch. For example, in the case of coping with COG (Chip On Glass) having a fine pitch with an anisotropic conductive film, the nearest inter-particle distance is preferably 0.5 times or more, more preferably more than 0.7 times the conductive particle diameter D, from the viewpoint of preventing occurrence of short circuits. On the other hand, the upper limit of the closest inter-particle distance may be determined according to the purpose of the filler-containing film, and for example, the closest inter-particle distance may be preferably 100 times or less, more preferably 50 times or less, the conductive particle diameter D in terms of ease of manufacturing the filler-containing film. In addition, from the viewpoint of the trapping property of the conductive particles 1 at the terminal at the time of anisotropic conductive connection, the closest inter-particle distance is preferably set to 4 times or less, more preferably 3 times or less, the conductive particle diameter D.
In the filler-containing film of the present invention, the area occupancy of the filler calculated by the following formula is preferably 35% or less, more preferably 0.3 to 30%.
Area occupancy (%) = [ number density of fillers in plan view ] × [ average value of plan view area of 1 filler ] ×100
Here, as the measurement region of the number density of the filler, a rectangular region having 1 side of 100 μm or more and a total area of the measurement regions of 2mm is preferably arbitrarily set for a plurality of sites (preferably 5 sites or more, more preferably 10 sites or more) 2 The above. The size and number of each region may be appropriately adjusted according to the state of the number density. For example, as an example of the case where the number density of the anisotropic conductive film for fine pitch use is large, 200 sites (2 mm) of a region having an area of 100 μm×100 μm arbitrarily selected from the anisotropic conductive film 2 ) The number density of the conductive particles in the above formula can be obtained by measuring the number density using an observation image obtained by a metal microscope or the like and averaging the measured number density. The region having an area of 100 [ mu ] m by 100 [ mu ] m is a region where 1 or more bumps are present in the object to be connected having an inter-bump space of 50 [ mu ] m or less.
The number density is not particularly limited as long as the area occupancy is within the above range, but in the case where the filler-containing film is an anisotropic conductive film, the number density is practically 30 pieces/mm 2 The above is preferable, and 150 to 70000 pieces/mm is preferable 2 In particular, in the case of fine pitch use, 6000 to 42000 pieces/mm are preferable 2 More preferably 10000 to 40000 pieces/mm 2 Even more preferably 15000 to 35000 pieces/mm 2 。
The number density of the filler may be obtained by measuring an observation image using image analysis software (for example, winROOF, san francisco, etc.), in addition to the above-described observation using a metal microscope. The observation method and the measurement method are not limited to the above.
The average value of the planar areas of 1 filler is obtained by measuring an observation image of the film surface using an electron microscope such as a metal microscope or SEM. Image analysis software may also be used. The observation method and the measurement method are not limited to the above.
The area occupation ratio is an index of a thrust force necessary for pressing the filler-containing film against a pressing jig (jig) of an article, and is preferably 35% or less, more preferably 0.3 to 30%. This is for the following reason. That is, in order to cope with the fine pitch, the anisotropic conductive film has conventionally been designed to reduce the inter-particle distance of the conductive particles within a range where short-circuiting does not occur, thereby increasing the number density. However, if the number density is increased in this way, the pushing force required for the pressing jig for pressing the anisotropic conductive film against the electronic component increases with an increase in the number of terminals of the electronic component and an increase in the total area of connection of each electronic component, and there is a concern that insufficient pressing may occur in the conventional pressing jig. The problem of the thrust force necessary for such a pressing jig is not limited to the anisotropic conductive film, but is common to all the filler-containing films. In contrast, by setting the area occupancy to preferably 35% or less, more preferably 30% or less as described above, the thrust force necessary for pressing the filler-containing film against the article can be suppressed to be low.
< Filler >
The filler 1 in the present invention is suitably selected from among known inorganic fillers (metals, metal oxides, metal nitrides, etc.), organic fillers (resin particles, rubber particles, etc.), fillers in which an organic material and an inorganic material are mixed (for example, particles having a core formed of a resin material and a surface coated with a metal (metal-coated resin particles), fillers having insulating fine particles adhered to the surface of conductive particles, fillers having surfaces of conductive particles subjected to insulation treatment, etc.), depending on the properties required for the application such as hardness and optical properties, depending on the application of the filler-containing film. For example, silica filler, titanium oxide filler, styrene filler, acrylic filler, melamine filler, various titanates, or the like can be used in the optical film or the matting film. Titanium oxide, magnesium titanate, zinc titanate, bismuth titanate, lanthanum oxide, calcium titanate, strontium titanate, barium zirconate titanate, lead zirconate titanate, mixtures thereof, and the like can be used as the film for a capacitor. The adhesive film may contain polymer rubber particles, silicone rubber particles, and the like. The anisotropic conductive film may contain conductive particles. Examples of the conductive particles include metal particles such as nickel, cobalt, silver, copper, gold, and palladium, alloy particles such as solder, metal-coated resin particles, and metal-coated resin particles having insulating fine particles attached to the surface thereof. More than 2 kinds may be used in combination. Among them, the metal-coated resin particles are preferable in that the resin particles rebound after connection, so that contact with the terminals is easily maintained and conduction performance is stable. Further, the surface of the conductive particle may be subjected to an insulating treatment which does not interfere with the conductive property by a known technique. The filler mentioned for the above-mentioned application is not limited to this application, and other applications may be incorporated into the filler-containing film as required. In addition, 2 or more kinds of fillers may be used in combination as needed in the filler-containing film for each application.
The particle diameter D of the filler 1 is appropriately determined according to the use of the filler-containing film. For example, in the anisotropic conductive film, it is preferable that the thickness of the film be 1 μm or more and 30 μm or less, and more preferably 3 μm or more and 9 μm or less, in order to cope with the variation in the wiring height, suppress the increase in on-resistance, and suppress the occurrence of short-circuiting.
The particle diameter D of the filler before being dispersed in the resin layer 2 can be measured by a general particle size distribution measuring apparatus, and the average particle diameter can be obtained by using the particle size distribution measuring apparatus. As an example of the particle size distribution measuring apparatus, FPIA-3000 (Malvern Co.). On the other hand, the particle diameter D of the filler in the filler-containing film (i.e., the particle diameter D after dispersing the filler in the resin layer) can be obtained by observation with an electron microscope such as SEM. In this case, the number of samples to be measured for the particle diameter D is desirably 200 or more. In the case where the shape of the filler is not spherical, the maximum length or the diameter of the shape simulating the spherical shape may be referred to as the particle diameter D of the filler based on the plane image or the cross-sectional image.
For example, in the case of using particles having insulating fine particles attached to the surface thereof as a filler in order to improve the insulating properties of conductive particles of an anisotropic conductive film, the particle diameter of the filler of the present invention means a particle diameter excluding the insulating fine particles on the surface.
< resin layer >
(viscosity of resin)
The minimum melt viscosity of the resin layer 2 in the present invention is not particularly limited, and may be appropriately determined depending on the application of the filler-containing film, the method for producing the filler-containing film, and the like. For example, the degree of the recesses 2b and 2c may be set to 1000pa·s by the method of producing the filler-containing film. On the other hand, as a method for producing a filler-containing film, when a method is performed in which a filler is held on the surface of a resin layer in a predetermined arrangement and the filler is pressed into the resin layer, it is preferable that the minimum melt viscosity of the resin is 1100Pa "s or more in terms of film forming of the resin layer.
As described in the method for producing a filler-containing film described later, from the viewpoint of forming the recess 2B around the exposed portion of the filler 1 pressed into the resin layer 2 as shown in fig. 1B or the like, or forming the recess 2c directly above the filler 1 pressed into the resin layer 2 as shown in fig. 4 and 6, it is preferably 1500Pa s or more, more preferably 2000Pa s or more, still more preferably 3000 to 15000Pa s, still more preferably 3000 to 10000Pa s. As an example, the minimum melt viscosity can be obtained by using a measuring plate having a diameter of 8mm while keeping the measurement pressure constant at 5g by using a rotary rheometer (manufactured by TA instruments corporation), and more specifically, by setting the temperature rise rate to 10 ℃/min, the measurement frequency to 10Hz, and the load variation to the measuring plate to 5g in the temperature range of 30 to 200 ℃.
By setting the lowest melt viscosity of the resin layer 2 to a high viscosity of 1500Pa or more and s, unnecessary movement of the filler can be suppressed during pressure bonding of the filler-containing film to the article, and particularly when the filler-containing film is an anisotropic conductive film, it is possible to prevent the conductive particles to be held between terminals during anisotropic conductive connection from flowing due to resin flow.
In addition, in the case of forming the filler dispersion layer 3 including the filler film 10A by pressing the filler 1 into the resin layer 2, when the filler 1 is pressed into the resin layer 2 so as to expose the filler 1 from the resin layer 2, the resin layer 2 becomes a viscous body of high viscosity that plastically deforms the resin layer 2 around the filler 1 to form the recess 2B (fig. 1B), or when the filler 1 is pressed into the resin layer 2 so as to embed the filler 1 in the resin layer 2 without exposing the filler 1 from the resin layer 2, the resin layer 2 directly above the filler 1 becomes a viscous body of high viscosity that forms the recess 2c (fig. 6) on the surface of the resin layer 2. Therefore, the lower limit of the viscosity of the resin layer 2 at 60 ℃ is preferably 3000Pa, s or more, more preferably 4000Pa, s or more, still more preferably 4500Pa, s or more, and the upper limit is preferably 20000Pa, s or less, more preferably 15000Pa, s or less, still more preferably 10000Pa, s or less. The measurement can be performed by the same measurement method as the lowest melt viscosity, and the extraction temperature is 60 ℃.
The lower limit of the specific viscosity of the resin layer 2 when the filler 1 is pressed into the resin layer 2 is preferably 3000 pa_s or more, more preferably 4000 pa_s or more, still more preferably 4500 pa_s or more, and the upper limit is preferably 20000 pa_s or less, more preferably 15000 pa_s or less, still more preferably 10000 pa_s or less, depending on the shape, depth, and the like of the recesses 2b, 2c to be formed. Further, such viscosity is obtained at preferably 40 to 80 ℃, more preferably 50 to 60 ℃.
As described above, by forming the recess 2B (fig. 1B) around the filler 1 exposed from the resin layer 2, the resistance received from the resin is reduced compared with the case without the recess 2B for flattening of the filler 1 generated when the filler-containing film is pressure-bonded to the article. Therefore, when the filler-containing film is an anisotropic conductive film, the conductive particles can be easily sandwiched between the terminals during anisotropic conductive connection, and thus the conductive performance and the trapping performance can be improved.
