WO2022181570A1 - Electromagentic wave shield film - Google Patents
Electromagentic wave shield film Download PDFInfo
- Publication number
- WO2022181570A1 WO2022181570A1 PCT/JP2022/007068 JP2022007068W WO2022181570A1 WO 2022181570 A1 WO2022181570 A1 WO 2022181570A1 JP 2022007068 W JP2022007068 W JP 2022007068W WO 2022181570 A1 WO2022181570 A1 WO 2022181570A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electromagnetic wave
- shielding film
- wave shielding
- protective layer
- layer
- Prior art date
Links
- 239000011241 protective layer Substances 0.000 claims abstract description 115
- 239000010410 layer Substances 0.000 claims abstract description 55
- 239000011231 conductive filler Substances 0.000 claims abstract description 40
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 69
- 239000012790 adhesive layer Substances 0.000 claims description 49
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 239000003822 epoxy resin Substances 0.000 claims description 16
- 229920000647 polyepoxide Polymers 0.000 claims description 16
- 239000004593 Epoxy Substances 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 235000021317 phosphate Nutrition 0.000 claims description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 abstract description 24
- 238000005452 bending Methods 0.000 abstract description 19
- 239000011342 resin composition Substances 0.000 description 28
- 238000012360 testing method Methods 0.000 description 26
- 239000000203 mixture Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000002923 metal particle Substances 0.000 description 16
- 229910002012 Aerosil® Inorganic materials 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- 238000007731 hot pressing Methods 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 239000004840 adhesive resin Substances 0.000 description 7
- 229920006223 adhesive resin Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 229920001225 polyester resin Polymers 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920000180 alkyd Polymers 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 125000005372 silanol group Chemical group 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920005678 polyethylene based resin Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- 229910002014 Aerosil® 130 Inorganic materials 0.000 description 1
- 229910002015 Aerosil® 150 Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 229910002018 Aerosil® 300 Inorganic materials 0.000 description 1
- 229910002019 Aerosil® 380 Inorganic materials 0.000 description 1
- 229910002013 Aerosil® 90 Inorganic materials 0.000 description 1
- 229910002020 Aerosil® OX 50 Inorganic materials 0.000 description 1
- 229910002021 Aerosil® TT 600 Inorganic materials 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical class NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- KYIMHWNKQXQBDG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC Chemical compound N=C=O.N=C=O.CCCCCC KYIMHWNKQXQBDG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 150000005332 diethylamines Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 150000003947 ethylamines Chemical class 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 150000003956 methylamines Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0084—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single continuous metallic layer on an electrically insulating supporting structure, e.g. metal foil, film, plating coating, electro-deposition, vapour-deposition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/095—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- 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
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
Definitions
- the present invention relates to an electromagnetic wave shielding film.
- shield printed wiring also referred to as “plate”
- the shield layer used in the electromagnetic wave shield film is formed of a thin metal layer formed by vapor deposition, sputtering, plating, or the like, or a conductive paste containing a high content of conductive filler.
- 5G, etc. will spread in earnest, high frequency and high speed transmission will advance in order to communicate large amounts of data, and noise countermeasures for electronic devices will become even more necessary.
- an electromagnetic wave shield film consists of a shield layer that serves as a main body that shields electromagnetic waves, and a protective layer (insulating layer) that protects the shield layer from external impacts, chemicals, solvents, water, etc. .
- Flexibility is required for the electromagnetic shielding film placed on the flexible printed wiring board, and flexibility is also required for the protective layer that is a component thereof.
- Patent Document 1 discloses a conductive shield layer having unevenness and an adhesive layer covering the unevenness, and the maximum peak height of the unevenness is is greater than the thickness of the adhesive layer.
- Patent Document 2 discloses an electromagnetic wave shielding film comprising a shield layer and an insulating layer laminated on the shield layer, wherein the insulating layer contains silica fine particles, and the silica fine particles in the insulating layer
- An electromagnetic wave shielding film is disclosed in which the content is 10 to 50 wt%.
- a resin composition for a protective layer used in such an electromagnetic wave shielding film contains an amorphous polyester resin, a curing agent, and a white pigment, and the amorphous polyester resin is ,
- the number average molecular weight Mn is less than 20,000
- the glass transition point Tg is 40 ° C. or higher
- the curing agent is a blocked isocyanate, a trimethylolpropane adduct of hexane diisocyanate, and an isocyanurate adduct of cyclohexane diisocyanate
- a resin composition is disclosed which is at least one selected from the group consisting of:
- a highly flexible protective layer has a low glass transition point and a low crosslink density. If the glass transition point of the protective layer is low, there is a problem that blocking is likely to occur when the electromagnetic wave shielding film is stored in a roll. In addition, if the cross-linking density of the resin constituting the protective layer is low, the electromagnetic wave shielding film will not be exposed to the steps such as openings provided to expose the ground circuit on the printed wiring board (hereinafter simply referred to as “steps on the printed wiring board”). ), the protective layer tends to have partially thin spots, the physical strength of the protective layer decreases, and moisture easily permeates the protective layer. As a result, there is a problem that the heat resistance and moisture resistance of the electromagnetic wave shielding film tend to deteriorate.
- the present invention is an invention made to solve the above problems, and an object of the present invention is to provide an electromagnetic wave shielding film that is less likely to cause blocking during roll storage and has excellent moisture resistance and bending resistance.
- the electromagnetic shielding film of the present invention is an electromagnetic shielding film in which a protective layer and a shielding layer are laminated, and the protective layer is a urethane having an acid value of 2000 to 4000 g/eq and a Tg of 0° C. or higher. and a non-conductive filler having an average particle size of 10 ⁇ m or less, wherein the weight ratio of the non-conductive filler to the total weight of the protective layer is 10 to 40% by weight.
- the urethane resin contained in the protective layer has an acid value of 2000 to 4000 g/eq.
- the acid value is within the above range, the cross-linking density is within a suitable range, so that when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing, the protective layer is less likely to have partially thin portions. .
- the physical strength of the protective layer is reduced, and moisture does not easily permeate the protective layer.
- the flex resistance and moisture resistance of the electromagnetic wave shielding film are improved. If the acid value is less than 2000 g/eq, the crosslink density becomes high and the protective layer becomes hard.
- the toughness of the protective layer is lowered, and the bending resistance tends to be lowered. If the acid value exceeds 4000 g/eq, the cross-linking density becomes low, and when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing, the protective layer tends to be partially thinned. As a result, the moisture resistance tends to be extremely lowered.
- the urethane-based resin contained in the protective layer has a Tg of 0° C. or higher. Therefore, when the electromagnetic wave shielding film of the present invention is stored in a roll, blocking is less likely to occur.
- the protective layer contains a non-conductive filler having an average particle size of 10 ⁇ m or less, and the weight ratio of the non-conductive filler to the total weight of the protective layer is 10 to 40% by weight. If the protective layer contains a non-conductive filler having an average particle diameter of 10 ⁇ m or less in the above weight ratio, the urethane resin contained in the protective layer is used when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing. can be prevented from flowing and part of the protective layer becoming thin. As a result, the electromagnetic wave shielding film has good moisture resistance and bending resistance.
- the weight ratio of the non-conductive filler is less than 10% by weight, it becomes difficult to obtain the effect of containing the non-conductive filler, and moisture resistance tends to decrease. If the weight ratio of the non-conductive filler exceeds 40% by weight, the protective layer becomes hard and the flexibility tends to decrease. As a result, the bending resistance tends to decrease.
- the protective layer preferably further contains an epoxy resin.
- the protective layer contains an epoxy resin, it is possible to suppress the flow of the urethane resin contained in the protective layer when the electromagnetic wave shielding film is arranged on the printed wiring board by hot pressing.
- the urethane-based resin preferably has a Tg of 0 to 60°C.
- the protective layer has appropriate fluidity when the electromagnetic wave shielding film of the present invention is hot-pressed onto a printed wiring board, so that part of the protective layer becomes thin. It is possible to prevent the moisture resistance and bending resistance of the electromagnetic wave shielding film from deteriorating.
- the urethane resin preferably has a weight average molecular weight of 100,000 to 2,000,000, more preferably 170,000 to 500,000.
- the weight-average molecular weight of the urethane-based resin is within the above range, the urethane-based resin has appropriate hardness and fluidity, so that the electromagnetic wave shielding film can be improved in heat resistance, moisture resistance, and bending resistance.
- the non-conductive filler is preferably at least one selected from the group consisting of silica and organic phosphates. Non-conductive fillers made of these materials can favorably improve the moisture resistance and bending resistance of the electromagnetic wave shielding film.
- the shield layer may be a conductive adhesive layer.
- the shield layer may be a metal layer, and an adhesive layer may be further laminated on the side of the shield layer on which the protective layer is not laminated.
- the electromagnetic wave shielding film of the present invention can suitably shield electromagnetic waves in any aspect. In addition, blocking hardly occurs when the electromagnetic wave shielding film is stored in a roll, and the heat resistance, moisture resistance, and bending resistance of the electromagnetic wave shielding film are sufficiently increased.
- the protective layer contains a urethane resin having an acid value of 2000 to 4000 g/eq and a Tg of 0° C. or higher, and a non-conductive filler having an average particle size of 10 ⁇ m or less.
- the weight ratio of the non-conductive filler to the total weight of the protective layer is 10 to 40% by weight. Therefore, the cross-linking density of the urethane-based resin is in an appropriate range, and the flex resistance and moisture resistance of the electromagnetic wave shielding film are improved.
- the Tg of the urethane-based resin is 0° C. or higher, blocking hardly occurs when the electromagnetic wave shielding film is stored in a roll.
- the protective layer contains a predetermined non-conductive filler, when the electromagnetic wave shielding film is placed on the printed wiring board by heat pressing, the urethane resin contained in the protective layer flows and part of the protective layer thinning can be prevented. Therefore, the protective layer is less likely to have partially thin portions. As a result, the electromagnetic wave shielding film has good moisture resistance and bending resistance.
- FIG. 1 is a cross-sectional view schematically showing an example of the electromagnetic wave shielding film of the present invention.
- FIG. 2A is a cross-sectional view schematically showing a printed wiring board preparation step in the method for manufacturing a shield printed wiring board using the electromagnetic wave shielding film of the present invention.
- FIG. 2B is a cross-sectional view schematically showing an electromagnetic shielding film placement step in the method for manufacturing a shield printed wiring board using the electromagnetic shielding film of the present invention.
- FIG. 2C is a cross-sectional view schematically showing a hot press step in the method for manufacturing a shield printed wiring board using the electromagnetic wave shielding film of the present invention.
- FIG. 2D is a cross-sectional view schematically showing an example of a shield printed wiring board manufactured using the electromagnetic wave shielding film of the present invention.
- FIG. 3 is a cross-sectional view schematically showing another example of the electromagnetic wave shielding film of the present invention.
- FIG. 4A is a schematic diagram showing a resistance value test method.
- FIG. 4B is a schematic diagram showing a resistance value test method.
- FIG. 5 is a diagram schematically showing a flex resistance test.
- FIG. 6 is a diagram schematically showing a blocking test.
- the electromagnetic wave shielding film of the present invention will be specifically described below.
- the present invention is not limited to the following embodiments, and can be appropriately modified and applied without changing the gist of the present invention.
- FIG. 1 is a cross-sectional view schematically showing an example of the electromagnetic wave shielding film of the present invention.
- the electromagnetic wave shielding film 10 shown in FIG. 1 is an electromagnetic wave shielding film in which a protective layer 20, a metal layer 30, and a conductive adhesive layer 40 are laminated in order.
- the metal layer 30 functions as a shield layer for shielding electromagnetic waves. Each configuration will be described below.
- the protective layer 20 contains urethane-based resin and non-conductive filler.
- the urethane-based resin contained in the protective layer 20 has an acid value of 2000 to 4000 g/eq.
- the acid value is preferably 2100-3900 g/eq, more preferably 2500-3500 g/eq.
- the cross-linking density is within a suitable range, so that when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing, the protective layer is less likely to have partially thin portions. .
- the physical strength of the protective layer is reduced, and moisture does not easily permeate the protective layer.
- the flex resistance and moisture resistance of the electromagnetic wave shielding film are improved.
- the acid value is less than 2000 g/eq
- the crosslink density becomes high and the protective layer becomes hard.
- the toughness of the protective layer is lowered, and the bending resistance tends to be lowered.
- the acid value exceeds 4000 g/eq
- the cross-linking density becomes low, and when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing, the protective layer tends to be partially thinned. As a result, the moisture resistance tends to be extremely lowered.
- the urethane-based resin contained in the protective layer 20 has a Tg of 0° C. or higher.
- Tg is preferably 0 to 60°C, more preferably 30 to 60°C.
- the protective layer has appropriate fluidity when the electromagnetic wave shielding film of the present invention is hot-pressed onto a printed wiring board.
- a protective layer may be formed in a transfer film. At this time, the adhesion between the protective layer and the transfer film is improved.
- the Tg of the urethane-based resin means a value measured according to differential scanning calorimetry (DSC) in JIS K7121.
- the weight average molecular weight of the urethane resin is preferably 100,000 to 2,000,000, more preferably 170,000 to 500,000.
- the urethane-based resin has appropriate hardness and fluidity, so that the heat resistance, moisture resistance, and flex resistance of the protective layer can be improved.
- the weight average molecular weight of the urethane-based resin can be measured by gel permeation chromatography (GPC) under the following conditions.
- Measuring instrument Alliance GPC System (manufactured by Waters) Column: Shodex GPC KF-806L (Showa Denko) Column temperature: 40°C Sample concentration: 0.05 wt%/THF Injection volume: 10 ⁇ L Standard sample: Tosoh: standard PS 500, Shodex standard PS SM-105 (set)
- the non-conductive filler contained in the protective layer 20 has an average particle diameter of 10 ⁇ m or less, and the weight ratio of the non-conductive filler to the total weight of the protective layer 20 is 10 to 40% by weight. Also, the weight ratio of the non-conductive filler is preferably 10 to 35% by weight, more preferably 10 to 25% by weight.
- the protective layer 20 contains the non-conductive filler in the above weight ratio, the urethane-based resin contained in the protective layer flows when the electromagnetic wave shielding film is placed on the printed wiring board by hot pressing, and a part of the protective layer is partially removed. It can prevent thinning. Therefore, the protective layer is less likely to have partially thin portions. As a result, the electromagnetic wave shielding film has good moisture resistance and bending resistance.
- the weight ratio of the non-conductive filler when the weight ratio of the non-conductive filler is 10 to 25% by mass, the flex resistance of the electromagnetic wave shielding film becomes better. If the weight ratio of the non-conductive filler is less than 10% by weight, it becomes difficult to obtain the effect of containing the non-conductive filler, and moisture resistance tends to decrease. If the weight ratio of the non-conductive filler exceeds 40% by weight, the protective layer becomes hard and the flexibility tends to decrease. As a result, the bending resistance tends to decrease.
- the non-conductive filler preferably has an average particle size of 100 nm to 10 ⁇ m.
- the average particle diameter of the non-conductive filler is 100 nm or more, it is possible to suitably prevent the urethane-based resin contained in the protective layer from flowing and partially thinning the protective layer.
- the average particle size of the non-conductive filler is 10 ⁇ m or less, the thickness of the entire protective layer can be reduced.
- the non-conductive filler is preferably at least one selected from the group consisting of silica and organic phosphates. Among these, silica is preferred. Non-conductive fillers made of these materials can favorably improve the moisture resistance and bending resistance of the electromagnetic wave shielding film.
- non-conductive filler is silica, colloidal silica, fumed silica, wet silica synthesized by wet method, dry silica synthesized by dry method, porous silica, non-porous silica, hydrophobic silica, various surfaces It may be treated hydrophilic silica.
- Hydrophobic silica is obtained, for example, by subjecting the silanol groups present on the surface of amorphous silica synthesized by a dry method or amorphous silica synthesized by a wet method to a surface treatment for imparting hydrophobicity.
- a surface treatment for imparting hydrophobicity can be manufactured.
- Examples of such surface treatment include treatment of coating the surface of amorphous silica with waxes such as paraffin wax, carnauba wax, amide wax, and polyethylene wax.
- the resulting hydrophobic silica exhibits hydrophobicity because the silanol groups on the surface of the amorphous silica are covered with a wax layer.
- amorphous silica is modified by hydrolysis or the like by adding organosilicon compounds such as tetramethylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, epoxy group-containing silane, or dimethyldichlorosilane, or amino group-containing organic compounds. Processing is also included. Hydrophobic silica thus obtained is obtained by chemically reacting silanol groups on the surface of amorphous silica with an organic silicon compound or the like, and has hydrophobic groups such as alkyl groups on its surface.
- hydrophobic silica examples include AEROSIL R972, AEROSIL R974, AEROSIL R976, AEROSIL R104, AEROSIL R106, AEROSIL R202, AEROSIL R805, AEROSIL R812, AEROSIL R812S, AEROSIL R816, AEROSIL R7200, AEROSIL R80, Nippon Aerosil Co., Ltd.), Cyrophobic 200, Cyrophobic 704, Cyrophobic 505, and Cyrophobic 603 (manufactured by Fuji Silysia Chemical Co., Ltd.).
- Hydrophilic silica can be produced, for example, by not chemically modifying the silanol groups present on the surface of amorphous silica synthesized by a dry method or amorphous silica synthesized by a wet method.
- hydrophilic silica include AEROSIL 90, AEROSIL 130, AEROSIL 150, AEROSIL 200, AEROSIL 300, AEROSIL 380, AEROSIL OX50, AEROSIL EG50, AEROSIL TT600 (manufactured by Nippon Aerosil Co., Ltd.), Silysia 250, Silysia 350, Silicia 450, Silicia 550, Silicia 740 (manufactured by Fuji Silysia Chemical Co., Ltd.) and the like.
- the non-conductive filler is an organic phosphate
- polyphosphates, metal phosphinates, and the like are included.
- the phosphinic acid metal salt aluminum salt, sodium salt, potassium salt, magnesium salt, calcium salt and the like can be used, among which aluminum salt is preferable.
- polyphosphates melamine salts, methylamine salts, ethylamine salts, diethylamine salts, triethylamine salts, ethylenediamine salts, piperazine salts, pyridine salts, triazine salts, ammonium salts and the like can be used, with melamine salts being preferred.
- the thickness of the protective layer 20 is not particularly limited, it is preferably 1 to 100 ⁇ m, more preferably 2 to 50 ⁇ m. If the thickness of the protective layer is less than 1 ⁇ m, the protective layer is too thin and is easily damaged. If the thickness of the protective layer exceeds 100 ⁇ m, the electromagnetic wave shielding film as a whole becomes thick and difficult to handle. Also, the flexibility of the protective layer is reduced.
- the protective layer 20 preferably further contains an epoxy resin.
- the protective layer 20 contains an epoxy resin, it is possible to suppress the flow of the urethane resin contained in the protective layer when the electromagnetic wave shielding film 10 is arranged on the printed wiring board by hot pressing.
- the acid value of the epoxy resin is preferably 100-500 g/eq, more preferably 150-450 g/eq.
- the protective layer 20 may optionally contain a curing accelerator, a tackifier, an antioxidant, a pigment, a dye, a plasticizer, an ultraviolet absorber, an antifoaming agent, a leveling agent, a filler, a flame retardant, and a viscosity adjuster. agents, anti-blocking agents and the like may also be included.
- the metal layer 30 of the electromagnetic wave shielding film 10 is not particularly limited as long as it can shield electromagnetic waves, and is preferably made of at least one selected from the group consisting of a copper layer, a silver layer and an aluminum layer. These metal layers have high conductivity and can suitably shield electromagnetic waves.
- the thickness of the metal layer 30 is not particularly limited, it is preferably 0.01 to 10 ⁇ m. If the thickness of the metal layer is less than 0.01 ⁇ m, it is difficult to obtain a sufficient shielding effect. If the thickness of the metal layer exceeds 10 ⁇ m, the electromagnetic wave shielding film becomes difficult to bend.
- the metal layer 30 may have through holes.
- the electromagnetic wave shielding film 10 is hot-pressed onto the printed wiring board.
- volatile components may occur between the conductive adhesive layer 40 and the metal layer 30 . If the metal layer 30 does not have through-holes, the volatile component expands due to heat and may separate the metal layer 30 and the conductive adhesive layer 40 from each other. However, if the metal layer 30 has through-holes, volatile components can pass through the through-holes, so that the metal layer 30 and the conductive adhesive layer 40 can be prevented from peeling off.
- the conductive adhesive layer 40 contains an adhesive resin composition and metal particles.
- the conductive adhesive layer 40 further includes a flame retardant, a flame retardant aid, a curing accelerator, a tackifier, an antioxidant, a pigment, a dye, a plasticizer, an ultraviolet absorber, an antifoaming agent, and a leveling agent. , fillers, viscosity modifiers and the like.
- the material of the adhesive resin composition contained in the conductive adhesive layer 40 is not particularly limited, but may be a styrene-based resin composition, a vinyl acetate-based resin composition, a polyester-based resin composition, a polyethylene-based resin composition, or polypropylene.
- Thermoplastic resin compositions such as resin compositions, imide resin compositions, amide resin compositions, acrylic resin compositions, phenol resin compositions, epoxy resin compositions, urethane resin compositions, melamine
- a thermosetting resin composition such as an alkyd-based resin composition or an alkyd-based resin composition can be used.
- the polyester-based resin composition is preferable.
- the material of the adhesive resin composition may be one of these alone or a combination of two or more.
- metal particles contained in the conductive adhesive layer 40 include silver, copper, nickel, aluminum, and silver-coated copper obtained by plating copper with silver. Since these metal particles have excellent conductivity, they can suitably impart conductivity to the conductive adhesive layer 40 . These metal particles may be contained singly in the conductive adhesive layer 40, or may be contained in a plurality of types.
- the size of the metal particles is not particularly limited, but the average particle size is preferably 0.5 to 20 ⁇ m.
- the weight ratio of the metal particles contained in the conductive adhesive layer 40 is preferably 2-60 wt %, more preferably 10-40 wt %. If the weight ratio of the metal particles is less than 2 wt %, the shielding properties of the electromagnetic wave shielding film tend to deteriorate. If the weight ratio of the metal particles exceeds 60 wt %, the conductive adhesive layer becomes brittle and the electromagnetic wave shielding film tends to break. Moreover, when the weight ratio of the metal particles is 40 wt % or less, the conductive adhesive layer can obtain anisotropic conductivity.
- the conductive adhesive layer 40 may have isotropic conductivity or anisotropic conductivity.
- the printed wiring board on which the electromagnetic wave shielding film 10 is arranged has good high-frequency signal transmission characteristics.
- the thickness of the conductive adhesive layer 40 is not particularly limited and can be appropriately set as necessary, but is preferably 0.5 to 30.0 ⁇ m. If the thickness of the conductive adhesive layer is less than 0.5 ⁇ m, it becomes difficult to obtain good conductivity. If the thickness of the conductive adhesive layer exceeds 30.0 ⁇ m, the thickness of the entire electromagnetic wave shielding film becomes thick and difficult to handle.
- An anchor coat layer may be formed between the protective layer 20 and the metal layer 30 in the electromagnetic wave shielding film 10 .
- Materials for the anchor coat layer include urethane resin, acrylic resin, core-shell type composite resin with urethane resin as the shell and acrylic resin as the core, epoxy resin, imide resin, amide resin, melamine resin, phenol resin, and urea-formaldehyde resin. , blocked isocyanate obtained by reacting polyisocyanate with a blocking agent such as phenol, polyvinyl alcohol, polyvinylpyrrolidone, and the like.
- the electromagnetic wave shielding film 10 has the conductive adhesive layer 40, but the electromagnetic wave shielding film of the present invention may have a non-conductive adhesive layer instead of the conductive adhesive layer.
- FIG. 2A is a cross-sectional view schematically showing a printed wiring board preparation step in the method for manufacturing a shield printed wiring board using the electromagnetic wave shielding film of the present invention.
- a printed wiring board 50 comprising a base film 51, a printed circuit 52 including a ground circuit 52a disposed on the base film 51, and a coverlay 53 covering the printed circuit 52 is prepared.
- the coverlay 53 has an opening 53a that exposes the ground circuit 52a.
- FIG. 2B is a cross-sectional view schematically showing an electromagnetic shielding film placement step in the method for manufacturing a shield printed wiring board using the electromagnetic shielding film of the present invention.
- the electromagnetic shielding film 10 is arranged on the printed wiring board 50 so that the conductive adhesive layer 40 of the electromagnetic shielding film 10 is in contact with the coverlay 53 of the printed wiring board 50 .
- FIG. 2C is a cross-sectional view schematically showing a hot press step in the method for manufacturing a shield printed wiring board using the electromagnetic wave shielding film of the present invention.
- the electromagnetic wave shielding film 10 is heat-pressed onto the printed wiring board 50 by heat-pressing the printed wiring board 50 on which the electromagnetic wave shielding film 10 is arranged in the direction of the arrow.
- the protective layer 20 contains a non-conductive filler having an average particle size of 10 ⁇ m or less, and the weight ratio of the non-conductive filler to the total weight of the protective layer 20 is 10 to 40% by weight. It is possible to prevent the urethane-based resin contained in the protective layer 20 from flowing and partially thinning the protective layer. Therefore, the protective layer 20 is less likely to be partially thin. As a result, the electromagnetic wave shielding film has good moisture resistance and bending resistance.
- the conductive adhesive layer 40 fills the opening 53a, and the conductive adhesive layer 40 and the ground circuit 52a are brought into contact with each other. Therefore, the metal layer 30 and the ground circuit 52a are electrically connected, and the electromagnetic wave shielding property is improved.
- Conditions for hot pressing are not particularly limited, but include, for example, conditions of 150 to 200° C., 2 to 5 MPa, and 1 to 60 minutes.
- FIG. 2D is a cross-sectional view schematically showing an example of a shield printed wiring board manufactured using the electromagnetic wave shielding film of the present invention. Through the above steps, as shown in FIG. 2D, the shield printed wiring board 1 using the electromagnetic wave shielding film 10 can be manufactured.
- FIG. 3 is a cross-sectional view schematically showing another example of the electromagnetic wave shielding film of the present invention.
- the electromagnetic wave shielding film 110 shown in FIG. 3 is an electromagnetic wave shielding film in which a protective layer 120 and a conductive adhesive layer 140 are laminated in order.
- the conductive adhesive layer 140 has isotropic conductivity and functions as a shield layer that shields electromagnetic waves.
- the preferred aspects of the protective layer 120 are the same as those of the protective layer 120 of the electromagnetic wave shielding film 10 described above.
- Conductive adhesive layer 140 includes an adhesive resin composition and metal particles.
- the conductive adhesive layer 140 further includes a flame retardant, a flame retardant aid, a curing accelerator, a tackifier, an antioxidant, a pigment, a dye, a plasticizer, an ultraviolet absorber, an antifoaming agent, and a leveling agent. , fillers, viscosity modifiers and the like.
- the material of the adhesive resin composition contained in the conductive adhesive layer 140 is not particularly limited, but may be a styrene-based resin composition, a vinyl acetate-based resin composition, a polyester-based resin composition, a polyethylene-based resin composition, or polypropylene.
- Thermoplastic resin compositions such as resin compositions, imide resin compositions, amide resin compositions, acrylic resin compositions, phenol resin compositions, epoxy resin compositions, urethane resin compositions, melamine
- a thermosetting resin composition such as an alkyd-based resin composition or an alkyd-based resin composition can be used.
- the polyester-based resin composition is preferred.
- the material of the adhesive resin composition may be one of these alone or a combination of two or more.
- Examples of the metal particles contained in the conductive adhesive layer 140 include silver, copper, nickel, aluminum, and silver-coated copper obtained by plating copper with silver. Since these metal particles have excellent conductivity, they can suitably impart conductivity to the conductive adhesive layer 140 . These metal particles may be contained singly in the conductive adhesive layer 140, or may be contained in a plurality of types.
- the size of the metal particles is not particularly limited, but the average particle size is preferably 0.5 to 20 ⁇ m.
- the weight ratio of the metal particles contained in the conductive adhesive layer 140 is preferably 40% by weight or more, more preferably 40 to 60% by weight. When the weight ratio of the metal particles is 40% by weight or more, the conductive adhesive layer 140 can obtain isotropic conductivity.
- Example 1 Urethane resin A (manufacturer: manufactured by Toyobo Co., Ltd., weight average molecular weight: 200,000) having an acid value of 3300 g/eq and a Tg of 40°C, an epoxy resin (acid value: 170 g/eq), and silica as a non-conductive filler Particles (average particle diameter: 2 ⁇ m) were kneaded at the ratio shown in Table 1 to prepare a protective layer composition.
- the numerical value of the composition in Table 1 means the weight%.
- a transfer film a polyethylene terephthalate film having one side subjected to release treatment was prepared.
- the release-treated surface of the transfer film was coated with the protective layer composition and heated at 100° C. for 2 minutes in an electric oven to prepare a protective layer having a thickness of 5 ⁇ m.
- a copper layer of 2 ⁇ m was formed on the protective layer by electroless plating. The copper layer becomes a shield layer.
- thermoplastic polyester resin as an adhesive resin composition
- silver-coated copper powder average particle diameter: 12 ⁇ m
- a conductive filler 60 parts by weight of silver-coated copper powder (average particle diameter: 12 ⁇ m) as a conductive filler are kneaded to prepare a conductive adhesive.
- the produced conductive adhesive was applied onto the copper layer and heated at 100° C. for 2 minutes using an electric oven to produce a conductive adhesive layer with a thickness of 20 ⁇ m.
- An electromagnetic wave shielding film according to Example 1 was produced through the above steps.
- Example 2 and 3 and Comparative Example were carried out in the same manner as in Example 1, except that the urethane resin of the type shown in Table 1 was used as the urethane resin used for the protective layer, and the composition of the protective layer was changed as shown in Table 1. Electromagnetic wave shielding films according to 1 to 8 were produced.
- Table 1 shows the acid value, weight average molecular weight, and Tg of the urethane resins B to E in Examples and Comparative Examples.
- FIG. 4A and 4B are schematic diagrams showing a resistance value test method.
- a test substrate 55 was prepared in which a metal pad 52b was formed on a base film 51 and a coverlay 53 having two openings 53a for exposing the metal pad 52b was arranged. The diameter of the opening 53a was set to 1 mm.
- the electromagnetic wave shielding film 10 according to each example and each comparative example was placed on the test substrate 55 so that the conductive adhesive layer 40 was in contact with the coverlay 53 .
- a pressing machine was used to heat-press under the conditions of 170° C., 3 MPa, and 30 min, thereby fabricating the test shield substrate 2 shown in FIG. 4B.
- a resistance measuring device R is connected to the two metal pads 52b, and the electrical resistance value (the electrical resistance in the thickness direction) of the conductive adhesive layer 40 of the test shield substrate 2 immediately after manufacturing is measured. value) is shown in Table 1.
- the test shield substrate 2 was subjected to thermal shock five times under conditions of 260° C. and 1 minute, and then the electric resistance value (thickness direction) of the conductive adhesive layer 40 of the test shield substrate 2 was measured in the same manner.
- Table 1 shows the results of measuring the electrical resistance value).
- the test shield substrate 2 was left in a high-temperature and high-humidity environment of 85° C. and 85% RH for 500 hours. Table 1 shows the results of measuring the electrical resistance value in the vertical direction.
- FIG. 5 is a diagram schematically showing a flex resistance test. The bending resistance of the electromagnetic wave shielding film was evaluated by the following method.
- ⁇ Operation (i)> three copper foil patterns (copper foil thickness 12 ⁇ m, line width 8 mm) forming a circuit imitating a wiring board are formed on a base member made of a polyimide film of 25 ⁇ m, and an insulating adhesive layer is formed thereon. and a coverlay (insulating film thickness: 37.5 ⁇ m) made of a polyimide film were laminated.
- a jig was prepared by fixing two rectangular glass epoxy plates 72 with a thickness of 0.4 mm on a baking plate 71 with a thickness of 2 mm so as to be parallel to each other. Then, the laminated body 61 was held between two glass epoxy plates 72 in a jig while being bent so that the electromagnetic wave shielding film 10 was on the outside.
- FIG. 6 is a diagram schematically showing a blocking test.
- the blocking resistance of the protective layer was evaluated by the following method.
- a polyethylene terephthalate film 80 having a thickness of 50 ⁇ m, a vertical dimension of 40 mm, and a horizontal dimension of 40 mm was coated with the protective layer composition according to each example and each comparative example, and was heated at 100° C. for 2 minutes using an electric oven.
- a specimen 81 for blocking test was produced by heating and producing a protective layer having a thickness of 5 ⁇ m.
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Laminated Bodies (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Polishing Bodies And Polishing Tools (AREA)
- Surgical Instruments (AREA)
Abstract
Provided is an electromagnetic wave shield film which is less likely to cause blocking when stored in a rolled form, and which has excellent moisture resistance and bending resistance. An electromagnetic wave shield film according to the present invention in which a protective layer and a shield layer are laminated is characterized in that: the protective layer includes a urethane resin having an acid value of 2,000-4,000 g/eq and a Tg of at least 0 °C, and a non-conductive filler having an average particle diameter of at most 10 μm; and the weight percentage of the non-conductive filler to the total weight of the protective layer is 10-40 wt%.
Description
本発明は、電磁波シールドフィルムに関する。
The present invention relates to an electromagnetic wave shielding film.
モバイル機器であるスマートフォン、タブレット端末等には、内部から発生する電磁波や外部から侵入する電磁波を遮蔽するために、電磁波シールドフィルムを貼り付けた、シールド付きフレキシブルプリント配線板（以下、「シールドプリント配線板」とも記載する）が用いられている。電磁波シールドフィルムに用いるシールド層は、蒸着、スパッタ、めっき等で形成された薄膜の金属層や、導電性フィラーを高充填配合した導電性ペースト等により形成されている。今後５Ｇ等が本格的に広がるようになれば、大容量のデータを通信するために、高周波、高速伝送化が進み、電子機器のノイズ対策はさらに必要となる。
Mobile devices such as smartphones and tablet terminals are equipped with shielded flexible printed wiring boards (hereafter referred to as "shield printed wiring (also referred to as "plate") is used. The shield layer used in the electromagnetic wave shield film is formed of a thin metal layer formed by vapor deposition, sputtering, plating, or the like, or a conductive paste containing a high content of conductive filler. In the future, when 5G, etc., will spread in earnest, high frequency and high speed transmission will advance in order to communicate large amounts of data, and noise countermeasures for electronic devices will become even more necessary.
一般的に、電磁波シールドフィルムは、電磁波を遮蔽する本体となるシールド層と、当該シールド層を外部からの衝撃や、薬品、溶剤、水等から保護するための保護層（絶縁層）とからなる。
In general, an electromagnetic wave shield film consists of a shield layer that serves as a main body that shields electromagnetic waves, and a protective layer (insulating layer) that protects the shield layer from external impacts, chemicals, solvents, water, etc. .