Further, by forming the recess 2c (fig. 4 and 6) in the surface of the resin layer 2 directly above the filler 1 buried without being exposed from the resin layer 2, the pressure when the filler-containing film is pressed against the article becomes more likely to be concentrated on the filler 1 than in the case where the recess 2c is not present. Therefore, when the filler-containing film is an anisotropic conductive film, the conductive particles can be easily sandwiched between the terminals during anisotropic conductive connection, and thus the trapping property and the conduction performance can be improved.
(layer thickness of resin layer)
In the filler-containing film of the present invention, the ratio (La/D) of the layer thickness La of the resin layer 2 to the particle diameter D of the filler 1 is preferably 0.6 to 10. The particle diameter D of the filler 1 herein means the average particle diameter thereof. If the layer thickness La of the resin layer 2 is too large, the filler tends to shift in position when the filler-containing film is pressed against an article. Therefore, when the filler-containing film is an optical film, the optical characteristics are not uniform. In addition, in the case where the filler-containing film is an anisotropic conductive film, the trapping property of conductive particles at the terminal is lowered at the time of anisotropic conductive connection. This tendency is remarkable when La/D exceeds 10. Therefore, la/D is more preferably 8 or less, still more preferably 6 or less. Conversely, if the layer thickness La of the resin layer 2 is too small to make La/D smaller than 0.6, it is difficult to maintain the filler 1 in a predetermined particle dispersed state or a predetermined arrangement by the resin layer 2. Therefore, in the case where the filler-containing film is an anisotropic conductive film, particularly, in the case where the terminal to be connected is high-density COG, the ratio (La/D) of the layer thickness La of the insulating resin layer 2 to the particle diameter D of the conductive particles 1 is preferably 0.8 to 2. On the other hand, when the risk of occurrence of short-circuits is considered to be low due to the bump layout of the electronic component to be connected, the lower limit of the ratio (La/D) may be 0.25 or more.
(composition of resin layer)
The resin layer 2 in the present invention may be formed of a thermoplastic resin composition, a high-viscosity adhesive resin composition, and a curable resin composition. The resin composition constituting the resin layer 2 is appropriately selected according to the use of the filler-containing film, and whether or not the resin layer 2 is insulating is determined according to the use of the filler-containing film.
The curable resin composition may be formed of, for example, a heat-polymerizable composition containing a heat-polymerizable compound and a heat-polymerization initiator. The photopolymerizable composition may contain a photopolymerization initiator as needed.
In the case of using a thermal polymerization initiator and a photopolymerization initiator in combination, a compound that functions as both a thermal polymerizable compound and a photopolymerizable compound may be used, or a photopolymerizable compound may be contained in addition to the thermal polymerizable compound. The photopolymerizable compound is preferably contained in addition to the thermally polymerizable compound. For example, a cationic curing initiator is used as a thermal polymerization initiator, an epoxy resin is used as a thermal polymerizable compound, a photo radical initiator is used as a photopolymerization initiator, and an acrylate compound is used as a photopolymerizable compound.
The photopolymerization initiator may be contained in a plurality of types of photoreactions having different wavelengths. Thus, the wavelength used for the photo-curing of the resin for forming the resin layer in the production of the filler-containing film and the photo-curing of the resin when the filler-containing film is pressed against the article can be used separately.
In the photo-curing at the time of producing the filler-containing film, all or a part of the photopolymerizable compound contained in the resin layer may be photo-cured. By this photo-curing, the arrangement of the filler 1 in the resin layer 2 is maintained or immobilized, and suppression of short-circuiting and improvement of trapping can be seen. In addition, the viscosity of the resin layer in the step of producing the filler-containing film can be suitably adjusted by the photo-curing.
The blending amount of the photopolymerizable compound in the resin layer is preferably 30 mass% or less, more preferably 10 mass% or less, and still more preferably less than 2 mass%. The reason is that if the photopolymerizable compound is too much, the pushing force required for pressing the filler-containing film into the article increases.
Examples of the heat-polymerizable composition include: a thermal radical polymerizable acrylate composition containing a (meth) acrylate compound and a thermal radical polymerization initiator, a thermal cationic polymerizable epoxy composition containing an epoxy compound and a thermal cationic polymerization initiator, and the like. Instead of the thermal cationic polymerizable epoxy composition containing a thermal cationic polymerization initiator, a thermal anionic polymerizable epoxy composition containing a thermal anionic polymerization initiator may be used. In addition, as long as no particular obstacle is caused, a plurality of polymerizable compositions may be used in combination. Examples of the combination use include a combination use of a thermal cation polymerizable compound and a thermal radical polymerizable compound.
Here, as the (meth) acrylate compound, a conventionally known thermally polymerizable (meth) acrylate monomer can be used. For example, a monofunctional (meth) acrylate monomer or a difunctional or more polyfunctional (meth) acrylate monomer may be used.
Examples of the thermal radical polymerization initiator include organic peroxides and azo compounds. In particular, an organic peroxide which does not generate nitrogen causing bubbles can be preferably used.
The amount of the thermal radical polymerization initiator used is preferably 2 to 60 parts by mass, more preferably 5 to 40 parts by mass, based on 100 parts by mass of the (meth) acrylate compound, since curing failure occurs when the amount is too small and the product life decreases when the amount is too large.
Examples of the epoxy compound include: bisphenol a type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, modified epoxy resin thereof, alicyclic epoxy resin, and the like, and 2 or more of them may be used in combination. In addition, an oxetane compound may be used in combination with the epoxy compound.
As the thermal cationic polymerization initiator, a compound known as a thermal cationic polymerization initiator of an epoxy compound, for example, an iodonium salt, a sulfonium salt, a phosphonium salt, a ferrocene, or the like which generates an acid from heat, and in particular, an aromatic sulfonium salt exhibiting good latency with respect to temperature can be preferably used.
The amount of the thermal cationic polymerization initiator used is preferably 2 to 60 parts by mass, more preferably 5 to 40 parts by mass, based on 100 parts by mass of the epoxy compound, since the curing tends to be poor if it is too small and the product life tends to be reduced if it is too large.
As the thermoanionic polymerization initiator, a conventionally used known curing agent can be used. For example, organic acid dihydrazide, dicyandiamide, amine compound, polyamidoamine compound, cyanate ester compound, phenol resin, acid anhydride, carboxylic acid, tertiary amine compound, imidazole, lewis acid, bronsted acid salt, polythiol-based curing agent, urea resin, melamine resin, isocyanate compound, blocked isocyanate compound, etc., may be used singly or in combination of 1 or 2 or more kinds thereof. Among them, a microcapsule-type latent curing agent having an imidazole-modified product as a core and a polyurethane coated on the surface thereof is preferably used.
The thermally polymerizable composition preferably contains a film-forming resin and a silane coupling agent. Examples of the film-forming resin include: phenoxy resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyurethane resin, butadiene resin, polyimide resin, polyamide resin, polyolefin resin, etc., and 2 or more of them may be used in combination. Among them, phenoxy resins can be preferably used from the viewpoints of film formability, workability, and connection reliability. The weight average molecular weight is preferably 10000 or more. Further, as the silane coupling agent, an epoxy silane coupling agent, an acrylic silane coupling agent, and the like can be mentioned. These silane coupling agents are mainly alkoxysilane derivatives.
In order to adjust the melt viscosity, the heat polymerizable composition may contain an insulating filler in addition to the filler 1. Examples thereof include silica powder and alumina powder. The insulating filler is preferably a fine filler having a particle diameter of 20 to 1000nm, and the blending amount is preferably 5 to 50 parts by mass based on 100 parts by mass of a thermally polymerizable compound (photopolymerizable composition) such as an epoxy compound. The insulating filler other than the filler 1 is preferably used in the case where the purpose of the filler-containing film is an anisotropic conductive film, but may not be insulating depending on the purpose, and may contain a conductive fine filler, for example. When the filler-containing film is an anisotropic conductive film, a finer insulating filler (so-called nanofiller) different from the filler 1 may be contained in the resin layer forming the filler-dispersed layer as needed.
The filler-containing film of the present invention may contain, in addition to the insulating or conductive filler, a softener, an accelerator, an anti-aging agent, a colorant (pigment, dye), an organic solvent, an ion scavenger, and the like.
< position of filler in the thickness direction of resin layer >
In the filler-containing film of the present invention, as described above, the filler 1 may be exposed from the resin layer 2 or may be embedded in the resin layer 2 without being exposed at the position of the filler 1 in the thickness direction of the resin layer 2, and the ratio (Lb/D) of the distance Lb (hereinafter referred to as the embedding amount) of the deepest portion of the filler to the tangential plane 2p at the central portion between adjacent fillers of the surface 2a of the resin layer where the recesses 2b, 2c are formed to the particle diameter D of the filler 1 (hereinafter referred to as the embedding ratio) is preferably 60% to 105%.
By setting the embedding rate (Lb/D) to 60% or more, the filler 1 is maintained in a predetermined particle dispersed state or a predetermined arrangement by the resin layer 2, and by setting the embedding rate to 105% or less, the resin amount of the resin layer functioning so that the filler flows unnecessarily when the filler-containing film is pressed against the article can be reduced.
In the present invention, the term "embedding rate (Lb/D)" means a value obtained by setting 80% or more, preferably 90% or more, and more preferably 96% or more of the total amount of filler contained in the filler-containing film to the embedding rate (Lb/D). Thus, the embedding rate of 60% to 105% means that the embedding rate of 80% to 90%, preferably 96% to 105%, of the total amount of filler contained in the filler-containing film is 60% to 105%.
By thus making the embedding rate (Lb/D) of the entire filler uniform, the pressing load when the filler-containing film is pressed against the article is applied uniformly to the filler. Therefore, the film-attached body formed by bonding the filler-containing film to the article by pressure bonding can ensure uniformity in quality such as optical characteristics and mechanical characteristics. In addition, when the filler-containing film is an anisotropic conductive film, the trapping state of the conductive particles at the terminal is improved and the stability of conduction is improved at the time of anisotropic conductive connection.
The embedding rate (Lb/D) can be increased by arbitrarily extracting 10 or more parts of the filler-containing film by 30mm 2 The above region was obtained by observing a part of the film cross section with SEM images and measuring 50 or more fillers in total. In order to further improve the accuracy, 200 or more fillers may be measured.
The measurement of the embedding rate (Lb/D) may be performed by performing focus adjustment on the planar view image, and the number of the embedded rate (Lb/D) may be obtained at a time. Alternatively, a laser type differential displacement sensor (manufactured by Keyence or the like) may be used for measurement of the implantation rate (Lb/D).