フレキシブルプリント配線板に配置される電磁波シールドフィルムには柔軟性が求められており、その構成要素である保護層にも柔軟性が求められている。
Flexibility is required for the electromagnetic shielding film placed on the flexible printed wiring board, and flexibility is also required for the protective layer that is a component thereof.
このようなフレキシブルプリント配線板に配置される電磁波シールドフィルムとして、特許文献１には、凹凸を有する導電性のシールド層と、前記凹凸を被覆する接着剤層とを備え、前記凹凸の最大山高さの値は、前記接着剤層の厚さよりも大きい、電磁波シールドフィルムが開示されている。
As an electromagnetic wave shielding film arranged on such a flexible printed wiring board, Patent Document 1 discloses a conductive shield layer having unevenness and an adhesive layer covering the unevenness, and the maximum peak height of the unevenness is is greater than the thickness of the adhesive layer.
また、特許文献２には、シールド層と、上記シールド層に積層された絶縁層とを備える電磁波シールドフィルムであって、上記絶縁層は、シリカ微粒子を含み、上記絶縁層中の前記シリカ微粒子の含有量は、１０～５０ｗｔ％であることを特徴とする電磁波シールドフィルムが開示されている。
Further, Patent Document 2 discloses an electromagnetic wave shielding film comprising a shield layer and an insulating layer laminated on the shield layer, wherein the insulating layer contains silica fine particles, and the silica fine particles in the insulating layer An electromagnetic wave shielding film is disclosed in which the content is 10 to 50 wt%.
また、特許文献３には、このような電磁波シールドフィルムに用いられる保護層用の樹脂組成物として、非晶性ポリエステル樹脂と、硬化剤と、白色顔料とを含み、上記非晶性ポリエステル樹脂は、数平均分子量Ｍｎが２０，０００未満であり、ガラス転移点Ｔｇが、４０℃以上であり、上記硬化剤は、ブロックイソシアネート、ヘキサンジイソシアネートのトリメチロールプロパンアダクト体及びシクロヘキサンジイソシアネートのイソシアヌレートアダクト体からなる群から選択される少なくとも１種であることを特徴とする樹脂組成物が開示されている。
Further, in Patent Document 3, a resin composition for a protective layer used in such an electromagnetic wave shielding film contains an amorphous polyester resin, a curing agent, and a white pigment, and the amorphous polyester resin is , The number average molecular weight Mn is less than 20,000, the glass transition point Tg is 40 ° C. or higher, and the curing agent is a blocked isocyanate, a trimethylolpropane adduct of hexane diisocyanate, and an isocyanurate adduct of cyclohexane diisocyanate A resin composition is disclosed which is at least one selected from the group consisting of:
一般的に、柔軟性が高い保護層はガラス転移点と架橋密度が低い。保護層のガラス転移点が低いと、電磁波シールドフィルムをロール保管する際にブロッキングが発生しやすくなるという問題がある。また、保護層を構成する樹脂の架橋密度が低いと、電磁波シールドフィルムを、プリント配線板におけるグランド回路を露出するために設けられた開口部等の段差箇所（以下、単に「プリント配線板における段差箇所」とも記載する）に熱プレスにより配置する際に、保護層に部分的に薄い箇所が生じやすくなり、保護層の物理的強度が低下したり、湿気が保護層を透過しやすくなる。その結果、電磁波シールドフィルムの耐熱性、耐湿性が低下しやすくなるという問題がある。
In general, a highly flexible protective layer has a low glass transition point and a low crosslink density. If the glass transition point of the protective layer is low, there is a problem that blocking is likely to occur when the electromagnetic wave shielding film is stored in a roll. In addition, if the cross-linking density of the resin constituting the protective layer is low, the electromagnetic wave shielding film will not be exposed to the steps such as openings provided to expose the ground circuit on the printed wiring board (hereinafter simply referred to as “steps on the printed wiring board”). ), the protective layer tends to have partially thin spots, the physical strength of the protective layer decreases, and moisture easily permeates the protective layer. As a result, there is a problem that the heat resistance and moisture resistance of the electromagnetic wave shielding film tend to deteriorate.
本発明は、上記問題点を解決するためになされた発明であり、本発明の目的は、ロール保管時にブロッキングが生じにくく、耐湿性及び耐屈曲性に優れる電磁波シールドフィルムを提供することである。
The present invention is an invention made to solve the above problems, and an object of the present invention is to provide an electromagnetic wave shielding film that is less likely to cause blocking during roll storage and has excellent moisture resistance and bending resistance.
本発明の電磁波シールドフィルムは、保護層と、シールド層とが積層された電磁波シールドフィルムであって、上記保護層は、酸価が２０００～４０００ｇ／ｅｑ、かつ、Ｔｇが０℃以上であるウレタン系樹脂と、平均粒径が１０μｍ以下である非導電性フィラーとを含み、上記保護層の全体重量に対する上記非導電性フィラーの重量割合は、１０～４０重量％であることを特徴とする。
The electromagnetic shielding film of the present invention is an electromagnetic shielding film in which a protective layer and a shielding layer are laminated, and the protective layer is a urethane having an acid value of 2000 to 4000 g/eq and a Tg of 0° C. or higher. and a non-conductive filler having an average particle size of 10 μm or less, wherein the weight ratio of the non-conductive filler to the total weight of the protective layer is 10 to 40% by weight.
本発明の電磁波シールドフィルムでは、保護層に含まれるウレタン系樹脂は、酸価が２０００～４０００ｇ／ｅｑである。
酸価が上記範囲であると、架橋密度が適度な範囲になるので、電磁波シールドフィルムをプリント配線板における段差箇所に熱プレスにより配置する際に、保護層に部分的に薄い箇所が生じにくくなる。そのため、保護層の物理的強度が低下したり、湿気が保護層を透過しにくくなる。その結果、電磁波シールドフィルムの耐屈曲性及び耐湿性が良好になる。
酸価が２０００ｇ／ｅｑ未満であると、架橋密度が高くなり保護層が硬くなる。その結果、保護層の靭性が低下し、耐屈曲性が低下しやすくなる。
酸価が４０００ｇ／ｅｑを超えると、架橋密度が低くなり、電磁波シールドフィルムをプリント配線板における段差箇所に熱プレスにより配置する際に、保護層に部分的に薄い箇所が生じやすくなる。その結果、耐湿性が極端に低下しやすくなる。 In the electromagnetic wave shielding film of the present invention, the urethane resin contained in the protective layer has an acid value of 2000 to 4000 g/eq.
When the acid value is within the above range, the cross-linking density is within a suitable range, so that when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing, the protective layer is less likely to have partially thin portions. . As a result, the physical strength of the protective layer is reduced, and moisture does not easily permeate the protective layer. As a result, the flex resistance and moisture resistance of the electromagnetic wave shielding film are improved.
If the acid value is less than 2000 g/eq, the crosslink density becomes high and the protective layer becomes hard. As a result, the toughness of the protective layer is lowered, and the bending resistance tends to be lowered.
If the acid value exceeds 4000 g/eq, the cross-linking density becomes low, and when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing, the protective layer tends to be partially thinned. As a result, the moisture resistance tends to be extremely lowered.
酸価が上記範囲であると、架橋密度が適度な範囲になるので、電磁波シールドフィルムをプリント配線板における段差箇所に熱プレスにより配置する際に、保護層に部分的に薄い箇所が生じにくくなる。そのため、保護層の物理的強度が低下したり、湿気が保護層を透過しにくくなる。その結果、電磁波シールドフィルムの耐屈曲性及び耐湿性が良好になる。
酸価が２０００ｇ／ｅｑ未満であると、架橋密度が高くなり保護層が硬くなる。その結果、保護層の靭性が低下し、耐屈曲性が低下しやすくなる。
酸価が４０００ｇ／ｅｑを超えると、架橋密度が低くなり、電磁波シールドフィルムをプリント配線板における段差箇所に熱プレスにより配置する際に、保護層に部分的に薄い箇所が生じやすくなる。その結果、耐湿性が極端に低下しやすくなる。 In the electromagnetic wave shielding film of the present invention, the urethane resin contained in the protective layer has an acid value of 2000 to 4000 g/eq.
When the acid value is within the above range, the cross-linking density is within a suitable range, so that when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing, the protective layer is less likely to have partially thin portions. . As a result, the physical strength of the protective layer is reduced, and moisture does not easily permeate the protective layer. As a result, the flex resistance and moisture resistance of the electromagnetic wave shielding film are improved.
If the acid value is less than 2000 g/eq, the crosslink density becomes high and the protective layer becomes hard. As a result, the toughness of the protective layer is lowered, and the bending resistance tends to be lowered.
If the acid value exceeds 4000 g/eq, the cross-linking density becomes low, and when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing, the protective layer tends to be partially thinned. As a result, the moisture resistance tends to be extremely lowered.
本発明の電磁波シールドフィルムでは、保護層に含まれるウレタン系樹脂は、Ｔｇが０℃以上である。
そのため、本発明の電磁波シールドフィルムをロール保管した際に、ブロッキングが生じにくくなる。 In the electromagnetic wave shielding film of the present invention, the urethane-based resin contained in the protective layer has a Tg of 0° C. or higher.
Therefore, when the electromagnetic wave shielding film of the present invention is stored in a roll, blocking is less likely to occur.
そのため、本発明の電磁波シールドフィルムをロール保管した際に、ブロッキングが生じにくくなる。 In the electromagnetic wave shielding film of the present invention, the urethane-based resin contained in the protective layer has a Tg of 0° C. or higher.
Therefore, when the electromagnetic wave shielding film of the present invention is stored in a roll, blocking is less likely to occur.
本発明の電磁波シールドフィルムでは、保護層が、平均粒径が１０μｍ以下である非導電性フィラーを含み、保護層の全体重量に対する非導電性フィラーの重量割合が、１０～４０重量％である。
保護層が上記重量割合の平均粒径が１０μｍ以下である非導電性フィラーを含むと、電磁波シールドフィルムをプリント配線板における段差箇所に熱プレスにより配置する際に、保護層に含まれるウレタン系樹脂が流動して保護層の一部が薄くなることを防ぐことができる。その結果、電磁波シールドフィルムの耐湿性及び耐屈曲性が良好になる。
非導電性フィラーの重量割合が１０重量％未満であると、非導電性フィラーを含む場合の効果が得られにくくなり、耐湿性が低下しやすくなる。
非導電性フィラーの重量割合が４０重量％を超えると、保護層が硬くなり柔軟性が低下しやすくなる。その結果、耐屈曲性が低下しやすくなる。 In the electromagnetic wave shielding film of the present invention, the protective layer contains a non-conductive filler having an average particle size of 10 μm or less, and the weight ratio of the non-conductive filler to the total weight of the protective layer is 10 to 40% by weight.
If the protective layer contains a non-conductive filler having an average particle diameter of 10 μm or less in the above weight ratio, the urethane resin contained in the protective layer is used when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing. can be prevented from flowing and part of the protective layer becoming thin. As a result, the electromagnetic wave shielding film has good moisture resistance and bending resistance.
If the weight ratio of the non-conductive filler is less than 10% by weight, it becomes difficult to obtain the effect of containing the non-conductive filler, and moisture resistance tends to decrease.
If the weight ratio of the non-conductive filler exceeds 40% by weight, the protective layer becomes hard and the flexibility tends to decrease. As a result, the bending resistance tends to decrease.
保護層が上記重量割合の平均粒径が１０μｍ以下である非導電性フィラーを含むと、電磁波シールドフィルムをプリント配線板における段差箇所に熱プレスにより配置する際に、保護層に含まれるウレタン系樹脂が流動して保護層の一部が薄くなることを防ぐことができる。その結果、電磁波シールドフィルムの耐湿性及び耐屈曲性が良好になる。
非導電性フィラーの重量割合が１０重量％未満であると、非導電性フィラーを含む場合の効果が得られにくくなり、耐湿性が低下しやすくなる。
非導電性フィラーの重量割合が４０重量％を超えると、保護層が硬くなり柔軟性が低下しやすくなる。その結果、耐屈曲性が低下しやすくなる。 In the electromagnetic wave shielding film of the present invention, the protective layer contains a non-conductive filler having an average particle size of 10 μm or less, and the weight ratio of the non-conductive filler to the total weight of the protective layer is 10 to 40% by weight.
If the protective layer contains a non-conductive filler having an average particle diameter of 10 μm or less in the above weight ratio, the urethane resin contained in the protective layer is used when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing. can be prevented from flowing and part of the protective layer becoming thin. As a result, the electromagnetic wave shielding film has good moisture resistance and bending resistance.
If the weight ratio of the non-conductive filler is less than 10% by weight, it becomes difficult to obtain the effect of containing the non-conductive filler, and moisture resistance tends to decrease.
If the weight ratio of the non-conductive filler exceeds 40% by weight, the protective layer becomes hard and the flexibility tends to decrease. As a result, the bending resistance tends to decrease.
本発明の電磁波シールドフィルムでは、上記保護層が、さらにエポキシ系樹脂を含むことが好ましい。
保護層がエポキシ系樹脂を含むと、電磁波シールドフィルムをプリント配線板に熱プレスにより配置する際に、保護層に含まれるウレタン系樹脂が流動することを抑制することができる。 In the electromagnetic wave shielding film of the present invention, the protective layer preferably further contains an epoxy resin.
When the protective layer contains an epoxy resin, it is possible to suppress the flow of the urethane resin contained in the protective layer when the electromagnetic wave shielding film is arranged on the printed wiring board by hot pressing.
保護層がエポキシ系樹脂を含むと、電磁波シールドフィルムをプリント配線板に熱プレスにより配置する際に、保護層に含まれるウレタン系樹脂が流動することを抑制することができる。 In the electromagnetic wave shielding film of the present invention, the protective layer preferably further contains an epoxy resin.
When the protective layer contains an epoxy resin, it is possible to suppress the flow of the urethane resin contained in the protective layer when the electromagnetic wave shielding film is arranged on the printed wiring board by hot pressing.
本発明の電磁波シールドフィルムでは、上記ウレタン系樹脂と、上記エポキシ系樹脂との重量比が、ウレタン系樹脂／エポキシ系樹脂＝４～４９であることが好ましい。
上記重量比が４未満であると、エポキシ系樹脂が多くなりすぎ、保護層が硬くなりやすくなる。その結果、保護層の柔軟性が低下し、耐屈曲性が低下する。
上記重量比が４９を超えると、エポキシ系樹脂が少なくなり、保護層が柔らかくなり、エポキシ系樹脂を含む効果を得られにくくなる。 In the electromagnetic wave shielding film of the present invention, it is preferable that the weight ratio of the urethane-based resin and the epoxy-based resin is urethane-based resin/epoxy-based resin=4 to 49.
If the weight ratio is less than 4, the amount of the epoxy resin is too large, and the protective layer tends to be hard. As a result, the flexibility of the protective layer is lowered and the bending resistance is lowered.
If the weight ratio exceeds 49, the amount of the epoxy resin decreases, the protective layer becomes soft, and it becomes difficult to obtain the effect of including the epoxy resin.
上記重量比が４未満であると、エポキシ系樹脂が多くなりすぎ、保護層が硬くなりやすくなる。その結果、保護層の柔軟性が低下し、耐屈曲性が低下する。
上記重量比が４９を超えると、エポキシ系樹脂が少なくなり、保護層が柔らかくなり、エポキシ系樹脂を含む効果を得られにくくなる。 In the electromagnetic wave shielding film of the present invention, it is preferable that the weight ratio of the urethane-based resin and the epoxy-based resin is urethane-based resin/epoxy-based resin=4 to 49.
If the weight ratio is less than 4, the amount of the epoxy resin is too large, and the protective layer tends to be hard. As a result, the flexibility of the protective layer is lowered and the bending resistance is lowered.
If the weight ratio exceeds 49, the amount of the epoxy resin decreases, the protective layer becomes soft, and it becomes difficult to obtain the effect of including the epoxy resin.
本発明の電磁波シールドフィルムでは、上記ウレタン系樹脂のＴｇが、０～６０℃であることが好ましい。
ウレタン系樹脂のＴｇが、０～６０℃であると、本発明の電磁波シールドフィルムをプリント配線板に熱プレスする際に保護層が適度な流動性を有するため、保護層の一部が薄くなって電磁波シールドフィルムの耐湿性及び耐屈曲性が低下することを防ぐことができる。 In the electromagnetic wave shielding film of the present invention, the urethane-based resin preferably has a Tg of 0 to 60°C.
When the Tg of the urethane-based resin is 0 to 60° C., the protective layer has appropriate fluidity when the electromagnetic wave shielding film of the present invention is hot-pressed onto a printed wiring board, so that part of the protective layer becomes thin. It is possible to prevent the moisture resistance and bending resistance of the electromagnetic wave shielding film from deteriorating.
ウレタン系樹脂のＴｇが、０～６０℃であると、本発明の電磁波シールドフィルムをプリント配線板に熱プレスする際に保護層が適度な流動性を有するため、保護層の一部が薄くなって電磁波シールドフィルムの耐湿性及び耐屈曲性が低下することを防ぐことができる。 In the electromagnetic wave shielding film of the present invention, the urethane-based resin preferably has a Tg of 0 to 60°C.
When the Tg of the urethane-based resin is 0 to 60° C., the protective layer has appropriate fluidity when the electromagnetic wave shielding film of the present invention is hot-pressed onto a printed wiring board, so that part of the protective layer becomes thin. It is possible to prevent the moisture resistance and bending resistance of the electromagnetic wave shielding film from deteriorating.
本発明の電磁波シールドフィルムでは、上記ウレタン系樹脂の重量平均分子量は、１００，０００～２，０００，０００であることが好ましく、１７０，０００～５００，０００であることがより好ましい。
ウレタン系樹脂の重量平均分子量は上記範囲であると、ウレタン系樹脂が適度な硬さ及び流動性になるので、電磁波シールドフィルムの耐熱性、耐湿性及び耐屈曲性を向上させることができる。 In the electromagnetic wave shielding film of the present invention, the urethane resin preferably has a weight average molecular weight of 100,000 to 2,000,000, more preferably 170,000 to 500,000.
When the weight-average molecular weight of the urethane-based resin is within the above range, the urethane-based resin has appropriate hardness and fluidity, so that the electromagnetic wave shielding film can be improved in heat resistance, moisture resistance, and bending resistance.
ウレタン系樹脂の重量平均分子量は上記範囲であると、ウレタン系樹脂が適度な硬さ及び流動性になるので、電磁波シールドフィルムの耐熱性、耐湿性及び耐屈曲性を向上させることができる。 In the electromagnetic wave shielding film of the present invention, the urethane resin preferably has a weight average molecular weight of 100,000 to 2,000,000, more preferably 170,000 to 500,000.
When the weight-average molecular weight of the urethane-based resin is within the above range, the urethane-based resin has appropriate hardness and fluidity, so that the electromagnetic wave shielding film can be improved in heat resistance, moisture resistance, and bending resistance.
本発明の電磁波シールドフィルムでは、上記非導電性フィラーは、シリカ及び有機リン酸塩からなる群から選択される少なくとも１種であることが好ましい。
これらの材料からなる非導電性フィラーは、電磁波シールドフィルムの耐湿性及び耐屈曲性を好適に向上させることができる。 In the electromagnetic wave shielding film of the present invention, the non-conductive filler is preferably at least one selected from the group consisting of silica and organic phosphates.
Non-conductive fillers made of these materials can favorably improve the moisture resistance and bending resistance of the electromagnetic wave shielding film.
これらの材料からなる非導電性フィラーは、電磁波シールドフィルムの耐湿性及び耐屈曲性を好適に向上させることができる。 In the electromagnetic wave shielding film of the present invention, the non-conductive filler is preferably at least one selected from the group consisting of silica and organic phosphates.
Non-conductive fillers made of these materials can favorably improve the moisture resistance and bending resistance of the electromagnetic wave shielding film.
本発明の電磁波シールドフィルムでは、上記シールド層は、導電性接着剤層であってもよい。
また、本発明の電磁波シールドフィルムでは、上記シールド層は、金属層であり、上記シールド層の上記保護層が積層されていない側の面には、さらに接着剤層が積層されていてもよい。
本発明の電磁波シールドフィルムは、いずれの態様であっても好適に電磁波を遮蔽することができる。また、電磁波シールドフィルムのロール保管時にブロッキングが生じにくく、電磁波シールドフィルムの耐熱性、耐湿性及び耐屈曲性が充分に高くなる。 In the electromagnetic wave shielding film of the present invention, the shield layer may be a conductive adhesive layer.
In the electromagnetic wave shielding film of the present invention, the shield layer may be a metal layer, and an adhesive layer may be further laminated on the side of the shield layer on which the protective layer is not laminated.
The electromagnetic wave shielding film of the present invention can suitably shield electromagnetic waves in any aspect. In addition, blocking hardly occurs when the electromagnetic wave shielding film is stored in a roll, and the heat resistance, moisture resistance, and bending resistance of the electromagnetic wave shielding film are sufficiently increased.
また、本発明の電磁波シールドフィルムでは、上記シールド層は、金属層であり、上記シールド層の上記保護層が積層されていない側の面には、さらに接着剤層が積層されていてもよい。
本発明の電磁波シールドフィルムは、いずれの態様であっても好適に電磁波を遮蔽することができる。また、電磁波シールドフィルムのロール保管時にブロッキングが生じにくく、電磁波シールドフィルムの耐熱性、耐湿性及び耐屈曲性が充分に高くなる。 In the electromagnetic wave shielding film of the present invention, the shield layer may be a conductive adhesive layer.
In the electromagnetic wave shielding film of the present invention, the shield layer may be a metal layer, and an adhesive layer may be further laminated on the side of the shield layer on which the protective layer is not laminated.
The electromagnetic wave shielding film of the present invention can suitably shield electromagnetic waves in any aspect. In addition, blocking hardly occurs when the electromagnetic wave shielding film is stored in a roll, and the heat resistance, moisture resistance, and bending resistance of the electromagnetic wave shielding film are sufficiently increased.
本発明の電磁波シールドフィルムでは、保護層が、酸価が２０００～４０００ｇ／ｅｑ、かつ、Ｔｇが０℃以上であるウレタン系樹脂と、平均粒径が１０μｍ以下である非導電性フィラーとを含み、保護層の全体重量に対する非導電性フィラーの重量割合が、１０～４０重量％である。
そのため、ウレタン系樹脂の架橋密度が適度な範囲となり、電磁波シールドフィルムの耐屈曲性及び耐湿性が良好になる。また、ウレタン系樹脂のＴｇが０℃以上であるので、電磁波シールドフィルムをロール保管した際に、ブロッキングが生じにくくなる。また、保護層に所定の非導電性フィラーが含まれることにより、電磁波シールドフィルムをプリント配線板に熱プレスにより配置する際に、保護層に含まれるウレタン系樹脂が流動して保護層の一部が薄くなることを防ぐことができる。そのため、保護層の部分的に薄い箇所が生じにくくなる。その結果、電磁波シールドフィルムの耐湿性及び耐屈曲性が良好になる。 In the electromagnetic wave shielding film of the present invention, the protective layer contains a urethane resin having an acid value of 2000 to 4000 g/eq and a Tg of 0° C. or higher, and a non-conductive filler having an average particle size of 10 μm or less. , the weight ratio of the non-conductive filler to the total weight of the protective layer is 10 to 40% by weight.
Therefore, the cross-linking density of the urethane-based resin is in an appropriate range, and the flex resistance and moisture resistance of the electromagnetic wave shielding film are improved. In addition, since the Tg of the urethane-based resin is 0° C. or higher, blocking hardly occurs when the electromagnetic wave shielding film is stored in a roll. In addition, since the protective layer contains a predetermined non-conductive filler, when the electromagnetic wave shielding film is placed on the printed wiring board by heat pressing, the urethane resin contained in the protective layer flows and part of the protective layer thinning can be prevented. Therefore, the protective layer is less likely to have partially thin portions. As a result, the electromagnetic wave shielding film has good moisture resistance and bending resistance.
そのため、ウレタン系樹脂の架橋密度が適度な範囲となり、電磁波シールドフィルムの耐屈曲性及び耐湿性が良好になる。また、ウレタン系樹脂のＴｇが０℃以上であるので、電磁波シールドフィルムをロール保管した際に、ブロッキングが生じにくくなる。また、保護層に所定の非導電性フィラーが含まれることにより、電磁波シールドフィルムをプリント配線板に熱プレスにより配置する際に、保護層に含まれるウレタン系樹脂が流動して保護層の一部が薄くなることを防ぐことができる。そのため、保護層の部分的に薄い箇所が生じにくくなる。その結果、電磁波シールドフィルムの耐湿性及び耐屈曲性が良好になる。 In the electromagnetic wave shielding film of the present invention, the protective layer contains a urethane resin having an acid value of 2000 to 4000 g/eq and a Tg of 0° C. or higher, and a non-conductive filler having an average particle size of 10 μm or less. , the weight ratio of the non-conductive filler to the total weight of the protective layer is 10 to 40% by weight.
Therefore, the cross-linking density of the urethane-based resin is in an appropriate range, and the flex resistance and moisture resistance of the electromagnetic wave shielding film are improved. In addition, since the Tg of the urethane-based resin is 0° C. or higher, blocking hardly occurs when the electromagnetic wave shielding film is stored in a roll. In addition, since the protective layer contains a predetermined non-conductive filler, when the electromagnetic wave shielding film is placed on the printed wiring board by heat pressing, the urethane resin contained in the protective layer flows and part of the protective layer thinning can be prevented. Therefore, the protective layer is less likely to have partially thin portions. As a result, the electromagnetic wave shielding film has good moisture resistance and bending resistance.
以下、本発明の電磁波シールドフィルムについて具体的に説明する。しかしながら、本発明は、以下の実施形態に限定されるものではなく、本発明の要旨を変更しない範囲において適宜変更して適用することができる。
The electromagnetic wave shielding film of the present invention will be specifically described below. However, the present invention is not limited to the following embodiments, and can be appropriately modified and applied without changing the gist of the present invention.
図１は、本発明の電磁波シールドフィルムの一例を模式的に示す断面図である。
図１に示す電磁波シールドフィルム１０は、保護層２０と、金属層３０と、導電性接着剤層４０とが順に積層された電磁波シールドフィルムである。
電磁波シールドフィルム１０において、金属層３０は電磁波を遮蔽するシールド層として機能する。
各構成について以下に説明する。 FIG. 1 is a cross-sectional view schematically showing an example of the electromagnetic wave shielding film of the present invention.
The electromagneticwave shielding film 10 shown in FIG. 1 is an electromagnetic wave shielding film in which a protective layer 20, a metal layer 30, and a conductive adhesive layer 40 are laminated in order.
In the electromagneticwave shielding film 10, the metal layer 30 functions as a shield layer for shielding electromagnetic waves.
Each configuration will be described below.
図１に示す電磁波シールドフィルム１０は、保護層２０と、金属層３０と、導電性接着剤層４０とが順に積層された電磁波シールドフィルムである。
電磁波シールドフィルム１０において、金属層３０は電磁波を遮蔽するシールド層として機能する。
各構成について以下に説明する。 FIG. 1 is a cross-sectional view schematically showing an example of the electromagnetic wave shielding film of the present invention.
The electromagnetic
In the electromagnetic
Each configuration will be described below.
（保護層）
電磁波シールドフィルム１０において、保護層２０は、ウレタン系樹脂及び非導電性フィラーを含む。 (protective layer)
In the electromagneticwave shielding film 10, the protective layer 20 contains urethane-based resin and non-conductive filler.
電磁波シールドフィルム１０において、保護層２０は、ウレタン系樹脂及び非導電性フィラーを含む。 (protective layer)
In the electromagnetic
保護層２０に含まれるウレタン系樹脂は、酸価が２０００～４０００ｇ／ｅｑである。酸価は、２１００～３９００ｇ／ｅｑであることが好ましく、２５００～３５００ｇ／ｅｑであることがより好ましい。
酸価が上記範囲であると、架橋密度が適度な範囲になるので、電磁波シールドフィルムをプリント配線板における段差箇所に熱プレスにより配置する際に、保護層に部分的に薄い箇所が生じにくくなる。そのため、保護層の物理的強度が低下したり、湿気が保護層を透過しにくくなる。その結果、電磁波シールドフィルムの耐屈曲性及び耐湿性が良好になる。
酸価が２０００ｇ／ｅｑ未満であると、架橋密度が高くなり、保護層が硬くなる。その結果、保護層の靭性が低下し、耐屈曲性が低下しやすくなる。
酸価が４０００ｇ／ｅｑを超えると、架橋密度が低くなり、電磁波シールドフィルムをプリント配線板における段差箇所に熱プレスにより配置する際に、保護層に部分的に薄い箇所が生じやすくなる。その結果、耐湿性が極端に低下しやすくなる。 The urethane-based resin contained in theprotective layer 20 has an acid value of 2000 to 4000 g/eq. The acid value is preferably 2100-3900 g/eq, more preferably 2500-3500 g/eq.
When the acid value is within the above range, the cross-linking density is within a suitable range, so that when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing, the protective layer is less likely to have partially thin portions. . As a result, the physical strength of the protective layer is reduced, and moisture does not easily permeate the protective layer. As a result, the flex resistance and moisture resistance of the electromagnetic wave shielding film are improved.
If the acid value is less than 2000 g/eq, the crosslink density becomes high and the protective layer becomes hard. As a result, the toughness of the protective layer is lowered, and the bending resistance tends to be lowered.
If the acid value exceeds 4000 g/eq, the cross-linking density becomes low, and when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing, the protective layer tends to be partially thinned. As a result, the moisture resistance tends to be extremely lowered.
酸価が上記範囲であると、架橋密度が適度な範囲になるので、電磁波シールドフィルムをプリント配線板における段差箇所に熱プレスにより配置する際に、保護層に部分的に薄い箇所が生じにくくなる。そのため、保護層の物理的強度が低下したり、湿気が保護層を透過しにくくなる。その結果、電磁波シールドフィルムの耐屈曲性及び耐湿性が良好になる。
酸価が２０００ｇ／ｅｑ未満であると、架橋密度が高くなり、保護層が硬くなる。その結果、保護層の靭性が低下し、耐屈曲性が低下しやすくなる。
酸価が４０００ｇ／ｅｑを超えると、架橋密度が低くなり、電磁波シールドフィルムをプリント配線板における段差箇所に熱プレスにより配置する際に、保護層に部分的に薄い箇所が生じやすくなる。その結果、耐湿性が極端に低下しやすくなる。 The urethane-based resin contained in the
When the acid value is within the above range, the cross-linking density is within a suitable range, so that when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing, the protective layer is less likely to have partially thin portions. . As a result, the physical strength of the protective layer is reduced, and moisture does not easily permeate the protective layer. As a result, the flex resistance and moisture resistance of the electromagnetic wave shielding film are improved.
If the acid value is less than 2000 g/eq, the crosslink density becomes high and the protective layer becomes hard. As a result, the toughness of the protective layer is lowered, and the bending resistance tends to be lowered.
If the acid value exceeds 4000 g/eq, the cross-linking density becomes low, and when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing, the protective layer tends to be partially thinned. As a result, the moisture resistance tends to be extremely lowered.
保護層２０に含まれるウレタン系樹脂は、Ｔｇが０℃以上である。Ｔｇは、０～６０℃であることが好ましく、３０～６０℃であることがより好ましい。
ウレタン系樹脂のＴｇが０℃以上であると、電磁波シールドフィルム１０をロール保管した際に、ブロッキングが生じにくくなる。
また、ウレタン系樹脂のＴｇが０～６０℃であると、本発明の電磁波シールドフィルムをプリント配線板に熱プレスする際に保護層が適度な流動性となる。
また、本発明の電磁波シールドフィルムを作製する場合、転写フィルムに保護層を形成する場合がある。この際、保護層と転写フィルムの密着性が向上する。
なお、ウレタン系樹脂のＴｇは、ＪＩＳ Ｋ７１２１における示差走査熱量測定（ＤＳＣ）に準拠して測定した値を意味する。 The urethane-based resin contained in theprotective layer 20 has a Tg of 0° C. or higher. Tg is preferably 0 to 60°C, more preferably 30 to 60°C.
When the Tg of the urethane-based resin is 0° C. or higher, blocking is less likely to occur when the electromagneticwave shielding film 10 is stored in a roll.
Further, when the Tg of the urethane-based resin is 0 to 60° C., the protective layer has appropriate fluidity when the electromagnetic wave shielding film of the present invention is hot-pressed onto a printed wiring board.
Moreover, when producing the electromagnetic wave shielding film of this invention, a protective layer may be formed in a transfer film. At this time, the adhesion between the protective layer and the transfer film is improved.
The Tg of the urethane-based resin means a value measured according to differential scanning calorimetry (DSC) in JIS K7121.
ウレタン系樹脂のＴｇが０℃以上であると、電磁波シールドフィルム１０をロール保管した際に、ブロッキングが生じにくくなる。
また、ウレタン系樹脂のＴｇが０～６０℃であると、本発明の電磁波シールドフィルムをプリント配線板に熱プレスする際に保護層が適度な流動性となる。
また、本発明の電磁波シールドフィルムを作製する場合、転写フィルムに保護層を形成する場合がある。この際、保護層と転写フィルムの密着性が向上する。
なお、ウレタン系樹脂のＴｇは、ＪＩＳ Ｋ７１２１における示差走査熱量測定（ＤＳＣ）に準拠して測定した値を意味する。 The urethane-based resin contained in the
When the Tg of the urethane-based resin is 0° C. or higher, blocking is less likely to occur when the electromagnetic
Further, when the Tg of the urethane-based resin is 0 to 60° C., the protective layer has appropriate fluidity when the electromagnetic wave shielding film of the present invention is hot-pressed onto a printed wiring board.
Moreover, when producing the electromagnetic wave shielding film of this invention, a protective layer may be formed in a transfer film. At this time, the adhesion between the protective layer and the transfer film is improved.
The Tg of the urethane-based resin means a value measured according to differential scanning calorimetry (DSC) in JIS K7121.
ウレタン系樹脂の重量平均分子量は、１００，０００～２，０００，０００であることが好ましく、１７０，０００～５００，０００であることがより好ましい。
ウレタン系樹脂の重量平均分子量は上記範囲であると、ウレタン系樹脂が適度な硬さ及び流動性になるので、保護層の耐熱性、耐湿性及び耐屈曲性を向上させることができる。
なお、ウレタン系樹脂の重量平均分子量は、以下の条件のゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定することができる。
測定器：Ａｌｌｉａｎｃｅ ＧＰＣ Ｓｙｓｔｅｍ（Ｗａｔｅｒｓ製）
カラム：Ｓｈｏｄｅｘ ＧＰＣ ＫＦ－８０６Ｌ（昭和電工）
カラム温度：４０℃
試料濃度：０．０５ｗｔ％／ＴＨＦ
注入量：１０μＬ
標準試料：東ソー：標準ＰＳ ５００、Ｓｈｏｄｅｘ標準ＰＳ ＳＭ－１０５（セット） The weight average molecular weight of the urethane resin is preferably 100,000 to 2,000,000, more preferably 170,000 to 500,000.