(scheme of embedding ratio of more than 60% and less than 100%)
As a more specific embedding scheme of the filler 1 having an embedding rate (Lb/D) of 60% or more and 105% or less, first, there is a scheme in which the filler 1 is embedded at an embedding rate of 60% or more and less than 100% so as to be exposed from the resin layer 2, as in the filler-containing film 10A shown in fig. 1B. In the filler-containing film 10A, a portion of the surface of the resin layer 2 in contact with the filler 1 exposed from the resin layer 2 and the vicinity thereof have a concave portion 2b recessed in a mortar shape with respect to a tangential plane 2p of the surface 2a of the resin layer in the central portion between adjacent fillers.
When the filler-containing film 10A having the recess 2b is produced by pressing the filler 1 into the resin layer 2, the lower limit of the viscosity of the resin layer 2 at the time of pressing the filler 1 is preferably 3000Pa seed s or more, more preferably 4000Pa seed s or more, further preferably 4500Pa seed s or more, and the upper limit is preferably 20000Pa seed s or less, more preferably 15000Pa seed s or less, further preferably 10000Pa seed s or less. Further, such a viscosity is preferably obtained at 40 to 80 ℃, more preferably 50 to 60 ℃.
(scheme of 100% burial Rate)
Next, in the filler-containing film of the present invention, as an embodiment of the embedding rate (Lb/D) of 100%, there is given: as in the filler-containing film 10B shown in fig. 2, the filler 1 has a mortar-like recess 2B around the filler 1 as in the filler-containing film 10A shown in fig. 1B, and the exposed diameter Lc of the filler 1 exposed from the resin layer 2 is smaller than the particle diameter D of the filler 1; as in the filler-containing film 10C shown in fig. 3A, the recess 2b around the exposed portion of the filler 1 is shown steeply in the vicinity of the filler 1, and the exposed diameter Lc of the filler 1 is substantially equal to the particle diameter D of the filler; as in the filler-containing film 10D shown in fig. 4, the resin layer 2 has shallow recesses 2c in the surface thereof, and the filler 1 is exposed from the resin layer 2 at the point 1a at the top 1a thereof.
The minute protruding portion 2q may be formed adjacent to the recess 2b of the resin layer 2 around the exposed portion of the filler or the recess 2c of the resin layer directly above the filler. An example of this is shown in fig. 3B.
These filler-containing films 10B, 10C', 10D have an embedding rate of 100%, and therefore the top 1a of the filler 1 is aligned on one face with the surface 2a of the resin layer 2. If the top 1a of the filler 1 is aligned on one surface with the surface 2a of the resin layer 2, the resin amount in the peripheral film thickness direction of each filler is less likely to become uneven when the filler-containing film is pressed against an article, as compared with the case where the filler 1 protrudes from the resin layer 2 as shown in fig. 1B, and the effect of reducing the movement of the filler due to the resin flow can be obtained. Even if the embedding rate is not strictly 100%, this effect can be obtained if the top of the filler 1 embedded in the resin layer 2 is aligned with the surface of the resin layer 2 to such an extent that it becomes one surface. In other words, when the embedding rate (Lb/D) is approximately 80 to 105%, particularly 90 to 100%, the top of the filler 1 embedded in the resin layer 2 and the surface of the resin layer 2 may be referred to as one surface, and thus the movement of the filler due to the resin flow can be reduced.
Among these filler-containing films 10B, 10C, and 10D, the filler 1 is exposed from the resin layer 2 even at the point 1 of the top 1a, and therefore the capturing property of the filler 1 of the article is also excellent, because the amount of resin around the filler 1 is less likely to become uneven in 10D, and the movement of the filler due to the resin flow can be eliminated. Therefore, when the filler-containing film is an anisotropic conductive film, an effect that even a slight movement of conductive particles trapped by the terminal during anisotropic conductive connection is less likely to occur can be expected. Therefore, this embodiment is particularly effective for an anisotropic conductive film used for a purpose of narrow pitch or bump pitch.
The filler-containing films 10B (fig. 2), 10C (fig. 3A), and 10D (fig. 4) having different shapes and depths of the recesses 2B and 2C can be produced by changing the viscosity, the press-in speed, the temperature, and the like of the resin layer 2 when the filler 1 is pressed in, as will be described later.
(scheme of embedding ratio exceeding 100%)
In the filler-containing film of the present invention, as the case where the embedding rate exceeds 100%, there may be mentioned: as in the filler-containing film 10E shown in fig. 5, the resin layer 2 around the exposed portion of the filler 1 has a recess 2b with respect to the cut surface 2 p; as in the filler-containing film 10F shown in fig. 6, the filler 1 is not exposed from the resin layer 2 (i.e., the exposed diameter lc=0), and the surface of the resin layer 2 directly above the filler 1 has a recess 2c with respect to the cut surface 2 p.
The filler-containing film 10E (fig. 5) having the recess 2b in the resin layer 2 around the exposed portion of the filler 1 and the filler-containing film 10F (fig. 6) having the recess 2c in the resin layer 2 directly above the filler 1 can be produced by changing the viscosity, press-in speed, temperature, or the like of the resin layer 2 at the time of press-in of the filler 1 when they are produced.
When the filler-containing film 10E shown in fig. 5 is pressed against an article, the filler 1 is directly pressed by the article, and therefore the article and the filler are easily joined, and when the filler-containing film is an anisotropic conductive film, the capturing property of conductive particles at terminals when the electronic component is anisotropically connected by the anisotropic conductive film is improved. In addition, when the filler-containing film 10F shown in fig. 6 is pressed against an article, the filler 1 is pressed not directly but via the resin layer 2, but the amount of resin present in the pressing direction is smaller than that in the state of fig. 8 (that is, the filler 1 is embedded at an embedding rate exceeding 100%, the filler 1 is not exposed from the resin layer 2, and the surface of the resin layer 2 is flat), so that a pressing force is easily applied to the filler, and unnecessary movement of the filler 1 due to resin flow at the time of pressing against the article is prevented.
In terms of the effect of easily taking up the above-described recess 2B (fig. 1B, 2, 3A, 3B, 5) of the resin layer 2 around the exposed portion of the filler, or the recess 2c (fig. 4, 6) of the resin layer directly above the filler, the ratio (Le/D) of the maximum depth Le of the recess 2B around the exposed portion of the filler 1 to the particle diameter D of the filler 1 is preferably less than 50%, more preferably less than 30%, further preferably 20 to 25%, the ratio (Ld/D) of the maximum diameter Ld of the recess 2B around the exposed portion of the filler 1 to the particle diameter D of the filler 1 is preferably 100% or more, more preferably 100 to 150%, and the ratio (Lf/D) of the maximum depth Lf of the recess 2c of the resin directly above the filler 1 to the particle diameter D of the filler 1 is more than 0, preferably less than 10%, more preferably 5% or less.
The exposed diameter Lc of the filler 1 may be equal to or smaller than the particle diameter D of the filler 1, and preferably 10 to 90% of the particle diameter D. As shown in fig. 4, the filler 1 may be exposed at 1 point on the top of the filler 1, or the filler 1 may be completely embedded in the resin layer 2, and the exposed diameter Lc may be 0.
On the other hand, if there is a region in which the top of the filler 1 embedded in the resin layer 2 and the surface of the resin layer 2 are substantially one surface, and the depth of the recesses 2b and 2c (the distance between the deepest portion of the recess and the tangential plane at the central portion between adjacent fillers) is locally concentrated at 10% or more of the particle diameter (hereinafter, simply referred to as "filler having a depth of 10% or more from one surface of the resin layer"), there is a possibility that the appearance of the filler-containing film is impaired even if there is no problem in terms of the performance and quality of the filler-containing film. In addition, when the filler-containing film is bonded to the article with the recesses 2b and 2c in such regions facing the article, the recesses 2b and 2c may bulge after bonding. For example, in the case where the filler-containing film is an anisotropic conductive film, if conductive particles having a recess depth of 10% or more on one surface of the insulating resin layer 2 are concentrated on one bump, the conductive particles may bulge after being connected to the bump, and the conductivity may be reduced. Therefore, in the region of 200 times or more the filler particle diameter from any filler having a depth of 10% or more from one surface of the resin layer 2, the ratio of the number of fillers having a depth of 10% or more from one surface of the resin layer to the total number of fillers is preferably 50% or less, more preferably 40% or less, still more preferably 30% or less. In contrast, in the region where the proportion exceeds 50%, it is preferable to make the recesses 2b, 2c shallow by spreading resin or the like on the surface of the filler-containing film. In this case, the viscosity of the scattered resin is preferably lower than that of the resin forming the resin layer 2, and it is desirable that the concentration of the scattered resin is diluted to such an extent that the dishing of the resin layer 2 can be confirmed after scattering. Providing the recesses 2b, 2c so as to be shallower can improve the problems of appearance and bulge described above.
In the filler-containing film 10G having an embedding rate (Lb/D) of less than 60%, as shown in fig. 7, the filler 1 tends to roll on the resin layer 2, and therefore, it is preferable to set the embedding rate (Lb/D) to 60% or more in terms of improving the capturing rate of the filler by the article when the filler is pressed against the article.
In addition, in the case where the embedding rate (Lb/D) exceeds 100%, when the surface of the resin layer 2 is flat as in the filler-containing film 10X shown in fig. 8, the amount of resin interposed between the filler 1 and the article becomes excessive. In addition, when the surface of the resin layer 2 bulges along the shape of the filler 1 as in the filler-containing film 10Y shown in fig. 9, the filler 1 tends to flow due to the resin flow of the resin layer 2 when the filler is pressed against an article. Further, since the packing 1 presses the article not by directly contacting the article but via the resin, the packing is also liable to flow by the resin flow.
In the present invention, the presence of the recesses 2b, 2c in the surface of the resin layer 2 can be confirmed by observing the cross section of the filler-containing film with a scanning electron microscope, or can be confirmed by observation in the field of view. The recesses 2b, 2c can also be observed with an optical microscope, a metal microscope. The size of the recesses 2b, 2c can be confirmed by focus adjustment or the like at the time of image observation. The same applies to the deep recesses after resin is applied as described above.
< variant of Filler-containing film >
(second insulating resin layer)
The filler-containing film of the present invention may be formed by laminating a layer having the recesses 2b formed in the resin layer 2 of the filler-dispersed layer 3, as in the filler-containing film 10H shown in fig. 10, with the lowest melt viscosity being preferably lower than that of the second resin layer 4 of the resin layer 2. The second resin layer and a third resin layer described later are layers that do not contain the filler 1 dispersed in the filler dispersion layer. As in the filler-containing film 10I shown in fig. 11, the second resin layer 4 having a lower minimum melt viscosity than the resin layer 2 may be laminated on the surface of the filler-dispersed layer 3 on which the recess 2b is not formed (the surface opposite to the surface on which the recess is formed) of the resin layer 2.
The second resin layer 4 may be made insulating or conductive depending on the purpose of the filler-containing film. By laminating the second resin layer 4, when the filler-containing film is in pressure contact with the article, even if the surface of the article has irregularities, the space formed by the irregularities can be filled with the second resin layer. Therefore, in the case where the filler-containing film is an anisotropic conductive film having an insulating resin layer as the second resin layer, when the anisotropic conductive film is used to anisotropically electrically connect electronic components facing each other, the space formed by the electrode and the bump of the electronic component can be filled with the second resin layer, and the adhesion between the electronic components can be improved.
In the case of anisotropically connecting electronic components facing each other using an anisotropic conductive film having the second resin layer 4, it is preferable that the second resin layer 4 is located on the first electronic component side such as an IC chip (in other words, the resin layer 2 is located on the second electronic component side such as a substrate) regardless of whether the second resin layer 4 is located on the formation surface of the recess 2 b. Thus, unintended movement of the conductive particles can be avoided, and the trapping property can be improved. In general, a first electronic component such as an IC chip is set to a pressing jig side, a second electronic component such as a substrate is set to a stage side, and after temporarily press-bonding an anisotropic conductive film to the second electronic component, the first electronic component is formally press-bonded to the second electronic component.
The lower the difference in the minimum melt viscosity between the resin layer 2 and the second resin layer 4, the more easily the space formed by the surface irregularities of the article to be thermally bonded with the filler-containing film is filled with the second resin layer, and therefore, the adhesiveness between the filler-containing film and the article is improved, or in the case of thermally bonding the opposing articles via the filler-containing film, the adhesiveness between the opposing articles is improved. In addition, the more this difference is present, the more the amount of movement of the resin layer 2 present in the filler dispersion layer 3 is relatively reduced with respect to the second resin layer 4, and the more the unnecessary flow of the filler held by the resin layer 2 can be reduced. Therefore, in the case of an anisotropic conductive film in which the filler-containing film is a second resin layer having insulating properties, the space formed by the electrode and the bump of the electronic component anisotropically conductively connected by the anisotropic conductive film is easily filled with the second resin layer 4, and an effect of improving the adhesion between the electronic components can be expected. In addition, the movement amount of the resin layer 2 holding the conductive particles in the filler dispersion layer 3 is relatively reduced with respect to the second resin layer, so that the trapping property of the conductive particles at the terminal is easily improved.
The lowest melt viscosity ratio of the resin layer 2 to the second resin layer 4 also depends on the ratio of the layer thicknesses of the resin layer 2 to the second resin layer 4, but practically preferably 2 or more, more preferably 5 or more, and still more preferably 8 or more. On the other hand, if the ratio is too large, when the long filler-containing film is formed into a package, resin may overflow or blocking may occur, and therefore, it is practically preferable that the lowest melt viscosity ratio of the resin layer 2 to the second resin layer 4 is 15 or less. The preferable minimum melt viscosity of the second resin layer 4 more specifically satisfies the above ratio, and is 3000Pa seed s or less, more preferably 2000Pa seed s or less, and particularly 100 to 2000Pa seed s.
The second resin layer 4 may be formed by adjusting the viscosity of the same resin composition as the resin layer 2.
The thickness of the second resin layer 4 may be appropriately set according to the use of the filler-containing film. In view of not excessively increasing the difficulty of the lamination process of the second resin layer 4, the particle diameter of the filler is preferably 0.2 to 50 times. In the case where the filler-containing film is the anisotropic conductive films 10H and 10I, the layer thickness of the second resin layer 4 is preferably 4 to 20 μm, and further preferably 1 to 8 times the diameter of the conductive particles.
In the anisotropic conductive films 10H and 10I, the minimum melt viscosity of the entire anisotropic conductive film in which the insulating resin layer 2 and the second resin layer 4 are bonded together is also dependent on the ratio of the thicknesses of the resin layer 2 and the second resin layer 4, but may be 8000 Pa/s or less in practical use, and may be 200 to 70000 Pa/s, preferably 200 to 4000 Pa/s, for easy filling between bumps.
(third resin layer)
The third resin layer may be provided on the opposite side to the second resin layer 4 with the resin layer 2 interposed therebetween. The third resin layer may also be made insulating or conductive depending on the purpose of the filler-containing film. For example, in the case of an anisotropic conductive film in which the filler-containing film is a third resin layer having insulating properties, the third resin layer may be made to function as an adhesive layer. The third resin layer may be provided to fill a space formed by the electrode and the bump of the electronic component, similarly to the second resin layer.
The resin composition, viscosity, and thickness of the third resin layer may be the same as or different from those of the second resin layer. The minimum melt viscosity of the filler-containing film in which the resin layer 2, the second resin layer 4 and the third resin are laminated is not particularly limited, and may be 8000Pa to s, 200 to 70000 Pa to s, or 200 to 4000Pa to s.
(other lamination schemes)
Depending on the application of the filler-containing film, the filler-dispersed layers may be laminated, a layer containing no filler such as a second resin layer may be interposed between the laminated filler-dispersed layers, and further, a second resin layer and a third resin layer may be provided on the outermost layer.
< method for producing filler-containing film >
The method for producing a filler-containing film of the present invention includes a step of forming a filler dispersion layer in which a filler is dispersed in a resin layer. The step of forming the filler dispersion layer includes: a step of holding a filler on the surface of the resin layer in a state in which the filler is dispersed, and a step of pressing the filler held on the surface of the resin layer into the resin layer.
In the step of pressing the filler into the resin layer, the viscosity, pressing speed, or temperature of the resin layer at the time of pressing the filler is adjusted so that the surface of the resin layer near the filler is recessed with respect to the tangential plane of the resin layer at the central portion between adjacent fillers.
The resin layer into which the filler is pressed is not particularly limited as long as the recesses 2b and 2c can be formed, but it is preferable that the lowest melt viscosity is 1100Pa s or more and the viscosity at 60 ℃ is 3000Pa s or more. Wherein the minimum melt viscosity is preferably 1500Pa, s or more, more preferably 2000Pa, s or more, still more preferably 3000 to 15000Pa, s or more preferably 3000 to 10000 Pa; the lower limit of the viscosity at 60℃is preferably 3000Pa, s or more, more preferably 4000Pa, s or more, still more preferably 4500Pa, s or more, and the upper limit is preferably 20000Pa, s or less, more preferably 15000Pa, s or less, still more preferably 10000Pa, s or less. Therefore, the minimum melt viscosity of the resin layer in which the filler is held on the surface is preferably set to the above range.
In the case where the filler-containing film is formed of a single layer of the filler-dispersed layer 3, the filler-containing film of the present invention can be produced, for example, by holding the filler 1 on the surface of the resin layer 2 in a predetermined arrangement, and pressing the filler 1 into the resin layer with a flat plate or a roll. In the case of producing a filler-containing film having an embedding rate exceeding 100%, the filler-containing film may be pressed by a pressing plate having projections corresponding to the arrangement of the fillers.
The amount of the filler 1 to be embedded in the resin layer 2 can be adjusted by the pressing force, temperature, etc. at the time of pressing the filler 1, and the shape and depth of the recesses 2b, 2c can be adjusted by the viscosity, pressing speed, temperature, etc. of the resin layer 2 at the time of pressing. For example, in the case of producing the anisotropic conductive film 10B (fig. 2) as the filler-containing film, it is preferable that the viscosity of the insulating resin layer 2 when the conductive particles 1 are pressed is 8000 Pa/s (60 ℃) in the case of producing the anisotropic conductive film 10C (fig. 3A), it is preferable that the viscosity of the insulating resin layer 2 when the conductive particles 1 are pressed is 12000 Pa/s (70 ℃) in the case of producing the anisotropic conductive film 10D (fig. 4), it is preferable that the viscosity of the insulating resin layer 2 when the conductive particles 1 are pressed is 4500 Pa/s (60 ℃) in the case of producing the anisotropic conductive film 10D (fig. 4), it is preferable that the viscosity of the insulating resin layer 2 when the conductive particles 1 are pressed is 7000 Pa/s (70 ℃) in the case of producing the anisotropic conductive film 10F (fig. 6), and it is preferable that the viscosity of the insulating resin layer 2 when the conductive particles 1 are pressed is 3500 Pa/s (70 ℃).
As a method for holding the filler 1 in the resin layer 2, a known method can be used. For example, the filler 1 is directly sprinkled on the resin layer 2, or the filler 1 is attached as a single layer to a biaxially stretchable film, the film is biaxially stretched, and the stretched film is pressed against the resin layer 2 to transfer the filler to the resin layer 2, thereby holding the filler 1 to the resin layer 2. In addition, a transfer die may be used to hold the filler 1 to the resin layer 2.
In the case of holding the filler 1 on the resin layer 2 using a transfer mold, for example, as the transfer mold, there can be used: a transfer printing plate of a printing method is used for a transfer printing plate in which an opening is formed by a known opening forming method such as photolithography for an inorganic material such as silicon, various ceramics, glass, stainless steel, or the like, or an organic material such as various resins. The transfer mold may have a plate shape, a roll shape, or the like. The present invention is not limited to the above-described method.
The second resin layer 4 having a lower viscosity than the resin layer 2 may be laminated on the surface of the resin layer 2 pressed with the filler on the side pressed with the filler or on the opposite side.
When the filler-containing film is pressure-bonded to an article or when the filler-containing film is used to pressure-bond an article to be opposed to each other, it is preferable that the filler-containing film be formed into a long strip to some extent in order to economically perform the pressure-bonding. Therefore, the length of the filler-containing film is preferably 5m or more, more preferably 10m or more, and still more preferably 25m or more. On the other hand, if the filler-containing film is too long, the conventional connecting device cannot be used when the filler-containing film is pressure-bonded to the article, and the operability is also poor. Accordingly, the length of the filler-containing film is preferably 5000m or less, more preferably 1000m or less, and still more preferably 500m or less. From the viewpoint of excellent handling properties, such a long body containing a filler film is preferably produced into a wound body wound around a winding core.