When the weight-average molecular weight of the urethane-based resin is within the above range, the urethane-based resin has appropriate hardness and fluidity, so that the heat resistance, moisture resistance, and flex resistance of the protective layer can be improved.
In addition, the weight average molecular weight of the urethane-based resin can be measured by gel permeation chromatography (GPC) under the following conditions.
Measuring instrument: Alliance GPC System (manufactured by Waters)
Column: Shodex GPC KF-806L (Showa Denko)
Column temperature: 40°C
Sample concentration: 0.05 wt%/THF
Injection volume: 10 μL
Standard sample: Tosoh: standard PS 500, Shodex standard PS SM-105 (set)
ウレタン系樹脂の重量平均分子量は上記範囲であると、ウレタン系樹脂が適度な硬さ及び流動性になるので、保護層の耐熱性、耐湿性及び耐屈曲性を向上させることができる。
なお、ウレタン系樹脂の重量平均分子量は、以下の条件のゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定することができる。
測定器：Ａｌｌｉａｎｃｅ ＧＰＣ Ｓｙｓｔｅｍ（Ｗａｔｅｒｓ製）
カラム：Ｓｈｏｄｅｘ ＧＰＣ ＫＦ－８０６Ｌ（昭和電工）
カラム温度：４０℃
試料濃度：０．０５ｗｔ％／ＴＨＦ
注入量：１０μＬ
標準試料：東ソー：標準ＰＳ ５００、Ｓｈｏｄｅｘ標準ＰＳ ＳＭ－１０５（セット） The weight average molecular weight of the urethane resin is preferably 100,000 to 2,000,000, more preferably 170,000 to 500,000.
When the weight-average molecular weight of the urethane-based resin is within the above range, the urethane-based resin has appropriate hardness and fluidity, so that the heat resistance, moisture resistance, and flex resistance of the protective layer can be improved.
In addition, the weight average molecular weight of the urethane-based resin can be measured by gel permeation chromatography (GPC) under the following conditions.
Measuring instrument: Alliance GPC System (manufactured by Waters)
Column: Shodex GPC KF-806L (Showa Denko)
Column temperature: 40°C
Sample concentration: 0.05 wt%/THF
Injection volume: 10 μL
Standard sample: Tosoh: standard PS 500, Shodex standard PS SM-105 (set)
保護層２０に含まれる非導電性フィラーは、平均粒径が１０μｍ以下であり、また、保護層２０の全体重量に対する非導電性フィラーの重量割合は、１０～４０重量％である。また、非導電性フィラーの重量割合は、１０～３５重量％であることが好ましく、１０～２５質量％であることがより好ましい。
保護層２０が上記重量割合の非導電性フィラーを含むと、電磁波シールドフィルムをプリント配線板に熱プレスにより配置する際に、保護層に含まれるウレタン系樹脂が流動して保護層の一部が薄くなることを防ぐことができる。そのため、保護層の部分的に薄い箇所が生じにくくなる。その結果、電磁波シールドフィルムの耐湿性及び耐屈曲性が良好になる。特に非導電性フィラーの重量割合が１０～２５質量％であると、電磁波シールドフィルムの耐屈曲性がより良好になる。
非導電性フィラーの重量割合が１０重量％未満であると、非導電性フィラーを含む場合の効果が得られにくくなり、耐湿性が低下しやすくなる。
非導電性フィラーの重量割合が４０重量％を超えると、保護層が硬くなり柔軟性が低下しやすくなる。その結果、耐屈曲性が低下しやすくなる。 The non-conductive filler contained in theprotective layer 20 has an average particle diameter of 10 μm or less, and the weight ratio of the non-conductive filler to the total weight of the protective layer 20 is 10 to 40% by weight. Also, the weight ratio of the non-conductive filler is preferably 10 to 35% by weight, more preferably 10 to 25% by weight.
When theprotective layer 20 contains the non-conductive filler in the above weight ratio, the urethane-based resin contained in the protective layer flows when the electromagnetic wave shielding film is placed on the printed wiring board by hot pressing, and a part of the protective layer is partially removed. It can prevent thinning. Therefore, the protective layer is less likely to have partially thin portions. As a result, the electromagnetic wave shielding film has good moisture resistance and bending resistance. In particular, when the weight ratio of the non-conductive filler is 10 to 25% by mass, the flex resistance of the electromagnetic wave shielding film becomes better.
If the weight ratio of the non-conductive filler is less than 10% by weight, it becomes difficult to obtain the effect of containing the non-conductive filler, and moisture resistance tends to decrease.
If the weight ratio of the non-conductive filler exceeds 40% by weight, the protective layer becomes hard and the flexibility tends to decrease. As a result, the bending resistance tends to decrease.
保護層２０が上記重量割合の非導電性フィラーを含むと、電磁波シールドフィルムをプリント配線板に熱プレスにより配置する際に、保護層に含まれるウレタン系樹脂が流動して保護層の一部が薄くなることを防ぐことができる。そのため、保護層の部分的に薄い箇所が生じにくくなる。その結果、電磁波シールドフィルムの耐湿性及び耐屈曲性が良好になる。特に非導電性フィラーの重量割合が１０～２５質量％であると、電磁波シールドフィルムの耐屈曲性がより良好になる。
非導電性フィラーの重量割合が１０重量％未満であると、非導電性フィラーを含む場合の効果が得られにくくなり、耐湿性が低下しやすくなる。
非導電性フィラーの重量割合が４０重量％を超えると、保護層が硬くなり柔軟性が低下しやすくなる。その結果、耐屈曲性が低下しやすくなる。 The non-conductive filler contained in the
When the
If the weight ratio of the non-conductive filler is less than 10% by weight, it becomes difficult to obtain the effect of containing the non-conductive filler, and moisture resistance tends to decrease.
If the weight ratio of the non-conductive filler exceeds 40% by weight, the protective layer becomes hard and the flexibility tends to decrease. As a result, the bending resistance tends to decrease.
また、非導電性フィラーは、平均粒径が１００ｎｍ～１０μｍであることが好ましい。
非導電性フィラーの平均粒径が１００ｎｍ以上であると、保護層に含まれるウレタン系樹脂が流動して保護層の一部が薄くなることを好適に防ぐことができる。
非導電性フィラーの平均粒径が１０μｍ以下であると、保護層全体の厚さを薄くすることができる。 Also, the non-conductive filler preferably has an average particle size of 100 nm to 10 μm.
When the average particle diameter of the non-conductive filler is 100 nm or more, it is possible to suitably prevent the urethane-based resin contained in the protective layer from flowing and partially thinning the protective layer.
When the average particle size of the non-conductive filler is 10 µm or less, the thickness of the entire protective layer can be reduced.
非導電性フィラーの平均粒径が１００ｎｍ以上であると、保護層に含まれるウレタン系樹脂が流動して保護層の一部が薄くなることを好適に防ぐことができる。
非導電性フィラーの平均粒径が１０μｍ以下であると、保護層全体の厚さを薄くすることができる。 Also, the non-conductive filler preferably has an average particle size of 100 nm to 10 μm.
When the average particle diameter of the non-conductive filler is 100 nm or more, it is possible to suitably prevent the urethane-based resin contained in the protective layer from flowing and partially thinning the protective layer.
When the average particle size of the non-conductive filler is 10 µm or less, the thickness of the entire protective layer can be reduced.
非導電性フィラーは、シリカ及び有機リン酸塩からなる群から選択される少なくとも１種であることが好ましい。これらの中ではシリカであることが好ましい。
これらの材料からなる非導電性フィラーは、電磁波シールドフィルムの耐湿性及び耐屈曲性を好適に向上させることができる。 The non-conductive filler is preferably at least one selected from the group consisting of silica and organic phosphates. Among these, silica is preferred.
Non-conductive fillers made of these materials can favorably improve the moisture resistance and bending resistance of the electromagnetic wave shielding film.
これらの材料からなる非導電性フィラーは、電磁波シールドフィルムの耐湿性及び耐屈曲性を好適に向上させることができる。 The non-conductive filler is preferably at least one selected from the group consisting of silica and organic phosphates. Among these, silica is preferred.
Non-conductive fillers made of these materials can favorably improve the moisture resistance and bending resistance of the electromagnetic wave shielding film.
非導電性フィラーがシリカである場合、コロイダルシリカ、フュームドシリカ、湿式法により合成された湿式シリカ、乾式法により合成された乾式シリカ、多孔性シリカ、無孔性シリカ、疎水性シリカ、各種表面処理を施した親水性シリカであってもよい。
When the non-conductive filler is silica, colloidal silica, fumed silica, wet silica synthesized by wet method, dry silica synthesized by dry method, porous silica, non-porous silica, hydrophobic silica, various surfaces It may be treated hydrophilic silica.
疎水性シリカは、例えば、乾式法で合成された非晶質シリカ又は湿式法で合成された非晶質シリカの表面に存在するシラノール基に、疎水性を付与するための表面処理を施すことで製造することができる。
このような表面処理としては、例えば、非晶質シリカの表面を、パラフィンワックス、カルナウバワックス、アミドワックス、ポリエチレンワックスなどのワックス類で被覆する処理が挙げられる。得られる疎水性シリカは、非晶質シリカ表面のシラノール基がワックス層により覆われるため、疎水性を示す。また、非晶質シリカにテトラメチルシラン、ビニルトリクロロシラン、ビニルトリメトキシシラン、エポキシ基含有シラン、ジメチルジクロロシランなどの有機ケイ素化合物やアミノ基含有有機化合物などを添加し、加水分解等で変性する処理も挙げられる。このようにして得られる疎水性シリカは、非晶質シリカ表面のシラノール基が、有機ケイ素化合物などと化学反応したものであり、その表面にアルキル基などの疎水性基を有している。 Hydrophobic silica is obtained, for example, by subjecting the silanol groups present on the surface of amorphous silica synthesized by a dry method or amorphous silica synthesized by a wet method to a surface treatment for imparting hydrophobicity. can be manufactured.
Examples of such surface treatment include treatment of coating the surface of amorphous silica with waxes such as paraffin wax, carnauba wax, amide wax, and polyethylene wax. The resulting hydrophobic silica exhibits hydrophobicity because the silanol groups on the surface of the amorphous silica are covered with a wax layer. In addition, amorphous silica is modified by hydrolysis or the like by adding organosilicon compounds such as tetramethylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, epoxy group-containing silane, or dimethyldichlorosilane, or amino group-containing organic compounds. Processing is also included. Hydrophobic silica thus obtained is obtained by chemically reacting silanol groups on the surface of amorphous silica with an organic silicon compound or the like, and has hydrophobic groups such as alkyl groups on its surface.
このような表面処理としては、例えば、非晶質シリカの表面を、パラフィンワックス、カルナウバワックス、アミドワックス、ポリエチレンワックスなどのワックス類で被覆する処理が挙げられる。得られる疎水性シリカは、非晶質シリカ表面のシラノール基がワックス層により覆われるため、疎水性を示す。また、非晶質シリカにテトラメチルシラン、ビニルトリクロロシラン、ビニルトリメトキシシラン、エポキシ基含有シラン、ジメチルジクロロシランなどの有機ケイ素化合物やアミノ基含有有機化合物などを添加し、加水分解等で変性する処理も挙げられる。このようにして得られる疎水性シリカは、非晶質シリカ表面のシラノール基が、有機ケイ素化合物などと化学反応したものであり、その表面にアルキル基などの疎水性基を有している。 Hydrophobic silica is obtained, for example, by subjecting the silanol groups present on the surface of amorphous silica synthesized by a dry method or amorphous silica synthesized by a wet method to a surface treatment for imparting hydrophobicity. can be manufactured.
Examples of such surface treatment include treatment of coating the surface of amorphous silica with waxes such as paraffin wax, carnauba wax, amide wax, and polyethylene wax. The resulting hydrophobic silica exhibits hydrophobicity because the silanol groups on the surface of the amorphous silica are covered with a wax layer. In addition, amorphous silica is modified by hydrolysis or the like by adding organosilicon compounds such as tetramethylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, epoxy group-containing silane, or dimethyldichlorosilane, or amino group-containing organic compounds. Processing is also included. Hydrophobic silica thus obtained is obtained by chemically reacting silanol groups on the surface of amorphous silica with an organic silicon compound or the like, and has hydrophobic groups such as alkyl groups on its surface.
このような疎水性シリカとしては、ＡＥＲＯＳＩＬ Ｒ９７２、ＡＥＲＯＳＩＬ Ｒ９７４、ＡＥＲＯＳＩＬ Ｒ９７６、ＡＥＲＯＳＩＬ Ｒ１０４、ＡＥＲＯＳＩＬ Ｒ１０６、ＡＥＲＯＳＩＬ Ｒ２０２、ＡＥＲＯＳＩＬ Ｒ８０５、ＡＥＲＯＳＩＬ Ｒ８１２、ＡＥＲＯＳＩＬ Ｒ８１２Ｓ、ＡＥＲＯＳＩＬ Ｒ８１６、ＡＥＲＯＳＩＬ Ｒ７２００、ＡＥＲＯＳＩＬ Ｒ８２００、ＡＥＲＯＳＩＬ Ｒ９２００（以上、日本アエロジル（株）製）、サイロホービック２００、サイロホービック７０４、サイロホービック５０５、サイロホービック６０３（以上、富士シリシア化学株式会社製）等が挙げられる。
Examples of such hydrophobic silica include AEROSIL R972, AEROSIL R974, AEROSIL R976, AEROSIL R104, AEROSIL R106, AEROSIL R202, AEROSIL R805, AEROSIL R812, AEROSIL R812S, AEROSIL R816, AEROSIL R7200, AEROSIL R80, Nippon Aerosil Co., Ltd.), Cyrophobic 200, Cyrophobic 704, Cyrophobic 505, and Cyrophobic 603 (manufactured by Fuji Silysia Chemical Co., Ltd.).
親水性シリカは、例えば、乾式法で合成された非晶質シリカ又は湿式法で合成された非晶質シリカの表面に存在するシラノール基に、化学修飾を行わないことで製造することができる。
このような親水性シリカとしては、ＡＥＲＯＳＩＬ ９０、ＡＥＲＯＳＩＬ １３０、ＡＥＲＯＳＩＬ １５０、ＡＥＲＯＳＩＬ ２００、ＡＥＲＯＳＩＬ ３００、ＡＥＲＯＳＩＬ ３８０、ＡＥＲＯＳＩＬ ＯＸ５０、ＡＥＲＯＳＩＬ ＥＧ５０、ＡＥＲＯＳＩＬ ＴＴ６００（以上、日本アエロジル（株）製）、サイリシア２５０、サイリシア３５０、サイリシア４５０、サイリシア５５０、サイリシア７４０（以上、富士シリシア化学株式会社製）等が挙げられる。 Hydrophilic silica can be produced, for example, by not chemically modifying the silanol groups present on the surface of amorphous silica synthesized by a dry method or amorphous silica synthesized by a wet method.
Examples of such hydrophilic silica include AEROSIL 90, AEROSIL 130, AEROSIL 150, AEROSIL 200, AEROSIL 300, AEROSIL 380, AEROSIL OX50, AEROSIL EG50, AEROSIL TT600 (manufactured by Nippon Aerosil Co., Ltd.), Silysia 250, Silysia 350, Silicia 450, Silicia 550, Silicia 740 (manufactured by Fuji Silysia Chemical Co., Ltd.) and the like.
このような親水性シリカとしては、ＡＥＲＯＳＩＬ ９０、ＡＥＲＯＳＩＬ １３０、ＡＥＲＯＳＩＬ １５０、ＡＥＲＯＳＩＬ ２００、ＡＥＲＯＳＩＬ ３００、ＡＥＲＯＳＩＬ ３８０、ＡＥＲＯＳＩＬ ＯＸ５０、ＡＥＲＯＳＩＬ ＥＧ５０、ＡＥＲＯＳＩＬ ＴＴ６００（以上、日本アエロジル（株）製）、サイリシア２５０、サイリシア３５０、サイリシア４５０、サイリシア５５０、サイリシア７４０（以上、富士シリシア化学株式会社製）等が挙げられる。 Hydrophilic silica can be produced, for example, by not chemically modifying the silanol groups present on the surface of amorphous silica synthesized by a dry method or amorphous silica synthesized by a wet method.
Examples of such hydrophilic silica include AEROSIL 90, AEROSIL 130, AEROSIL 150, AEROSIL 200, AEROSIL 300, AEROSIL 380, AEROSIL OX50, AEROSIL EG50, AEROSIL TT600 (manufactured by Nippon Aerosil Co., Ltd.), Silysia 250, Silysia 350, Silicia 450, Silicia 550, Silicia 740 (manufactured by Fuji Silysia Chemical Co., Ltd.) and the like.
非導電性フィラーが有機リン酸塩である場合、ポリリン酸塩及びホスフィン酸金属塩等が挙げられる。ホスフィン酸金属塩としては、アルミニウム塩、ナトリウム塩、カリウム塩、マグネシウム塩、及びカルシウム塩等を用いることができ、中でもアルミニウム塩が好ましい。ポリリン酸塩としては、メラミン塩、メチルアミン塩、エチルアミン塩、ジエチルアミン塩、トリエチルアミン塩、エチレンジアミン塩、ピペラジン塩、ピリジン塩、トリアジン塩、及びアンモニウム塩等を用いることができ、中でもメラミン塩が好ましい。
When the non-conductive filler is an organic phosphate, polyphosphates, metal phosphinates, and the like are included. As the phosphinic acid metal salt, aluminum salt, sodium salt, potassium salt, magnesium salt, calcium salt and the like can be used, among which aluminum salt is preferable. As polyphosphates, melamine salts, methylamine salts, ethylamine salts, diethylamine salts, triethylamine salts, ethylenediamine salts, piperazine salts, pyridine salts, triazine salts, ammonium salts and the like can be used, with melamine salts being preferred.