< method for Using Filler-containing film >
The filler-containing film of the present invention can be used by being attached to an article in the same manner as the conventional filler-containing film, and the article is not particularly limited as long as the filler-containing film can be attached. Can be attached to various articles by crimping, preferably thermocompression bonding, depending on the purpose of the filler-containing film. The bonding may be performed by irradiation with light or by a combination of heat and light. For example, when the resin layer of the filler-containing film has sufficient adhesiveness to an article to which the filler-containing film is to be attached, the filler-containing film is lightly pressed against the article to obtain a film-attached body in which the filler-containing film is attached to the surface of one article. In this case, the surface of the article is not limited to a flat surface, and may have irregularities or may be curved as a whole. When the article is film-shaped or flat-plate-shaped, the filler-containing film may be bonded to the article using a pressure-bonding roller. Thus, the filler of the filler-containing film can be directly bonded to the article.
Further, a filler-containing film may be interposed between the first article and the second article facing each other, and the 2 articles facing each other may be joined together by a thermocompression bonding roller or a crimping tool to sandwich the filler between the articles. The filler-containing film may be sandwiched between the articles without bringing the filler into direct contact with the articles.
In particular, in the case where the filler-containing film is set as an anisotropic conductive film, it can be preferably used for: when a first electronic component such as an IC chip, an IC module, or an FPC is anisotropically connected to a second electronic component such as an FPC, a glass substrate, a plastic substrate, a rigid substrate, or a ceramic substrate via the anisotropic conductive film by using a thermocompression bonding tool. IC chips or wafer stacks using anisotropic conductive films may also be multilayered. The electronic component connected by the anisotropic conductive film of the present invention is not limited to the above-described electronic component. In recent years, the present invention is applicable to various electronic components.
Accordingly, the present invention includes a bonded body obtained by bonding the filler-containing film of the present invention to various articles by pressure bonding, and a method for producing the bonded body. In particular, when the filler-containing film is an anisotropic conductive film, a method for producing a connection structure in which electronic components are anisotropically and electrically connected to each other by using the anisotropic conductive film, and a connection structure obtained by the method, that is, a connection structure in which electronic components are anisotropically and electrically connected to each other by the anisotropic conductive film of the present invention are also included.
As a method for connecting electronic components using an anisotropic conductive film, when the anisotropic conductive film is formed of a single layer of the conductive particle dispersed layer 3, it is possible to manufacture a second electronic component such as various substrates by temporarily adhering and temporarily bonding the conductive particles 1 of the anisotropic conductive film from the side where the conductive particles 1 are embedded in the surface, and thermally bonding the non-embedded side of the conductive particles 1 of the anisotropic conductive film by temporarily bonding the non-embedded surface to the first electronic component such as an IC chip. In the case where the insulating resin layer of the anisotropic conductive film contains not only the thermal polymerization initiator and the thermal polymerizable compound but also the photopolymerization initiator and the photopolymerizable compound (the same as the thermal polymerizable compound is also possible), a pressure bonding method using both light and heat may be used. As long as this is done, unintended movement of the conductive particles can be suppressed to a minimum. The side not embedded with the conductive particles may be temporarily attached to the second electronic component and used. The anisotropic conductive film may be temporarily attached to the first electronic component instead of the second electronic component.
When the anisotropic conductive film is formed of a laminate of the conductive particle dispersion layer 3 and the second insulating resin layer 4, the conductive particle dispersion layer 3 is temporarily adhered to and temporarily pressure-bonded to the second electronic components such as various substrates, and the temporarily pressure-bonded anisotropic conductive film is placed with the second insulating resin layer 4 side thereof aligned with the first electronic components such as IC chips, and thermally pressure-bonded. The second insulating resin layer 4 side of the anisotropic conductive film may be temporarily attached to the first electronic component. The conductive particle dispersion layer 3 side may be temporarily attached to the first electronic component and used.
Examples
The following specifically describes an anisotropic conductive film as an embodiment of the filler-containing film of the present invention by way of examples.
Examples 1 to 15 and comparative examples 1 to 3
(1) Manufacture of anisotropic conductive films
The resin compositions to be formed into the insulating resin layer, the second insulating resin layer and the adhesive layer were prepared by blending as shown in tables 1A and 1B.
The resin composition to be formed into the insulating resin layer was coated on a PET film having a film thickness of 50 μm by a bar coater, and dried in an oven at 80 ℃ for 5 minutes, to form the insulating resin layers having the thicknesses shown in tables 2A and 2B on the PET film. In the same manner, a second insulating resin layer and an adhesive layer were formed on the PET film at the thicknesses shown in table 2A and table 2B, respectively.
However, in comparative example 3, conductive particles were mixed in a resin composition for forming an insulating resin layer, and an insulating resin layer (number density 70000/mm 2 )。
On the other hand, a mold was prepared so that the inter-particle distance in the square lattice arrangement shown in FIG. 1A in a plan view of the conductive particles 1 was equal to the particle diameter of the conductive particles, and the number density of the conductive particles was 28000 pieces/mm 2 . That is, the convex pattern of the mold is square lattice arrangement, and the pitch of the convex on the lattice axis is 2 times the average conductive particle diameter (3 μm), the lattice axis and the anisotropic conductive film Such a mold is produced by injecting particles of a known transparent resin into the mold in a molten state at an angle θ of 15 ° in the short side direction, and cooling and solidifying the resin mold to form a resin mold having a concave arrangement pattern shown in fig. 1A.
As the conductive particles, conductive particles in which insulating fine particles (average particle diameter of 0.3 μm) described in japanese patent application laid-open publication No. 2014-132567 are adhered to the surface of metal-coated resin particles (product of water chemical industry, AUL703, average particle diameter of 3 μm) were prepared, the conductive particles were filled in recesses of a resin mold, the insulating resin layer was coated thereon, and the resin was adhered by pressing at 60 ℃ under 0.5 MPa. Then, the insulating resin layer was peeled off from the mold, and the conductive particles on the insulating resin layer were pressed into the insulating resin layer by pressing (pressing condition: 60 to 70 ℃ C., 0.5 MPa), whereby anisotropic conductive films composed of a single layer of the conductive particle-dispersed layer were produced (examples 6 to 10, 14 and comparative example 2). The embedding state of the conductive particles is controlled by the press-in condition.
The conductive particle dispersion layer thus produced was laminated with the second insulating resin layer, whereby a two-layer anisotropic conductive film was produced (examples 1 to 5, 11 to 13, comparative example 1). In comparative example 3, the insulating resin layer in which the conductive particles are dispersed as described above was laminated with the second insulating resin layer. In this case, the surface of the conductive particle dispersion layer to be laminated with the second insulating resin layer is the surface of the insulating resin layer in which the conductive particles are pressed or the surface opposite to the surface as shown in table 2.
Further, the same two-layer anisotropic conductive film was laminated with an adhesive layer, thereby producing a three-layer anisotropic conductive film (example 15).
(2) Embedded state
The anisotropic conductive films of examples 1 to 15 and comparative examples 1 to 3 were cut by a cutting line passing through conductive particles, and the cross sections thereof were observed by a metal microscope. Examples 4 to 10 and 14 and comparative example 2 in which the conductive particles were exposed on the surface of the anisotropic conductive film or in which the conductive particles were located in the vicinity of the film surface of the anisotropic conductive film were observed on the film surface with a metal microscope. Fig. 12A shows a cross-sectional photograph of example 2, fig. 12B shows a cross-sectional photograph of example 3, fig. 12C shows a cross-sectional photograph of comparative example 3, fig. 13A shows a top surface photograph of example 4, and fig. 13B shows a top surface photograph of example 8.
In examples 1 to 7, 9 to 15 and comparative example 1, both the conductive particles having an embedding rate of less than 60% and the conductive particles having an embedding rate of more than 100% were exposed from the insulating resin layer, and the recesses 2B were observed in the surface of the insulating resin layer around the conductive particles in examples 1 to 7, 9 to 15 (fig. 12A, 12B, 13A). In comparative example 3, the embedding rate was less than 100%, but the conductive particles were not exposed from the insulating resin layer, and no recesses 2b and 2c were observed. In the photographs of fig. 12A, 12B, and 12C, the metal layer 1p of the conductive particle 1 has a dark circle, and the insulating particle layer 1q attached to the metal layer 1p has a light color.
In example 8, the conductive particles were completely embedded in the insulating resin layer, but the recesses 2c were observed on the surface of the insulating resin layer directly above the conductive particle layer, although the conductive particles were not exposed from the insulating resin layer (fig. 13B). In comparative example 2, the embedding rate was slightly higher than 100%, and the conductive particles were not exposed from the insulating resin layer, but the surface of the resin layer was flat, and no dishing was observed on the surface of the resin layer directly above the conductive particles.
(3) Evaluation
The anisotropic conductive films of the examples and comparative examples produced in (1) were measured and evaluated for (a) initial on-resistance, (b) on-reliability, (c) particle trapping property, and (d) positional deviation as follows. The results are shown in tables 2A and 2B.
(a) Initial on-resistance
The anisotropic conductive films of examples and comparative examples were cut at a sufficient area to be connected, sandwiched between an evaluation IC having conductive characteristics and a glass substrate, and heated and pressurized (180 ℃ C., 60MPa, 5 seconds) to obtain respective evaluation connectors, and the on-resistance of the obtained evaluation connectors was measured by a four-terminal method. The initial on-resistance is preferably 2Ω or less, more preferably 0.6Ω or less in practical use.
Here, the evaluation ICs and the glass substrate were assigned to the terminal patterns and the dimensions were as follows. When the evaluation IC is connected to the glass substrate, the long side direction of the anisotropic conductive film overlaps the short side direction of the bump.
IC for evaluating conduction characteristics
Outline 1.8X20.0 mm
Thickness of 0.5mm
Bump specification size 30×85 μm, bump-to-bump distance 50 μm, bump height 15 μm.
Glass substrate (ITO wiring)
1737F manufactured by Corning Co., ltd
The outline is 30X 50mm
Thickness of 0.5mm
Electrode ITO wiring
(b) Conduction reliability
The on-resistance after the evaluation connection material prepared in (a) was placed in a constant temperature bath having a temperature of 85℃and a humidity of 85% RH for 500 hours was measured in the same manner as the initial on-resistance. The conduction reliability is preferably 6Ω or less, more preferably 4Ω or less in practical use.
(c) Particle trapping property
Using an evaluation IC having particle trapping property, the alignment of the evaluation IC and a glass substrate (ITO wiring) corresponding to the terminal pattern was shifted by 6 μm, and the resultant was heated and pressurized (180 ℃, 60MPa, 5 seconds), and the number of trapping of conductive particles was measured in 100 regions of 6 μm×66.6 μm where the bumps of the evaluation IC and the terminals of the substrate were overlapped, to obtain the lowest number of trapping, and the evaluation was performed according to the following criteria. The practical use is preferably B-evaluation or more.
IC for evaluating particle trapping property
Outline 1.6X29.8 mm
Thickness of 0.3mm
Bump specification size 12×66.6 μm, bump pitch 22 μm (L/s=12 μm/10 μm), bump height 12 μm.
Evaluation criterion for particle-trapping property
More than A5
More than B3 and less than 5
C is less than 3.
(d) Positional offset
The same evaluation IC as in (c) was used, and the evaluation IC was placed on a glass substrate (ITO wiring) corresponding to the terminal pattern, and heated and pressurized (180 ℃, 60MPa, 5 seconds). In this case, the inter-particle distance before heating and pressing and the inter-particle distance after heating and pressing (measured by observation from the indentation on the glass side) were measured by a metal microscope, and the average value was obtained, and the inter-particle distance was calculated by the following formula and evaluated according to the following criteria. Practically, C is preferably not less than the evaluation.
In comparative example 3, the conductive particles were randomly dispersed, and therefore, no evaluation of positional deviation was performed.
Particle gap = 100 x P1/P0
(wherein P1 is an average value of inter-particle distances after heating and pressurizing,
P0: average value of inter-particle distance before heating and pressurizing).
Evaluation criterion for positional deviation
The particle gap of A is less than 160%
The particle gap of B exceeds 160% and is less than 180%
C particle gap exceeds 180% and is 200% or less
The D particle gap exceeds 200%. [ Table 2A ]
[ Table 2B ]
As is clear from tables 2A and 2B, examples 1 to 3 in which the embedding rate of the conductive particles was 60 to 105%, the conductive particles protruded from the insulating resin layer and having the recesses 2B, and example 8 in which the conductive particles were completely embedded in the insulating resin layer and having the recesses 2c, the initial on-resistance and on-reliability were sufficiently low, and the particle trapping property and the evaluation of positional deviation were also good; however, in comparative example 1 in which the embedding ratio was within this range, the conductive particles were protruded from the insulating resin layer, but the conductive particles were not completely embedded in the insulating resin layer, and in comparative example 2 in which the conductive particles were not recessed 2c, the positional deviation was evaluated as D, and the conductive particles could not be held at the time of connection, and the connection with a fine pitch could not be handled. It is also clear that comparative example 3, in which the conductive particles 1 were covered with the insulating resin layer 2 and protruded from the surface of the insulating resin layer 2 at the central portion between adjacent conductive particles, had no recess 2b nor recess 2c in the vicinity of the conductive particles 1, had poor conduction reliability. From this, it is assumed that if the surface of the insulating resin layer 2 bulges along the shape of the conductive particles 1, the conductive particles are easily affected by the resin flow during anisotropic conductive connection, and the press-in of the conductive particles into the terminal is insufficient.
It is also clear that the lowest melt viscosity of the insulating resin layers in examples 1 to 3 and 8 was 2000Pa, s or more, and the melt viscosity at 60℃was 3000Pa, s or more, but the lowest melt viscosity in comparative examples 1 and 2 was 1000Pa, s, and the melt viscosity at 60℃was 1500Pa, s, and the viscosity at the time of pressing was reduced by adjusting the pressing conditions of the conductive particles, so that the recesses 2b and 2c were not formed. On the other hand, in comparative example 3, the lowest melt viscosity and the viscosity at 60 ℃ were the same as those of examples 1 to 3, but the recesses 2b, 2c were not formed because the conductive particle dispersion layer was not formed by pressing the conductive particles into the insulating resin layer, but the conductive particles were dispersed in the resin composition for forming the insulating resin layer and coated to form the conductive particle dispersion layer.
It was found that, even when the melt viscosity was as low as that of example 11 (minimum melt viscosity 2000 Pa. S, 60 ℃ melt viscosity 3000 Pa. S) and as high as that of example 12 (minimum melt viscosity 10000 Pa. S, 60 ℃ melt viscosity 15000 Pa. S) with respect to example 3 (minimum melt viscosity 6000 Pa. S, 60 ℃ melt viscosity 8000 Pa. S), the positional displacement was not less than the B evaluation, and there was no problem in practical use, in the case of forming the recess 2B around the conductive particle.
It is also clear that the embedding rate of the conductive particles in examples 1 to 3 and 8 was 60 to 105%, and the evaluation of the positional deviation in example 13, in which the embedding rate was less than 60%, was reduced.
As is clear from examples 4 and 5 and examples 6 and 7, the anisotropic conductive film was practically satisfactory in both cases of using a double layer type conductive particle dispersion layer and a second insulating resin layer and using a single layer type conductive particle dispersion layer. It is also clear from examples 2, 3, 13 and 15 that the particle trapping property is practically good even in a three-layer type in which an adhesive layer is further provided on a two-layer anisotropic conductive film.
As is clear from examples 3 and 4 and 5, in the case where the anisotropic conductive film is a double layer type of the conductive particle dispersed layer and the second insulating resin layer, the evaluation of particle trapping property and positional deviation is practically good when the second insulating resin layer is laminated on the surface of the insulating resin layer in which the conductive particles are pressed and when the second insulating resin layer is laminated on the opposite side thereof.
It is also clear from examples 6, 7, 9, 10 and example 14 that the ratio La/D of the layer thickness La to the particle diameter D of the conductive particles with respect to the insulating resin layer is 10 or less, and if it exceeds 10, the evaluation of the positional deviation is reduced.
The same diluted resin composition was sprayed on the exposed surfaces of the conductive particles of the anisotropic conductive films of examples 4 and 5, and the surfaces were slightly smoothed, and the obtained products were evaluated in the same manner, so that substantially the same results were obtained.
Further, the initial on-resistance evaluation connectors of all examples were carried out in the same manner as the method for measuring the number of short circuits described in the example of japanese patent application laid-open publication 2016-085983, and the number of short circuits between 100 bumps was confirmed, and as a result, no short circuit was observed. Further, the anisotropic conductive films of all examples were found to have a short circuit occurrence rate of less than 50ppm as a result of the measurement method of the short circuit occurrence rate described in the examples of Japanese patent application laid-open No. 2016-085982, and it was confirmed that there was no problem in practical use.
Experimental examples 1 to 4
(production of anisotropic conductive film)
In order to examine the influence of the resin composition of the insulating resin layer on the film forming ability and the conduction characteristics of the anisotropic conductive film for COG connection, the resin compositions for forming the insulating resin layer and the second insulating resin layer were prepared by blending as shown in table 3. In this case, the minimum melt viscosity of the resin composition is adjusted by the preparation conditions of the resin composition. Using the obtained resin composition, an insulating resin layer was formed in the same manner as in example 1, and conductive particles were pressed into the insulating resin layer to produce an anisotropic conductive film composed of a single layer of a conductive particle-dispersed layer, and a second insulating resin layer was laminated on the side of the insulating resin layer into which conductive particles were pressed, to produce an anisotropic conductive film shown in table 4. In this case, the configuration of the conductive particles is the same as that of embodiment 1. In addition, by appropriately adjusting the pressing conditions of the conductive particles, the conductive particles were in the embedded state shown in table 4.
In the process of producing the anisotropic conductive film, after the conductive particles were pressed into the insulating resin layer, the film shape was not maintained in experimental example 4 (film shape evaluation: NG), but the film shape was maintained in experimental examples other than this (film shape evaluation: OK). Therefore, the anisotropic conductive films of the examples other than the example 4 were observed with a metal microscope to measure the embedded state of the conductive particles, and the following evaluation was performed.
In each experimental example except experimental example 4, the recesses around the conductive particles exposed from the insulating resin layer, the recesses of the insulating resin layer directly above the conductive particles, or both of them were observed. In table 4, the measured values of the dents were most clearly observed in each of the experimental examples. The observed buried state satisfies the aforementioned preferred range.
(evaluation)
(a) Initial on-resistance and on-reliability
The initial on-resistance and the on-reliability were evaluated in the same manner as in example 1. The evaluation criteria for this case are as follows. The results are shown in Table 4.
Evaluation criterion of initial on-resistance
OK:2.0Ω or less
NG: greater than 2.0 omega
Evaluation criterion for conduction reliability
OK:6.0Ω or less
NG: greater than 6.0 omega
(b) Particle trapping property
Particle trapping was evaluated in the same manner as in example 1.
As a result, experimental examples 1 to 3 were all above B-decision.
(c) Incidence of short circuit
The occurrence rate of short circuit was evaluated in the same manner as in example 1.
As a result, it was found that experimental examples 1 to 3 were each less than 50ppm and had no practical problem.
As is clear from table 4, when the lowest melt viscosity of the insulating resin layer was 800Pa seed s, it was difficult to form a film having depressions in the insulating resin layer in the vicinity of the conductive particles. On the other hand, it is found that when the minimum melt viscosity of the insulating resin layer is 1500Pa and s or more, the surface of the insulating resin layer in the vicinity of the conductive particles can be recessed by adjusting the conditions at the time of embedding the conductive particles, and thus the obtained anisotropic conductive film has good conduction characteristics when used in COG. In all of the experimental examples 1 to 3, the initial on-resistance was 0.6Ω or less, and the on-reliability was 4Ω or less, showing good results.
Experimental examples 5 to 8
(production of anisotropic conductive film)
For the anisotropic conductive film for FOG connection, in order to investigate the influence of the resin composition of the insulating resin layer on the film forming ability and the conduction characteristics, the resin compositions to be formed into the insulating resin layer and the second insulating resin layer were blended as shown in table 5. In this case, the arrangement of the conductive particles was set to a number density of 15000 pieces/mm 2 Is arranged with one of lattice axes inclined by 15 DEG with respect to the longitudinal direction of the anisotropic conductive film. In addition, the minimum melt viscosity of the resin composition is adjusted by the preparation conditions of the resin composition. Using the obtained resin composition, an insulating resin layer was formed in the same manner as in example 1, and conductive particles were pressed into the insulating resin layer to produce a conductive filmAn anisotropic conductive film comprising a single layer of the particle dispersion layer was further produced by laminating a second insulating resin layer on the side of the insulating resin layer in which the conductive particles were pressed, and the anisotropic conductive film shown in table 6 was produced. In this case, by appropriately adjusting the press-in conditions of the conductive particles, the conductive particles were in the embedded state shown in table 6.