保護層２０の厚さは、特に限定されないが、１～１００μｍであることが好ましく、２～５０μｍであることがより好ましい。
保護層の厚さが１μｍ未満であると、保護層が薄すぎるので破損しやすくなる。
保護層の厚さが１００μｍを超えると、電磁波シールドフィルム全体が厚くなり、扱いにくくなる。また、保護層の柔軟性が低下する。 Although the thickness of theprotective layer 20 is not particularly limited, it is preferably 1 to 100 μm, more preferably 2 to 50 μm.
If the thickness of the protective layer is less than 1 μm, the protective layer is too thin and is easily damaged.
If the thickness of the protective layer exceeds 100 μm, the electromagnetic wave shielding film as a whole becomes thick and difficult to handle. Also, the flexibility of the protective layer is reduced.
保護層の厚さが１μｍ未満であると、保護層が薄すぎるので破損しやすくなる。
保護層の厚さが１００μｍを超えると、電磁波シールドフィルム全体が厚くなり、扱いにくくなる。また、保護層の柔軟性が低下する。 Although the thickness of the
If the thickness of the protective layer is less than 1 μm, the protective layer is too thin and is easily damaged.
If the thickness of the protective layer exceeds 100 μm, the electromagnetic wave shielding film as a whole becomes thick and difficult to handle. Also, the flexibility of the protective layer is reduced.
保護層２０は、さらにエポキシ系樹脂を有することが好ましい。
保護層２０がエポキシ系樹脂を含むと、電磁波シールドフィルム１０をプリント配線板に熱プレスにより配置する際に、保護層に含まれるウレタン系樹脂が流動することを抑制することができる。 Theprotective layer 20 preferably further contains an epoxy resin.
When theprotective layer 20 contains an epoxy resin, it is possible to suppress the flow of the urethane resin contained in the protective layer when the electromagnetic wave shielding film 10 is arranged on the printed wiring board by hot pressing.
保護層２０がエポキシ系樹脂を含むと、電磁波シールドフィルム１０をプリント配線板に熱プレスにより配置する際に、保護層に含まれるウレタン系樹脂が流動することを抑制することができる。 The
When the
エポキシ系樹脂の酸価は、１００～５００ｇ／ｅｑであることが好ましく、１５０～４５０ｇ／ｅｑであることがより好ましい。
The acid value of the epoxy resin is preferably 100-500 g/eq, more preferably 150-450 g/eq.
電磁波シールドフィルム１０では、保護層２０におけるウレタン系樹脂と、エポキシ系樹脂との重量比は、ウレタン系樹脂／エポキシ系樹脂＝４～４９であることが好ましく、１０～４０であることがより好ましい。
上記重量比が４未満であると、エポキシ系樹脂が多くなりすぎ、保護層が硬くなりやすくなる。その結果、保護層の柔軟性が低下し、耐屈曲性が低下する。
上記重量比が４９を超えると、エポキシ系樹脂が少なくなり、保護層が柔らかくなり、エポキシ系樹脂を含む効果を得られにくくなる。 In the electromagneticwave shielding film 10, the weight ratio of the urethane-based resin and the epoxy-based resin in the protective layer 20 is preferably urethane-based resin/epoxy-based resin=4 to 49, and more preferably 10 to 40. .
If the weight ratio is less than 4, the amount of the epoxy resin is too large, and the protective layer tends to be hard. As a result, the flexibility of the protective layer is lowered and the bending resistance is lowered.
If the weight ratio exceeds 49, the amount of the epoxy resin decreases, the protective layer becomes soft, and it becomes difficult to obtain the effect of including the epoxy resin.
上記重量比が４未満であると、エポキシ系樹脂が多くなりすぎ、保護層が硬くなりやすくなる。その結果、保護層の柔軟性が低下し、耐屈曲性が低下する。
上記重量比が４９を超えると、エポキシ系樹脂が少なくなり、保護層が柔らかくなり、エポキシ系樹脂を含む効果を得られにくくなる。 In the electromagnetic
If the weight ratio is less than 4, the amount of the epoxy resin is too large, and the protective layer tends to be hard. As a result, the flexibility of the protective layer is lowered and the bending resistance is lowered.
If the weight ratio exceeds 49, the amount of the epoxy resin decreases, the protective layer becomes soft, and it becomes difficult to obtain the effect of including the epoxy resin.
保護層２０には、必要に応じて、硬化促進剤、粘着性付与剤、酸化防止剤、顔料、染料、可塑剤、紫外線吸収剤、消泡剤、レベリング剤、充填材、難燃剤、粘度調節剤、ブロッキング防止剤等が含まれていてもよい。
The protective layer 20 may optionally contain a curing accelerator, a tackifier, an antioxidant, a pigment, a dye, a plasticizer, an ultraviolet absorber, an antifoaming agent, a leveling agent, a filler, a flame retardant, and a viscosity adjuster. agents, anti-blocking agents and the like may also be included.
（金属層）
電磁波シールドフィルム１０の金属層３０は、電磁波をシールドできれば、特に限定されず、銅層、銀層及びアルミニウム層からなる群から選択される少なくとも１種からなることが好ましい。
これらの金属層は、導電性が高く、好適に電磁波をシールドすることができる。 (metal layer)
Themetal layer 30 of the electromagnetic wave shielding film 10 is not particularly limited as long as it can shield electromagnetic waves, and is preferably made of at least one selected from the group consisting of a copper layer, a silver layer and an aluminum layer.
These metal layers have high conductivity and can suitably shield electromagnetic waves.
電磁波シールドフィルム１０の金属層３０は、電磁波をシールドできれば、特に限定されず、銅層、銀層及びアルミニウム層からなる群から選択される少なくとも１種からなることが好ましい。
これらの金属層は、導電性が高く、好適に電磁波をシールドすることができる。 (metal layer)
The
These metal layers have high conductivity and can suitably shield electromagnetic waves.
金属層３０の厚さは特に限定されないが、０．０１～１０μｍであることが好ましい。
金属層の厚さが０．０１μｍ未満では、充分なシールド効果が得られにくい。
金属層の厚さが１０μｍを超えると電磁波シールドフィルムが屈曲しにくくなる。 Although the thickness of themetal layer 30 is not particularly limited, it is preferably 0.01 to 10 μm.
If the thickness of the metal layer is less than 0.01 μm, it is difficult to obtain a sufficient shielding effect.
If the thickness of the metal layer exceeds 10 μm, the electromagnetic wave shielding film becomes difficult to bend.
金属層の厚さが０．０１μｍ未満では、充分なシールド効果が得られにくい。
金属層の厚さが１０μｍを超えると電磁波シールドフィルムが屈曲しにくくなる。 Although the thickness of the
If the thickness of the metal layer is less than 0.01 μm, it is difficult to obtain a sufficient shielding effect.
If the thickness of the metal layer exceeds 10 μm, the electromagnetic wave shielding film becomes difficult to bend.
電磁波シールドフィルム１０では、金属層３０は、貫通孔を有していてもよい。
電磁波シールドフィルム１０は、プリント配線板に熱プレスされることになる。この際、導電性接着剤層４０と、金属層３０との間に揮発成分が生じることがある。
金属層３０に貫通孔が形成されていない場合、この揮発成分が熱により膨張し、金属層３０と導電性接着剤層４０を剥離することがある。しかし、金属層３０に貫通孔が形成されていると、揮発成分が貫通孔を通過することができるので、金属層３０と導電性接着剤層４０とが剥離することを防ぐことができる。 In the electromagneticwave shielding film 10, the metal layer 30 may have through holes.
The electromagneticwave shielding film 10 is hot-pressed onto the printed wiring board. At this time, volatile components may occur between the conductive adhesive layer 40 and the metal layer 30 .
If themetal layer 30 does not have through-holes, the volatile component expands due to heat and may separate the metal layer 30 and the conductive adhesive layer 40 from each other. However, if the metal layer 30 has through-holes, volatile components can pass through the through-holes, so that the metal layer 30 and the conductive adhesive layer 40 can be prevented from peeling off.
電磁波シールドフィルム１０は、プリント配線板に熱プレスされることになる。この際、導電性接着剤層４０と、金属層３０との間に揮発成分が生じることがある。
金属層３０に貫通孔が形成されていない場合、この揮発成分が熱により膨張し、金属層３０と導電性接着剤層４０を剥離することがある。しかし、金属層３０に貫通孔が形成されていると、揮発成分が貫通孔を通過することができるので、金属層３０と導電性接着剤層４０とが剥離することを防ぐことができる。 In the electromagnetic
The electromagnetic
If the
（導電性接着剤層）
導電性接着剤層４０は、接着性樹脂組成物と金属粒子とを含む。
なお、導電性接着剤層４０は、さらに、難燃剤、難燃助剤、硬化促進剤、粘着性付与剤、酸化防止剤、顔料、染料、可塑剤、紫外線吸収剤、消泡剤、レベリング剤、充填材、粘度調節剤等を含んでいてもよい。 (Conductive adhesive layer)
The conductiveadhesive layer 40 contains an adhesive resin composition and metal particles.
The conductiveadhesive layer 40 further includes a flame retardant, a flame retardant aid, a curing accelerator, a tackifier, an antioxidant, a pigment, a dye, a plasticizer, an ultraviolet absorber, an antifoaming agent, and a leveling agent. , fillers, viscosity modifiers and the like.
導電性接着剤層４０は、接着性樹脂組成物と金属粒子とを含む。
なお、導電性接着剤層４０は、さらに、難燃剤、難燃助剤、硬化促進剤、粘着性付与剤、酸化防止剤、顔料、染料、可塑剤、紫外線吸収剤、消泡剤、レベリング剤、充填材、粘度調節剤等を含んでいてもよい。 (Conductive adhesive layer)
The conductive
The conductive
導電性接着剤層４０に含まれる接着性樹脂組成物の材料としては、特に限定されないが、スチレン系樹脂組成物、酢酸ビニル系樹脂組成物、ポリエステル系樹脂組成物、ポリエチレン系樹脂組成物、ポリプロピレン系樹脂組成物、イミド系樹脂組成物、アミド系樹脂組成物、アクリル系樹脂組成物等の熱可塑性樹脂組成物や、フェノール系樹脂組成物、エポキシ系樹脂組成物、ウレタン系樹脂組成物、メラミン系樹脂組成物、アルキッド系樹脂組成物等の熱硬化性樹脂組成物等を用いることができる。
これらの中では、ポリエステル系樹脂組成物であることが好ましい。
接着性樹脂組成物の材料はこれらの１種単独であってもよく、２種以上の組み合わせであってもよい。 The material of the adhesive resin composition contained in the conductiveadhesive layer 40 is not particularly limited, but may be a styrene-based resin composition, a vinyl acetate-based resin composition, a polyester-based resin composition, a polyethylene-based resin composition, or polypropylene. Thermoplastic resin compositions such as resin compositions, imide resin compositions, amide resin compositions, acrylic resin compositions, phenol resin compositions, epoxy resin compositions, urethane resin compositions, melamine A thermosetting resin composition such as an alkyd-based resin composition or an alkyd-based resin composition can be used.
Among these, the polyester-based resin composition is preferable.
The material of the adhesive resin composition may be one of these alone or a combination of two or more.
これらの中では、ポリエステル系樹脂組成物であることが好ましい。
接着性樹脂組成物の材料はこれらの１種単独であってもよく、２種以上の組み合わせであってもよい。 The material of the adhesive resin composition contained in the conductive
Among these, the polyester-based resin composition is preferable.
The material of the adhesive resin composition may be one of these alone or a combination of two or more.
導電性接着剤層４０に含まれる金属粒子としては、銀、銅、ニッケル、アルミニウム、銅に銀めっきを施した銀コート銅等が挙げられる。
これらの金属粒子は導電性に優れるので、導電性接着剤層４０に好適に導電性を付与することができる。
これらの金属粒子は、導電性接着剤層４０に一種単独で含まれていてもよく、複数種類が含まれていてもよい。 Examples of metal particles contained in the conductiveadhesive layer 40 include silver, copper, nickel, aluminum, and silver-coated copper obtained by plating copper with silver.
Since these metal particles have excellent conductivity, they can suitably impart conductivity to the conductiveadhesive layer 40 .
These metal particles may be contained singly in the conductiveadhesive layer 40, or may be contained in a plurality of types.
これらの金属粒子は導電性に優れるので、導電性接着剤層４０に好適に導電性を付与することができる。
これらの金属粒子は、導電性接着剤層４０に一種単独で含まれていてもよく、複数種類が含まれていてもよい。 Examples of metal particles contained in the conductive
Since these metal particles have excellent conductivity, they can suitably impart conductivity to the conductive
These metal particles may be contained singly in the conductive
金属粒子の大きさは特に限定されないが、平均粒径が０．５～２０μｍであることが好ましい。
The size of the metal particles is not particularly limited, but the average particle size is preferably 0.5 to 20 μm.
導電性接着剤層４０に含まれる金属粒子の重量割合は、２～６０ｗｔ％であることが好ましく、１０～４０ｗｔ％であることがより好ましい。
金属粒子の重量割合が２ｗｔ％未満であると、電磁波シールドフィルムのシールド性が低下しやすくなる。
金属粒子の重量割合が６０ｗｔ％を超えると、導電性接着剤層が脆くなり、電磁波シールドフィルムが破損しやすくなる。
また、金属粒子の重量割合が４０ｗｔ％以下であると、導電性接着剤層が、異方導電性を得ることができる。 The weight ratio of the metal particles contained in the conductiveadhesive layer 40 is preferably 2-60 wt %, more preferably 10-40 wt %.
If the weight ratio of the metal particles is less than 2 wt %, the shielding properties of the electromagnetic wave shielding film tend to deteriorate.
If the weight ratio of the metal particles exceeds 60 wt %, the conductive adhesive layer becomes brittle and the electromagnetic wave shielding film tends to break.
Moreover, when the weight ratio of the metal particles is 40 wt % or less, the conductive adhesive layer can obtain anisotropic conductivity.
金属粒子の重量割合が２ｗｔ％未満であると、電磁波シールドフィルムのシールド性が低下しやすくなる。
金属粒子の重量割合が６０ｗｔ％を超えると、導電性接着剤層が脆くなり、電磁波シールドフィルムが破損しやすくなる。
また、金属粒子の重量割合が４０ｗｔ％以下であると、導電性接着剤層が、異方導電性を得ることができる。 The weight ratio of the metal particles contained in the conductive
If the weight ratio of the metal particles is less than 2 wt %, the shielding properties of the electromagnetic wave shielding film tend to deteriorate.
If the weight ratio of the metal particles exceeds 60 wt %, the conductive adhesive layer becomes brittle and the electromagnetic wave shielding film tends to break.
Moreover, when the weight ratio of the metal particles is 40 wt % or less, the conductive adhesive layer can obtain anisotropic conductivity.
電磁波シールドフィルム１０では、導電性接着剤層４０は、等方導電性を有していてもよく、異方導電性を有していてもよい。
導電性接着剤層４０が異方導電性を有すると、電磁波シールドフィルム１０が配置されたプリント配線板において、高周波信号の送電特性が良好になる。 In theelectromagnetic shielding film 10, the conductive adhesive layer 40 may have isotropic conductivity or anisotropic conductivity.
When the conductiveadhesive layer 40 has anisotropic conductivity, the printed wiring board on which the electromagnetic wave shielding film 10 is arranged has good high-frequency signal transmission characteristics.
導電性接着剤層４０が異方導電性を有すると、電磁波シールドフィルム１０が配置されたプリント配線板において、高周波信号の送電特性が良好になる。 In the
When the conductive
導電性接着剤層４０の厚さは、特に限定されず、必要に応じ適宜設定することができるが、０．５～３０．０μｍであることが望ましい。
導電性接着剤層の厚さが０．５μｍ未満であると、良好な導電性が得られにくくなる。
導電性接着剤層の厚さが３０．０μｍを超えると、電磁波シールドフィルム全体の厚さが厚くなり扱いにくくなる。 The thickness of the conductiveadhesive layer 40 is not particularly limited and can be appropriately set as necessary, but is preferably 0.5 to 30.0 μm.
If the thickness of the conductive adhesive layer is less than 0.5 μm, it becomes difficult to obtain good conductivity.
If the thickness of the conductive adhesive layer exceeds 30.0 μm, the thickness of the entire electromagnetic wave shielding film becomes thick and difficult to handle.
導電性接着剤層の厚さが０．５μｍ未満であると、良好な導電性が得られにくくなる。
導電性接着剤層の厚さが３０．０μｍを超えると、電磁波シールドフィルム全体の厚さが厚くなり扱いにくくなる。 The thickness of the conductive
If the thickness of the conductive adhesive layer is less than 0.5 μm, it becomes difficult to obtain good conductivity.
If the thickness of the conductive adhesive layer exceeds 30.0 μm, the thickness of the entire electromagnetic wave shielding film becomes thick and difficult to handle.
電磁波シールドフィルム１０では、保護層２０と金属層３０との間にアンカーコート層が形成されていてもよい。
アンカーコート層の材料としては、ウレタン樹脂、アクリル樹脂、ウレタン樹脂をシェルとしアクリル樹脂をコアとするコア・シェル型複合樹脂、エポキシ樹脂、イミド樹脂、アミド樹脂、メラミン樹脂、フェノール樹脂、尿素ホルムアルデヒド樹脂、ポリイソシアネートにフェノール等のブロック化剤を反応させて得られたブロックイソシアネート、ポリビニルアルコール、ポリビニルピロリドン等が挙げられる。 An anchor coat layer may be formed between theprotective layer 20 and the metal layer 30 in the electromagnetic wave shielding film 10 .