In the process of producing the anisotropic conductive film, after the conductive particles were pressed into the insulating resin layer, the film shape was not maintained in experimental example 8 (film shape evaluation: NG), but the film shape was maintained in experimental examples other than this (film shape evaluation: OK). Therefore, the anisotropic conductive films of the examples other than the example 8 were observed with a metal microscope to measure the embedded state of the conductive particles, and the following evaluation was performed.
In each experimental example except experimental example 8, the recesses around the conductive particles exposed from the insulating resin layer, the recesses of the insulating resin layer directly above the conductive particles, or both of them were observed. In table 6, the measured values of the dents were most clearly observed in each of the experimental examples. The observed buried state satisfies the aforementioned preferred range.
(evaluation)
(a) Initial on-resistance and on-reliability
The (i) initial on-resistance and (ii) on-reliability were evaluated as follows. The results are shown in Table 6.
(i) Initial on-resistance
The anisotropic conductive films obtained in each experimental example were cut in a sufficient area for connection, and heated and pressed (180 ℃, 4.5MPa, 5 seconds) with a tool width of 1.5mm of a thermocompression bonding tool between an FPC for evaluation of the conductive characteristics and an alkali-free glass substrate, to obtain each connection for evaluation. The on-resistance of the obtained evaluation connector was measured by the four terminal method, and the measured value was evaluated according to the following criteria.
FPC for evaluating conduction characteristics:
terminal pitch 20 μm
Terminal width/inter-terminal spacing 8.5 μm/11.5 μm
Polyimide film thickness (PI)/copper foil thickness (Cu) =38/8, sn plated.
Alkali-free glass substrate:
electrode ITO wiring
Thickness of 0.7mm
Evaluation criterion of initial on-resistance
OK: less than 2.0 omega
NG:2.0Ω or more
(ii) Conduction reliability
The on-resistance after the evaluation connection material prepared in (i) was placed in a constant temperature bath having a temperature of 85℃and a humidity of 85% RH for 500 hours was measured in the same manner as the initial on-resistance, and the measured value was evaluated according to the following criteria.
Evaluation criterion for conduction reliability
OK: less than 5.0 omega
NG:5.0Ω or more
(b) Particle trapping property
The number of trapping of the conductive particles was measured for 100 terminals of the evaluation connector fabricated in (i), and the lowest number of trapping was obtained. If the minimum capture number is 10 or more, there is no practical problem.
The number of the lowest capture in each of experimental examples 5 to 7 was 10 or more.
(c) Incidence of short circuit
The number of short circuits of the evaluation connector produced in (i) was measured, and the occurrence rate of short circuits was determined from the measured number of short circuits and the number of gaps of the evaluation connector. The short circuit occurrence rates of examples 5 to 7 were all less than 50ppm, and it was confirmed that there was no problem in practical use.
As is clear from table 6, when the minimum melt viscosity of the insulating resin layer was 800Pa seed s, it was difficult to form a film having depressions on the surface of the insulating resin layer in the vicinity of the conductive particles. On the other hand, it is found that when the minimum melt viscosity of the insulating resin layer is 1500Pa and s or more, the surface of the insulating resin layer in the vicinity of the conductive particles can be recessed by adjusting the conditions at the time of embedding the conductive particles, and thus the obtained anisotropic conductive film has good conduction characteristics when used in FOG.
Symbol description
1 filler, conductive particles
1a Filler Top
Metal layer of 1p conductive particles
1q insulating particle layer
2 resin layer
2a surface of resin layer
2b recess
2c recess
2p section
2q protruding portion
3 filler dispersion layer, conductive particle dispersion layer
4 a second resin layer, a second insulating resin layer
10A, 10B, 10C', 10D, 10E, 10F, 10G, 10H, 10I filler-containing film and anisotropic conductive film
20 terminals
A lattice axis
D particle diameter of filler and particle diameter of conductive particle
Layer thickness of La resin layer
Lb embedding amount (distance of deepest portion of filler from tangent plane at central portion between adjacent fillers)
Lc exposed diameter
Maximum diameter of Ld dent
Maximum depth of recess around exposed portion of Le filler
Maximum depth of recess in resin directly above Lf filler
The long side direction of the theta terminal makes an angle with the lattice axis of the arrangement of the conductive particles.
Claims (51)
1. A filler-containing film having a filler dispersion layer in which a filler is dispersed in a resin layer,
wherein the surface of the resin layer near the filler has a recess with respect to the tangential plane of the resin layer at the central portion between adjacent fillers.
2. The filler-containing film of claim 1, wherein a recess is formed on the surface of the resin layer around the filler exposed from the resin layer.
3. The filler-containing film of claim 2, wherein the ratio (Le/D) of the depth Le of the recess from the tangential plane to the particle diameter D of the filler is less than 50%.
4. The filler-containing film of claim 2 or 3, wherein the ratio (Ld/D) of the maximum diameter Ld of the recess to the particle diameter D of the filler is 100% or more.
5. The filler-containing film of claim 1, wherein a recess is formed on the surface of the resin layer directly above the filler buried in the resin layer and not exposed from the resin layer.
6. The filler-containing film of claim 1, wherein the filler is in contact with a cut surface of the resin layer at a central portion between adjacent fillers, and a recess is formed on a surface of the resin layer around the contact.
7. The filler-containing film of claim 5 or 6, wherein the ratio (Lf/D) of the depth Lf of the depression from the tangential plane to the particle diameter D of the filler is less than 10%.
8. The filler-containing film according to any one of claims 1 to 7, wherein the ratio (La/D) of the layer thickness La of the resin layer to the particle diameter D of the filler is 0.6 to 10.
9. The filler-containing film according to any one of claims 1 to 8, wherein a ratio (Lb/D) of a distance Lb of a deepest portion of the filler to a tangential plane at a central portion between adjacent fillers of the surface where the recess is formed of the resin layer to a particle diameter D of the filler is 60% to 105%.
10. The filler-containing film according to any one of claims 1 to 9, wherein the fillers are disposed in non-contact with each other.
11. The filler-containing film according to any one of claims 1 to 10, wherein the closest inter-particle distance of the filler is 0.5 times or more the particle diameter of the filler.
12. The filler-containing film according to any one of claims 1 to 11, wherein a second resin layer is laminated on a surface opposite to the surface of the resin layer of the filler dispersion layer on which the depressions are formed.
13. The filler-containing film according to any one of claims 1 to 11, wherein a second resin layer is laminated on the surface of the resin layer of the filler dispersion layer on which the depressions are formed.
14. The filler-containing film of claim 12 or 13, wherein the second resin layer has a lower minimum melt viscosity than the resin layer of the filler dispersion layer.
15. The filler-containing film according to any one of claims 12 to 14, wherein the lowest melt viscosity ratio of the resin layer of the filler dispersion layer to the second resin layer is 2 or more.
16. The filler-containing film of any one of claims 1 to 15, wherein the viscosity of the resin layer of the filler dispersion layer at 60 ℃ is 3000 to 20000pa seed s.
17. The filler-containing film of any one of claims 1-16, wherein the filler is a conductive particle.
18. The filler-containing film of claim 17, wherein the resin layer of the filler dispersion layer is an insulating resin layer, and the filler-containing film is used as an anisotropic conductive film.
19. The filler-containing film of any one of claims 1 to 18, wherein the fillers do not contact each other when the filler-containing film is viewed from above.
20. The filler-containing film according to claim 19, wherein the recess is a portion of the surface of the resin layer around the filler in the vicinity of the filler with respect to the above-mentioned tangential plane defect, or a portion of the resin layer directly above the filler in the vicinity of the filler, in which the resin amount of the resin layer directly above the filler is reduced as compared with when the surface of the resin layer directly above the filler is located in the above-mentioned tangential plane.
21. The filler-containing film of any one of claims 1 to 20, wherein the resin layer contains a thermally polymerizable compound and a thermal polymerization initiator.
22. The filler-containing film of any one of claims 1 to 21, wherein the resin layer contains a minute insulating filler different from the filler.
23. The filler-containing film of claim 22, wherein the insulating filler has a particle diameter of 20 to 1000nm.
24. The filler-containing film according to claim 22 or 23, wherein when the resin layer contains a thermally polymerizable compound and a thermal polymerization initiator, the content of the insulating filler is 5 to 50 parts by mass based on 100 parts by mass of the thermally polymerizable compound.
25. The filler-containing film of any one of claims 1 to 24, wherein the resin layer has a minimum melt viscosity of 1000Pa or greater than or equal to s.
26. The filler-containing film of any one of claims 1 to 25, wherein a second resin layer is further laminated on the filler dispersion layer.
27. The filled film of claim 26 wherein the filled film is further provided with a third resin layer.
28. The filler-containing film of any one of claims 1 to 27, wherein the minimum melt viscosity of the filler-containing film as a whole is 8000Pa seed s or less.
29. The filler-containing film of any one of claims 1 to 28, wherein the filler-containing film is formed into a package having a length of 5m or more.
30. A filler-containing film having a filler dispersion layer in which a filler is dispersed in a resin layer,
wherein the fillers do not contact each other when the filler-containing film is viewed in plan,
the surface of the resin layer near the filler has a recess with respect to the tangential plane of the resin layer at the central portion between adjacent fillers,
the ratio (Lb/D) of the distance Lb from the tangential plane to the deepest part of the filler to the particle diameter D of the filler is the embedding rate, and 80% or more of the total number of fillers has an embedding rate of 60% or more and 105% or less.
31. A filler-containing film having a filler dispersion layer in which a filler is dispersed in a resin layer,
Wherein the fillers do not contact each other when the filler-containing film is viewed in plan,
the surface of the resin layer near the filler has a recess with respect to the tangential plane of the resin layer at the central portion between adjacent fillers,
the recess is a portion where the surface of the resin layer is defective with respect to the tangential plane in the vicinity of the filler, or a portion where the resin layer directly above the filler in the vicinity of the filler is reduced in resin amount compared with the case where the surface of the resin layer directly above the filler is located in the tangential plane,
the ratio (Lb/D) of the distance Lb from the tangential plane to the deepest part of the filler to the particle diameter D of the filler is the embedding rate, and 80% or more of the total number of fillers has an embedding rate of 60% or more and 105% or less.
32. A filler-containing film having a filler dispersion layer in which a filler is dispersed in a resin layer,
wherein the surface of the resin layer near the filler has a recess with respect to the tangential plane of the resin layer at the central portion between adjacent fillers,
the resin layer contains a minute insulating filler different from the above filler,
the ratio (Lb/D) of the distance Lb from the tangential plane to the deepest part of the filler to the particle diameter D of the filler is the embedding rate, and 80% or more of the total number of fillers has an embedding rate of 60% or more and 105% or less.