Materials for the anchor coat layer include urethane resin, acrylic resin, core-shell type composite resin with urethane resin as the shell and acrylic resin as the core, epoxy resin, imide resin, amide resin, melamine resin, phenol resin, and urea-formaldehyde resin. , blocked isocyanate obtained by reacting polyisocyanate with a blocking agent such as phenol, polyvinyl alcohol, polyvinylpyrrolidone, and the like.
アンカーコート層の材料としては、ウレタン樹脂、アクリル樹脂、ウレタン樹脂をシェルとしアクリル樹脂をコアとするコア・シェル型複合樹脂、エポキシ樹脂、イミド樹脂、アミド樹脂、メラミン樹脂、フェノール樹脂、尿素ホルムアルデヒド樹脂、ポリイソシアネートにフェノール等のブロック化剤を反応させて得られたブロックイソシアネート、ポリビニルアルコール、ポリビニルピロリドン等が挙げられる。 An anchor coat layer may be formed between the
Materials for the anchor coat layer include urethane resin, acrylic resin, core-shell type composite resin with urethane resin as the shell and acrylic resin as the core, epoxy resin, imide resin, amide resin, melamine resin, phenol resin, and urea-formaldehyde resin. , blocked isocyanate obtained by reacting polyisocyanate with a blocking agent such as phenol, polyvinyl alcohol, polyvinylpyrrolidone, and the like.
上記電磁波シールドフィルム１０は、導電性接着剤層４０を備えているが、本発明の電磁波シールドフィルムは、導電性接着剤層に代えて非導電性の接着剤層を備えていてもよい。
The electromagnetic wave shielding film 10 has the conductive adhesive layer 40, but the electromagnetic wave shielding film of the present invention may have a non-conductive adhesive layer instead of the conductive adhesive layer.
次に、電磁波シールドフィルム１０をプリント配線板に配置するシールドプリント配線板の製造方法について説明する。
Next, a method for manufacturing a shield printed wiring board in which the electromagnetic wave shielding film 10 is arranged on the printed wiring board will be described.
（プリント配線板準備工程）
図２Ａは、本発明の電磁波シールドフィルムを用いたシールドプリント配線板の製造方法における、プリント配線板準備工程を模式的に示す断面図である。
本工程では、ベースフィルム５１と、ベースフィルム５１の上に配置されたグランド回路５２ａを含むプリント回路５２と、プリント回路５２を覆うカバーレイ５３とからなるプリント配線板５０を準備する。なお、カバーレイ５３には、グランド回路５２ａを露出する開口部５３ａが形成されている。 (Printed wiring board preparation process)
FIG. 2A is a cross-sectional view schematically showing a printed wiring board preparation step in the method for manufacturing a shield printed wiring board using the electromagnetic wave shielding film of the present invention.
In this step, a printedwiring board 50 comprising a base film 51, a printed circuit 52 including a ground circuit 52a disposed on the base film 51, and a coverlay 53 covering the printed circuit 52 is prepared. The coverlay 53 has an opening 53a that exposes the ground circuit 52a.
図２Ａは、本発明の電磁波シールドフィルムを用いたシールドプリント配線板の製造方法における、プリント配線板準備工程を模式的に示す断面図である。
本工程では、ベースフィルム５１と、ベースフィルム５１の上に配置されたグランド回路５２ａを含むプリント回路５２と、プリント回路５２を覆うカバーレイ５３とからなるプリント配線板５０を準備する。なお、カバーレイ５３には、グランド回路５２ａを露出する開口部５３ａが形成されている。 (Printed wiring board preparation process)
FIG. 2A is a cross-sectional view schematically showing a printed wiring board preparation step in the method for manufacturing a shield printed wiring board using the electromagnetic wave shielding film of the present invention.
In this step, a printed
（電磁波シールドフィルム配置工程）
図２Ｂは、本発明の電磁波シールドフィルムを用いたシールドプリント配線板の製造方法における、電磁波シールドフィルム配置工程を模式的に示す断面図である。
本工程では、電磁波シールドフィルム１０の導電性接着剤層４０は、プリント配線板５０のカバーレイ５３に接触するように、電磁波シールドフィルム１０をプリント配線板５０に配置する。 (Electromagnetic wave shielding film placement process)
FIG. 2B is a cross-sectional view schematically showing an electromagnetic shielding film placement step in the method for manufacturing a shield printed wiring board using the electromagnetic shielding film of the present invention.
In this step, theelectromagnetic shielding film 10 is arranged on the printed wiring board 50 so that the conductive adhesive layer 40 of the electromagnetic shielding film 10 is in contact with the coverlay 53 of the printed wiring board 50 .
図２Ｂは、本発明の電磁波シールドフィルムを用いたシールドプリント配線板の製造方法における、電磁波シールドフィルム配置工程を模式的に示す断面図である。
本工程では、電磁波シールドフィルム１０の導電性接着剤層４０は、プリント配線板５０のカバーレイ５３に接触するように、電磁波シールドフィルム１０をプリント配線板５０に配置する。 (Electromagnetic wave shielding film placement process)
FIG. 2B is a cross-sectional view schematically showing an electromagnetic shielding film placement step in the method for manufacturing a shield printed wiring board using the electromagnetic shielding film of the present invention.
In this step, the
（熱プレス工程）
図２Ｃは、本発明の電磁波シールドフィルムを用いたシールドプリント配線板の製造方法における、熱プレス工程を模式的に示す断面図である。
次に、電磁波シールドフィルム１０が配置されたプリント配線板５０を矢印の方向に熱プレスすることにより電磁波シールドフィルム１０をプリント配線板５０に熱プレスする。 (Heat press process)
FIG. 2C is a cross-sectional view schematically showing a hot press step in the method for manufacturing a shield printed wiring board using the electromagnetic wave shielding film of the present invention.
Next, the electromagneticwave shielding film 10 is heat-pressed onto the printed wiring board 50 by heat-pressing the printed wiring board 50 on which the electromagnetic wave shielding film 10 is arranged in the direction of the arrow.
図２Ｃは、本発明の電磁波シールドフィルムを用いたシールドプリント配線板の製造方法における、熱プレス工程を模式的に示す断面図である。
次に、電磁波シールドフィルム１０が配置されたプリント配線板５０を矢印の方向に熱プレスすることにより電磁波シールドフィルム１０をプリント配線板５０に熱プレスする。 (Heat press process)
FIG. 2C is a cross-sectional view schematically showing a hot press step in the method for manufacturing a shield printed wiring board using the electromagnetic wave shielding film of the present invention.
Next, the electromagnetic
保護層２０は、平均粒径が１０μｍ以下である非導電性フィラーを含み、保護層２０の全体重量に対する非導電性フィラーの重量割合は、１０～４０重量％であるため、熱プレスする際、保護層２０に含まれるウレタン系樹脂が流動して保護層の一部が薄くなることを防ぐことができる。そのため、保護層２０の部分的に薄い箇所が生じにくくなる。その結果、電磁波シールドフィルムの耐湿性及び耐屈曲性が良好になる。
The protective layer 20 contains a non-conductive filler having an average particle size of 10 μm or less, and the weight ratio of the non-conductive filler to the total weight of the protective layer 20 is 10 to 40% by weight. It is possible to prevent the urethane-based resin contained in the protective layer 20 from flowing and partially thinning the protective layer. Therefore, the protective layer 20 is less likely to be partially thin. As a result, the electromagnetic wave shielding film has good moisture resistance and bending resistance.
また、熱プレスにより、導電性接着剤層４０が開口部５３ａを埋め、導電性接着剤層４０とグランド回路５２ａとが接触することになる。
そのため、金属層３０とグランド回路５２ａとが電気的に接続され、電磁波シールド性が向上する。 Further, by hot pressing, the conductiveadhesive layer 40 fills the opening 53a, and the conductive adhesive layer 40 and the ground circuit 52a are brought into contact with each other.
Therefore, themetal layer 30 and the ground circuit 52a are electrically connected, and the electromagnetic wave shielding property is improved.
そのため、金属層３０とグランド回路５２ａとが電気的に接続され、電磁波シールド性が向上する。 Further, by hot pressing, the conductive
Therefore, the
熱プレスの条件としては、特に限定されないが、例えば、１５０～２００℃、２～５ＭＰａ、１～６０ｍｉｎの条件が挙げられる。
Conditions for hot pressing are not particularly limited, but include, for example, conditions of 150 to 200° C., 2 to 5 MPa, and 1 to 60 minutes.
図２Ｄは、本発明の電磁波シールドフィルムを用いて製造されたシールドプリント配線板の一例を模式的に示す断面図である。
以上の工程を経て、図２Ｄに示すように、電磁波シールドフィルム１０を用いたシールドプリント配線板１を製造することができる。 FIG. 2D is a cross-sectional view schematically showing an example of a shield printed wiring board manufactured using the electromagnetic wave shielding film of the present invention.
Through the above steps, as shown in FIG. 2D, the shield printed wiring board 1 using the electromagneticwave shielding film 10 can be manufactured.
以上の工程を経て、図２Ｄに示すように、電磁波シールドフィルム１０を用いたシールドプリント配線板１を製造することができる。 FIG. 2D is a cross-sectional view schematically showing an example of a shield printed wiring board manufactured using the electromagnetic wave shielding film of the present invention.
Through the above steps, as shown in FIG. 2D, the shield printed wiring board 1 using the electromagnetic
次に、本発明の電磁波シールドフィルムの別の態様を説明する。
図３は、本発明の電磁波シールドフィルムの別の一例を模式的に示す断面図である。
図３に示す電磁波シールドフィルム１１０は、保護層１２０と、導電性接着剤層１４０とが順に積層された電磁波シールドフィルムである。
電磁波シールドフィルム１１０において、導電性接着剤層１４０は等方導電性を有し、電磁波を遮蔽するシールド層として機能する。 Next, another aspect of the electromagnetic wave shielding film of the present invention will be described.
FIG. 3 is a cross-sectional view schematically showing another example of the electromagnetic wave shielding film of the present invention.
The electromagneticwave shielding film 110 shown in FIG. 3 is an electromagnetic wave shielding film in which a protective layer 120 and a conductive adhesive layer 140 are laminated in order.
In the electromagneticwave shielding film 110, the conductive adhesive layer 140 has isotropic conductivity and functions as a shield layer that shields electromagnetic waves.
図３は、本発明の電磁波シールドフィルムの別の一例を模式的に示す断面図である。
図３に示す電磁波シールドフィルム１１０は、保護層１２０と、導電性接着剤層１４０とが順に積層された電磁波シールドフィルムである。
電磁波シールドフィルム１１０において、導電性接着剤層１４０は等方導電性を有し、電磁波を遮蔽するシールド層として機能する。 Next, another aspect of the electromagnetic wave shielding film of the present invention will be described.
FIG. 3 is a cross-sectional view schematically showing another example of the electromagnetic wave shielding film of the present invention.
The electromagnetic
In the electromagnetic
電磁波シールドフィルム１１０において、保護層１２０の好ましい態様は、上記電磁波シールドフィルム１０の保護層１２０と同じである。
In the electromagnetic wave shielding film 110, the preferred aspects of the protective layer 120 are the same as those of the protective layer 120 of the electromagnetic wave shielding film 10 described above.
電磁波シールドフィルム１１０において、導電性接着剤層１４０の好ましい態様について以下に説明する。
Preferred aspects of the conductive adhesive layer 140 in the electromagnetic wave shielding film 110 will be described below.
導電性接着剤層１４０は、接着性樹脂組成物と金属粒子とを含む。
なお、導電性接着剤層１４０は、さらに、難燃剤、難燃助剤、硬化促進剤、粘着性付与剤、酸化防止剤、顔料、染料、可塑剤、紫外線吸収剤、消泡剤、レベリング剤、充填材、粘度調節剤等を含んでいてもよい。 Conductive adhesive layer 140 includes an adhesive resin composition and metal particles.
In addition, the conductive adhesive layer 140 further includes a flame retardant, a flame retardant aid, a curing accelerator, a tackifier, an antioxidant, a pigment, a dye, a plasticizer, an ultraviolet absorber, an antifoaming agent, and a leveling agent. , fillers, viscosity modifiers and the like.
なお、導電性接着剤層１４０は、さらに、難燃剤、難燃助剤、硬化促進剤、粘着性付与剤、酸化防止剤、顔料、染料、可塑剤、紫外線吸収剤、消泡剤、レベリング剤、充填材、粘度調節剤等を含んでいてもよい。 Conductive adhesive layer 140 includes an adhesive resin composition and metal particles.
In addition, the conductive adhesive layer 140 further includes a flame retardant, a flame retardant aid, a curing accelerator, a tackifier, an antioxidant, a pigment, a dye, a plasticizer, an ultraviolet absorber, an antifoaming agent, and a leveling agent. , fillers, viscosity modifiers and the like.
導電性接着剤層１４０に含まれる接着性樹脂組成物の材料としては、特に限定されないが、スチレン系樹脂組成物、酢酸ビニル系樹脂組成物、ポリエステル系樹脂組成物、ポリエチレン系樹脂組成物、ポリプロピレン系樹脂組成物、イミド系樹脂組成物、アミド系樹脂組成物、アクリル系樹脂組成物等の熱可塑性樹脂組成物や、フェノール系樹脂組成物、エポキシ系樹脂組成物、ウレタン系樹脂組成物、メラミン系樹脂組成物、アルキッド系樹脂組成物等の熱硬化性樹脂組成物等を用いることができる。
これらの中では、ポリエステル系樹脂組成物であることが好ましい。
接着性樹脂組成物の材料はこれらの１種単独であってもよく、２種以上の組み合わせであってもよい。 The material of the adhesive resin composition contained in the conductive adhesive layer 140 is not particularly limited, but may be a styrene-based resin composition, a vinyl acetate-based resin composition, a polyester-based resin composition, a polyethylene-based resin composition, or polypropylene. Thermoplastic resin compositions such as resin compositions, imide resin compositions, amide resin compositions, acrylic resin compositions, phenol resin compositions, epoxy resin compositions, urethane resin compositions, melamine A thermosetting resin composition such as an alkyd-based resin composition or an alkyd-based resin composition can be used.
Among these, the polyester-based resin composition is preferred.
The material of the adhesive resin composition may be one of these alone or a combination of two or more.
これらの中では、ポリエステル系樹脂組成物であることが好ましい。
接着性樹脂組成物の材料はこれらの１種単独であってもよく、２種以上の組み合わせであってもよい。 The material of the adhesive resin composition contained in the conductive adhesive layer 140 is not particularly limited, but may be a styrene-based resin composition, a vinyl acetate-based resin composition, a polyester-based resin composition, a polyethylene-based resin composition, or polypropylene. Thermoplastic resin compositions such as resin compositions, imide resin compositions, amide resin compositions, acrylic resin compositions, phenol resin compositions, epoxy resin compositions, urethane resin compositions, melamine A thermosetting resin composition such as an alkyd-based resin composition or an alkyd-based resin composition can be used.
Among these, the polyester-based resin composition is preferred.
The material of the adhesive resin composition may be one of these alone or a combination of two or more.
導電性接着剤層１４０に含まれる金属粒子としては、銀、銅、ニッケル、アルミニウム、銅に銀めっきを施した銀コート銅等が挙げられる。
これらの金属粒子は導電性に優れるので、導電性接着剤層１４０に好適に導電性を付与することができる。
これらの金属粒子は、導電性接着剤層１４０に一種単独で含まれていてもよく、複数種類が含まれていてもよい。 Examples of the metal particles contained in the conductive adhesive layer 140 include silver, copper, nickel, aluminum, and silver-coated copper obtained by plating copper with silver.
Since these metal particles have excellent conductivity, they can suitably impart conductivity to the conductive adhesive layer 140 .
These metal particles may be contained singly in the conductive adhesive layer 140, or may be contained in a plurality of types.
これらの金属粒子は導電性に優れるので、導電性接着剤層１４０に好適に導電性を付与することができる。
これらの金属粒子は、導電性接着剤層１４０に一種単独で含まれていてもよく、複数種類が含まれていてもよい。 Examples of the metal particles contained in the conductive adhesive layer 140 include silver, copper, nickel, aluminum, and silver-coated copper obtained by plating copper with silver.
Since these metal particles have excellent conductivity, they can suitably impart conductivity to the conductive adhesive layer 140 .
These metal particles may be contained singly in the conductive adhesive layer 140, or may be contained in a plurality of types.
金属粒子の大きさは特に限定されないが、平均粒径が０．５～２０μｍであることが好ましい。
The size of the metal particles is not particularly limited, but the average particle size is preferably 0.5 to 20 μm.
導電性接着剤層１４０に含まれる金属粒子の重量割合は、４０重量％以上であることが好ましく、４０～６０重量％であることがより好ましい。
金属粒子の重量割合が４０重量％以上であると、導電性接着剤層１４０が等方導電性を得ることができる。 The weight ratio of the metal particles contained in the conductive adhesive layer 140 is preferably 40% by weight or more, more preferably 40 to 60% by weight.
When the weight ratio of the metal particles is 40% by weight or more, the conductive adhesive layer 140 can obtain isotropic conductivity.
金属粒子の重量割合が４０重量％以上であると、導電性接着剤層１４０が等方導電性を得ることができる。 The weight ratio of the metal particles contained in the conductive adhesive layer 140 is preferably 40% by weight or more, more preferably 40 to 60% by weight.
When the weight ratio of the metal particles is 40% by weight or more, the conductive adhesive layer 140 can obtain isotropic conductivity.