33. A filler-containing film having a filler dispersion layer in which a filler is dispersed in a resin layer,
wherein the surface of the resin layer near the filler has a recess with respect to the tangential plane of the resin layer at the central portion between adjacent fillers,
the minimum melt viscosity of the resin layer is 1000 Pa-s or more,
the ratio (Lb/D) of the distance Lb from the tangential plane to the deepest part of the filler to the particle diameter D of the filler is the embedding rate, and 80% or more of the total number of fillers has an embedding rate of 60% or more and 105% or less.
34. A filler-containing film having a filler dispersion layer in which a filler is dispersed in a resin layer,
wherein a second resin layer is further laminated on the filler dispersion layer,
the surface of the resin layer near the filler has a recess with respect to the tangential plane of the resin layer at the central portion between adjacent fillers,
the lowest melt viscosity of the whole filler-containing film is 8000Pa and s or less,
the ratio (Lb/D) of the distance Lb from the tangential plane to the deepest part of the filler to the particle diameter D of the filler is the embedding rate, and 80% or more of the total number of fillers has an embedding rate of 60% or more and 105% or less.
35. A filler-containing film having a filler dispersion layer in which a filler is dispersed in a resin layer,
wherein the surface of the resin layer near the filler has a recess with respect to the tangential plane of the resin layer at the central portion between adjacent fillers,
The ratio (Lb/D) of the distance Lb from the tangential plane to the deepest part of the filler to the particle diameter D of the filler is the embedding rate, and 80% or more of the total number of fillers has an embedding rate of 60% or more and 105% or less,
the filler-containing film is formed into a package having a length of 5m or more.
36. The filler-containing film of claim 35, wherein a second resin layer is further laminated on the filler dispersion layer.
37. The filled film of claim 36 wherein the filled film is further provided with a third resin layer.
38. A filler-containing film having a filler dispersion layer in which a filler is dispersed in a resin layer,
wherein the fillers do not contact each other when the filler-containing film is viewed in plan,
the surface of the resin layer near the filler has a recess with respect to the tangential plane of the resin layer at the central portion between adjacent fillers,
a recess is formed on the surface of the resin layer directly above the filler which is buried in the resin layer but not exposed from the resin layer, or the filler is in contact with a tangential plane of the resin layer at the central portion between adjacent fillers, and a recess is formed on the surface of the resin layer around the contact.
39. A film-attached body, wherein the filler-containing film according to any one of claims 1 to 38 is attached to an article.
40. A connection structure in which a first article and a second article are connected via the filler-containing film of any one of claims 1 to 38.
41. The connection structure according to claim 40, wherein the first electronic component and the second electronic component are connected via the filler-containing film as an anisotropic conductive film according to claim 18.
42. A method for producing a connection structure, wherein a first article and a second article are pressure-bonded via the filler-containing film according to any one of claims 1 to 38.
43. A method of manufacturing a connection structure, wherein the first article and the second article are a first electronic component and a second electronic component, respectively, and the first electronic component and the second electronic component are thermally bonded via the filler-containing film for anisotropic conductive film according to claim 18, whereby the connection structure is manufactured in which the first electronic component and the second electronic component are connected.
44. A method for producing a filler-containing film, which comprises a step of forming a filler-dispersed layer in which a filler is dispersed in a resin layer,
the filler dispersion layer forming step includes: a step of holding a filler on the surface of the resin layer, and a step of pressing the filler held on the surface of the resin layer into the resin layer;
In the step of holding the filler on the surface of the resin layer, the filler is held on the surface of the resin layer in a state in which the filler is dispersed,
in the step of pressing the filler into the resin layer, the viscosity, pressing speed, or temperature of the resin layer at the time of pressing the filler is adjusted so that the surface of the resin layer near the filler is recessed with respect to the tangential plane of the resin layer at the central portion between adjacent fillers.
45. The method for producing a filler-containing film according to claim 44, wherein in the step of holding the filler on the surface of the resin layer, a resin layer having a minimum melt viscosity of 1100Pa seed s or more and a viscosity of 3000Pa seed s or more at 60℃is used as the resin layer.
46. The method for producing a filler-containing film according to claim 44 or 45, wherein,
in the step of holding the filler on the surface of the resin layer, the filler is held on the surface of the resin layer in a predetermined arrangement,
in the step of pressing the filler into the resin layer, the filler is pressed into the resin layer by a platen or a roller.
47. The method for producing a filler-containing film according to any one of claims 44 to 46, wherein in the step of holding the filler on the surface of the resin layer, the filler is held on the surface of the resin layer in a predetermined arrangement by filling the filler in a transfer mold and transferring the filler to the resin layer.
48. The method for producing a filler-containing film according to claim 44 to 47, wherein conductive particles are used as the filler.
49. The method for producing a filler-containing film according to any one of claims 44 to 48, wherein the anisotropic conductive film is produced as the filler-containing film using the insulating resin layer as the resin layer of the filler dispersion layer.
50. The method for producing a filler-containing film according to any one of claims 44 to 49, wherein a second resin layer is further laminated on the filler-dispersed layer.
51. The method for producing a filler-containing film according to claim 50, wherein the filler-containing film is further provided with a third resin layer.
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-179042 | 2016-09-13 | ||
| JP2016179042 | 2016-09-13 | ||
| JP2017-084913 | 2017-04-23 | ||
| JP2017084913 | 2017-04-23 | ||
| JP2017158302 | 2017-08-20 | ||
| JP2017-158302 | 2017-08-20 | ||
| JP2017166277A JP7081097B2 (en) | 2016-09-13 | 2017-08-30 | Filler-containing film |
| JP2017-166277 | 2017-08-30 | ||
| CN201780052909.3A CN109642037A (en) | 2016-09-13 | 2017-08-31 | Containing filled film |
| PCT/JP2017/031318 WO2018051799A1 (en) | 2016-09-13 | 2017-08-31 | Filler-containing film |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780052909.3A Division CN109642037A (en) | 2016-09-13 | 2017-08-31 | Containing filled film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116003858A true CN116003858A (en) | 2023-04-25 |
Family
ID=61618854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211291848.5A Pending CN116003858A (en) | 2016-09-13 | 2017-08-31 | Filler-containing film |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7352114B2 (en) |
| KR (2) | KR20220080204A (en) |
| CN (1) | CN116003858A (en) |
| TW (2) | TW202227543A (en) |
| WO (1) | WO2018051799A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024042720A1 (en) * | 2022-08-26 | 2024-02-29 | 株式会社レゾナック | Adhesive film for circuit connection, connection structure, and methods for producing same |
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| JP2004207689A (en) * | 2002-12-12 | 2004-07-22 | Tokyo Electron Ltd | Anisotropic conductive film, method for manufacturing the same, and probe |
| CN104541416A (en) * | 2012-08-24 | 2015-04-22 | 迪睿合电子材料有限公司 | Anisotropic-conductive-film manufacturing method and anisotropic conductive film |
| CN105358642A (en) * | 2013-07-29 | 2016-02-24 | 迪睿合株式会社 | Method for producing conductive adhesive film, conductive adhesive film, and method for producing connection body |
| JP2016103476A (en) * | 2014-11-17 | 2016-06-02 | デクセリアルズ株式会社 | Anisotropically conductive film |
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| JP2003064324A (en) | 2001-06-11 | 2003-03-05 | Hitachi Chem Co Ltd | Anisotropic electroconductive adhesive film, connection method for circuit board using the same and circuit board connected body |
| JP2006015680A (en) | 2004-07-05 | 2006-01-19 | Oike Ind Co Ltd | Lusterless film |
| JP2013103368A (en) | 2011-11-11 | 2013-05-30 | Sekisui Chem Co Ltd | Multi-layer film |
| TWI810551B (en) | 2012-08-24 | 2023-08-01 | 日商迪睿合股份有限公司 | Intermediate product film, anisotropic conductive film, connection structure, and method for manufacturing the connection structure |
| JP6221285B2 (en) | 2013-03-21 | 2017-11-01 | 日立化成株式会社 | Circuit member connection method |
| JP6264897B2 (en) | 2014-01-23 | 2018-01-24 | トヨタ自動車株式会社 | High dielectric constant film and film capacitor |
| WO2015141830A1 (en) * | 2014-03-20 | 2015-09-24 | デクセリアルズ株式会社 | Anisotropic conductive film and manufacturing method thereof |
| JP7081097B2 (en) | 2016-09-13 | 2022-06-07 | デクセリアルズ株式会社 | Filler-containing film |
-
2017
- 2017-08-31 WO PCT/JP2017/031318 patent/WO2018051799A1/en active Application Filing
- 2017-08-31 CN CN202211291848.5A patent/CN116003858A/en active Pending
- 2017-08-31 KR KR1020227018479A patent/KR20220080204A/en not_active Application Discontinuation
- 2017-08-31 KR KR1020187036915A patent/KR20190010879A/en not_active Application Discontinuation
- 2017-09-05 TW TW111107350A patent/TW202227543A/en unknown
- 2017-09-05 TW TW106130309A patent/TWI759326B/en active
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2022
- 2022-05-25 JP JP2022084941A patent/JP7352114B2/en active Active
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| JPH07308632A (en) * | 1994-05-17 | 1995-11-28 | Sumitomo Metal Ind Ltd | Metal plate with good lubricity, and manufacture of the same |
| JP2004207689A (en) * | 2002-12-12 | 2004-07-22 | Tokyo Electron Ltd | Anisotropic conductive film, method for manufacturing the same, and probe |
| CN104541416A (en) * | 2012-08-24 | 2015-04-22 | 迪睿合电子材料有限公司 | Anisotropic-conductive-film manufacturing method and anisotropic conductive film |
| CN105358642A (en) * | 2013-07-29 | 2016-02-24 | 迪睿合株式会社 | Method for producing conductive adhesive film, conductive adhesive film, and method for producing connection body |
| JP2016103476A (en) * | 2014-11-17 | 2016-06-02 | デクセリアルズ株式会社 | Anisotropically conductive film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7352114B2 (en) | 2023-09-28 |
| TW202227543A (en) | 2022-07-16 |
| KR20190010879A (en) | 2019-01-31 |
| KR20220080204A (en) | 2022-06-14 |
| TWI759326B (en) | 2022-04-01 |
| TW201825563A (en) | 2018-07-16 |
| JP2022126655A (en) | 2022-08-30 |
| WO2018051799A1 (en) | 2018-03-22 |
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