以下に本発明をより具体的に説明する実施例を示すが、本発明はこれらの実施例に限定されるものではない。
EXAMPLES The present invention will be described below in more detail with examples, but the present invention is not limited to these examples.
（実施例１）
酸価が３３００ｇ／ｅｑ、Ｔｇが４０℃のウレタン樹脂Ａ（製造元：東洋紡社製、重量平均分子量：２００，０００）と、エポキシ樹脂（酸価：１７０ｇ／ｅｑ）と、非導電性フィラーとしてシリカ粒子（平均粒径：２μｍ）とを表１に示す割合で混錬し、保護層用組成物を作製した。
なお、表１中の組成の数値は、重量％を意味している。 (Example 1)
Urethane resin A (manufacturer: manufactured by Toyobo Co., Ltd., weight average molecular weight: 200,000) having an acid value of 3300 g/eq and a Tg of 40°C, an epoxy resin (acid value: 170 g/eq), and silica as a non-conductive filler Particles (average particle diameter: 2 μm) were kneaded at the ratio shown in Table 1 to prepare a protective layer composition.
In addition, the numerical value of the composition in Table 1 means the weight%.
酸価が３３００ｇ／ｅｑ、Ｔｇが４０℃のウレタン樹脂Ａ（製造元：東洋紡社製、重量平均分子量：２００，０００）と、エポキシ樹脂（酸価：１７０ｇ／ｅｑ）と、非導電性フィラーとしてシリカ粒子（平均粒径：２μｍ）とを表１に示す割合で混錬し、保護層用組成物を作製した。
なお、表１中の組成の数値は、重量％を意味している。 (Example 1)
Urethane resin A (manufacturer: manufactured by Toyobo Co., Ltd., weight average molecular weight: 200,000) having an acid value of 3300 g/eq and a Tg of 40°C, an epoxy resin (acid value: 170 g/eq), and silica as a non-conductive filler Particles (average particle diameter: 2 μm) were kneaded at the ratio shown in Table 1 to prepare a protective layer composition.
In addition, the numerical value of the composition in Table 1 means the weight%.
次に、転写フィルムとして、片面に剥離処理を施したポリエチレンテレフタレートフィルムを準備した。
次に、転写フィルムの剥離処理面に保護層用組成物を塗工し、電気オーブンを用い、１００℃で２分間加熱し、厚さ５μｍの保護層を作製した。
その後、保護層の上に、無電解めっきにより２μｍの銅層を形成した。当該銅層は、シールド層となる。 Next, as a transfer film, a polyethylene terephthalate film having one side subjected to release treatment was prepared.
Next, the release-treated surface of the transfer film was coated with the protective layer composition and heated at 100° C. for 2 minutes in an electric oven to prepare a protective layer having a thickness of 5 μm.
After that, a copper layer of 2 μm was formed on the protective layer by electroless plating. The copper layer becomes a shield layer.
次に、転写フィルムの剥離処理面に保護層用組成物を塗工し、電気オーブンを用い、１００℃で２分間加熱し、厚さ５μｍの保護層を作製した。
その後、保護層の上に、無電解めっきにより２μｍの銅層を形成した。当該銅層は、シールド層となる。 Next, as a transfer film, a polyethylene terephthalate film having one side subjected to release treatment was prepared.
Next, the release-treated surface of the transfer film was coated with the protective layer composition and heated at 100° C. for 2 minutes in an electric oven to prepare a protective layer having a thickness of 5 μm.
After that, a copper layer of 2 μm was formed on the protective layer by electroless plating. The copper layer becomes a shield layer.
次に、接着性樹脂組成物として熱可塑性ポリエステル樹脂を４０重量部と、導電性フィラーとして銀コート銅粉（平均粒径：１２μｍ）を６０重量部とを混錬して導電性接着剤を作製した。
そして、銅層の上に、作製した導電性接着剤を塗工し、電気オーブンを用い、１００℃で２分間加熱し、厚さ２０μｍの導電性接着剤層を作製した。
上記工程を経て実施例１に係る電磁波シールドフィルムを作製した。 Next, 40 parts by weight of a thermoplastic polyester resin as an adhesive resin composition and 60 parts by weight of silver-coated copper powder (average particle diameter: 12 μm) as a conductive filler are kneaded to prepare a conductive adhesive. did.
Then, the produced conductive adhesive was applied onto the copper layer and heated at 100° C. for 2 minutes using an electric oven to produce a conductive adhesive layer with a thickness of 20 μm.
An electromagnetic wave shielding film according to Example 1 was produced through the above steps.
そして、銅層の上に、作製した導電性接着剤を塗工し、電気オーブンを用い、１００℃で２分間加熱し、厚さ２０μｍの導電性接着剤層を作製した。
上記工程を経て実施例１に係る電磁波シールドフィルムを作製した。 Next, 40 parts by weight of a thermoplastic polyester resin as an adhesive resin composition and 60 parts by weight of silver-coated copper powder (average particle diameter: 12 μm) as a conductive filler are kneaded to prepare a conductive adhesive. did.
Then, the produced conductive adhesive was applied onto the copper layer and heated at 100° C. for 2 minutes using an electric oven to produce a conductive adhesive layer with a thickness of 20 μm.
An electromagnetic wave shielding film according to Example 1 was produced through the above steps.
（実施例２～３）及び（比較例１～８）
保護層に用いるウレタン系樹脂として表１に示す種類のウレタン樹脂を用い、保護層の組成を表１に示すように変更した以外は、実施例１と同様に、実施例２～３及び比較例１～８に係る電磁波シールドフィルムを作製した。 (Examples 2-3) and (Comparative Examples 1-8)
Examples 2 and 3 and Comparative Example were carried out in the same manner as in Example 1, except that the urethane resin of the type shown in Table 1 was used as the urethane resin used for the protective layer, and the composition of the protective layer was changed as shown in Table 1. Electromagnetic wave shielding films according to 1 to 8 were produced.
保護層に用いるウレタン系樹脂として表１に示す種類のウレタン樹脂を用い、保護層の組成を表１に示すように変更した以外は、実施例１と同様に、実施例２～３及び比較例１～８に係る電磁波シールドフィルムを作製した。 (Examples 2-3) and (Comparative Examples 1-8)
Examples 2 and 3 and Comparative Example were carried out in the same manner as in Example 1, except that the urethane resin of the type shown in Table 1 was used as the urethane resin used for the protective layer, and the composition of the protective layer was changed as shown in Table 1. Electromagnetic wave shielding films according to 1 to 8 were produced.
なお、実施例及び比較例におけるウレタン樹脂Ｂ～Ｅの酸価、重量平均分子量、Ｔｇは表１の通りである。
Table 1 shows the acid value, weight average molecular weight, and Tg of the urethane resins B to E in Examples and Comparative Examples.
（抵抗値試験）
図４Ａ及び図４Ｂは、抵抗値試験の方法を示す模式図である。
まず、図４Ａに示すように、ベースフィルム５１に、金属パッド５２ｂが形成され、金属パッド５２ｂを露出する２つの開口部５３ａを有するカバーレイ５３が配置された試験基板５５を準備した。なお開口部５３ａの直径は１ｍｍとした。
次に、導電性接着剤層４０が、カバーレイ５３に接触するように、各実施例及び各比較例に係る電磁波シールドフィルム１０を試験基板５５に配置した。
その後、プレス機を用いて１７０℃、３ＭＰａ、３０ｍｉｎの条件で熱プレスすることにより、図４Ｂに示す試験用シールド基板２を作製した。
次に、図４Ｂに示すように、２つの金属パッド５２ｂに抵抗測定器Ｒを接続し、製造直後の試験用シールド基板２の導電性接着剤層４０の電気抵抗値（厚さ方向の電気抵抗値）を測定した結果を表１に示す。
また、試験用シールド基板２に、２６０℃、１ｍｉｎの条件で熱衝撃を５回加え、その後、同様の方法で、試験用シールド基板２の導電性接着剤層４０の電気抵抗値（厚さ方向の電気抵抗値）を測定した結果を表１に示す。
また、試験用シールド基板２を、８５℃、８５％ＲＨの高温高湿環境下に５００ｈｒ放置し、その後、同様の方法で試験用シールド基板２の導電性接着剤層４０の電気抵抗値（厚さ方向の電気抵抗値）を測定した結果を表１に示す。 (Resistance value test)
4A and 4B are schematic diagrams showing a resistance value test method.
First, as shown in FIG. 4A, atest substrate 55 was prepared in which a metal pad 52b was formed on a base film 51 and a coverlay 53 having two openings 53a for exposing the metal pad 52b was arranged. The diameter of the opening 53a was set to 1 mm.
Next, the electromagneticwave shielding film 10 according to each example and each comparative example was placed on the test substrate 55 so that the conductive adhesive layer 40 was in contact with the coverlay 53 .
After that, a pressing machine was used to heat-press under the conditions of 170° C., 3 MPa, and 30 min, thereby fabricating thetest shield substrate 2 shown in FIG. 4B.
Next, as shown in FIG. 4B, a resistance measuring device R is connected to the twometal pads 52b, and the electrical resistance value (the electrical resistance in the thickness direction) of the conductive adhesive layer 40 of the test shield substrate 2 immediately after manufacturing is measured. value) is shown in Table 1.
In addition, thetest shield substrate 2 was subjected to thermal shock five times under conditions of 260° C. and 1 minute, and then the electric resistance value (thickness direction) of the conductive adhesive layer 40 of the test shield substrate 2 was measured in the same manner. Table 1 shows the results of measuring the electrical resistance value).
In addition, thetest shield substrate 2 was left in a high-temperature and high-humidity environment of 85° C. and 85% RH for 500 hours. Table 1 shows the results of measuring the electrical resistance value in the vertical direction.
図４Ａ及び図４Ｂは、抵抗値試験の方法を示す模式図である。
まず、図４Ａに示すように、ベースフィルム５１に、金属パッド５２ｂが形成され、金属パッド５２ｂを露出する２つの開口部５３ａを有するカバーレイ５３が配置された試験基板５５を準備した。なお開口部５３ａの直径は１ｍｍとした。
次に、導電性接着剤層４０が、カバーレイ５３に接触するように、各実施例及び各比較例に係る電磁波シールドフィルム１０を試験基板５５に配置した。
その後、プレス機を用いて１７０℃、３ＭＰａ、３０ｍｉｎの条件で熱プレスすることにより、図４Ｂに示す試験用シールド基板２を作製した。
次に、図４Ｂに示すように、２つの金属パッド５２ｂに抵抗測定器Ｒを接続し、製造直後の試験用シールド基板２の導電性接着剤層４０の電気抵抗値（厚さ方向の電気抵抗値）を測定した結果を表１に示す。
また、試験用シールド基板２に、２６０℃、１ｍｉｎの条件で熱衝撃を５回加え、その後、同様の方法で、試験用シールド基板２の導電性接着剤層４０の電気抵抗値（厚さ方向の電気抵抗値）を測定した結果を表１に示す。
また、試験用シールド基板２を、８５℃、８５％ＲＨの高温高湿環境下に５００ｈｒ放置し、その後、同様の方法で試験用シールド基板２の導電性接着剤層４０の電気抵抗値（厚さ方向の電気抵抗値）を測定した結果を表１に示す。 (Resistance value test)
4A and 4B are schematic diagrams showing a resistance value test method.
First, as shown in FIG. 4A, a
Next, the electromagnetic
After that, a pressing machine was used to heat-press under the conditions of 170° C., 3 MPa, and 30 min, thereby fabricating the
Next, as shown in FIG. 4B, a resistance measuring device R is connected to the two
In addition, the
In addition, the
（耐屈曲性試験）
図５は、耐屈曲性試験を模式的に示す図である。
電磁波シールドフィルムの耐屈曲性を以下の方法で評価した。 (Bend resistance test)
FIG. 5 is a diagram schematically showing a flex resistance test.
The bending resistance of the electromagnetic wave shielding film was evaluated by the following method.
図５は、耐屈曲性試験を模式的に示す図である。
電磁波シールドフィルムの耐屈曲性を以下の方法で評価した。 (Bend resistance test)
FIG. 5 is a diagram schematically showing a flex resistance test.
The bending resistance of the electromagnetic wave shielding film was evaluated by the following method.
＜操作（ｉ）＞
まず、ポリイミドフィルム２５μｍからなるベース部材の上に配線基板を模した回路を形成した３本の銅箔パターン（銅箔厚み１２μｍ、ライン巾８ｍｍ）が形成され、その上に絶縁性の接着剤層およびポリイミドフィルムからなるカバーレイ（絶縁フィルム厚み３７．５μｍ）が積層された試験用プリント配線基板６０を準備した。 <Operation (i)>
First, three copper foil patterns (copper foil thickness 12 μm, line width 8 mm) forming a circuit imitating a wiring board are formed on a base member made of a polyimide film of 25 μm, and an insulating adhesive layer is formed thereon. and a coverlay (insulating film thickness: 37.5 μm) made of a polyimide film were laminated.
まず、ポリイミドフィルム２５μｍからなるベース部材の上に配線基板を模した回路を形成した３本の銅箔パターン（銅箔厚み１２μｍ、ライン巾８ｍｍ）が形成され、その上に絶縁性の接着剤層およびポリイミドフィルムからなるカバーレイ（絶縁フィルム厚み３７．５μｍ）が積層された試験用プリント配線基板６０を準備した。 <Operation (i)>
First, three copper foil patterns (copper foil thickness 12 μm, line width 8 mm) forming a circuit imitating a wiring board are formed on a base member made of a polyimide film of 25 μm, and an insulating adhesive layer is formed thereon. and a coverlay (insulating film thickness: 37.5 μm) made of a polyimide film were laminated.
＜操作（ｉｉ）＞
次に各実施例及び各比較例に係る電磁波シールドフィルム１０と試験用プリント配線基板６０とを、電磁波シールドフィルム１０の接着剤層がプリント配線板６０のカバーレイと接するように、プレス機を用いて温度：１７０℃、時間：３０分、圧力：２～３ＭＰａの条件で接着し、積層体６１を作製した。 <Operation (ii)>
Next, the electromagneticwave shielding film 10 according to each example and each comparative example and the test printed wiring board 60 are put together using a pressing machine so that the adhesive layer of the electromagnetic wave shielding film 10 is in contact with the coverlay of the printed wiring board 60. A laminate 61 was produced by bonding under the conditions of temperature: 170° C., time: 30 minutes, and pressure: 2 to 3 MPa.
次に各実施例及び各比較例に係る電磁波シールドフィルム１０と試験用プリント配線基板６０とを、電磁波シールドフィルム１０の接着剤層がプリント配線板６０のカバーレイと接するように、プレス機を用いて温度：１７０℃、時間：３０分、圧力：２～３ＭＰａの条件で接着し、積層体６１を作製した。 <Operation (ii)>
Next, the electromagnetic
＜操作（ｉｉｉ）＞
次に、厚さ２ｍｍのベーク板７１上に、厚さ０．４ｍｍの矩形状のガラスエポキシ板７２を２本、平行となるように固定した治具を作製した。そして、積層体６１を電磁波シールドフィルム１０が外側となるように折り曲げた状態で治具における２本のガラスエポキシ板７２の間で保持した。 <Operation (iii)>
Next, a jig was prepared by fixing two rectangularglass epoxy plates 72 with a thickness of 0.4 mm on a baking plate 71 with a thickness of 2 mm so as to be parallel to each other. Then, the laminated body 61 was held between two glass epoxy plates 72 in a jig while being bent so that the electromagnetic wave shielding film 10 was on the outside.
次に、厚さ２ｍｍのベーク板７１上に、厚さ０．４ｍｍの矩形状のガラスエポキシ板７２を２本、平行となるように固定した治具を作製した。そして、積層体６１を電磁波シールドフィルム１０が外側となるように折り曲げた状態で治具における２本のガラスエポキシ板７２の間で保持した。 <Operation (iii)>
Next, a jig was prepared by fixing two rectangular
＜操作（ｉｖ）＞
次いで、折り曲げた状態で保持された積層体６１の上に、厚さ２ｍｍのベーク板７３および１ｋｇの標準分銅７４を載置し、１０秒間保持した。 <Operation (iv)>
Next, abaking plate 73 with a thickness of 2 mm and a standard weight 74 with a weight of 1 kg were placed on the laminate 61 held in the folded state and held for 10 seconds.
次いで、折り曲げた状態で保持された積層体６１の上に、厚さ２ｍｍのベーク板７３および１ｋｇの標準分銅７４を載置し、１０秒間保持した。 <Operation (iv)>
Next, a
＜操作（ｖ）＞
１０秒間保持した後、ベーク板７３および標準分銅７４を取り除き、積層体６１を１分間放置した。 <Operation (v)>
After holding for 10 seconds, thebaking plate 73 and the standard weight 74 were removed, and the laminate 61 was left for 1 minute.
１０秒間保持した後、ベーク板７３および標準分銅７４を取り除き、積層体６１を１分間放置した。 <Operation (v)>
After holding for 10 seconds, the
上記操作（ｉｖ）～（ｖ）の動作を１０回繰り返し、各実施例及び各比較例に係る電磁波シールドフィルムの保護層を目視で観察し、耐屈曲性を評価した。
評価基準は以下の通りである。結果を表１に示す。
◎：クラックが観察されなかった
○：クラックが観察されたが、クラック箇所から保護層の下の層（銅層）は露出しなかった
×：クラックが観察され、クラック箇所から保護層の下の層（銅層）が露出した The above operations (iv) to (v) were repeated 10 times, and the protective layer of the electromagnetic wave shielding film according to each example and each comparative example was visually observed to evaluate the bending resistance.
Evaluation criteria are as follows. Table 1 shows the results.
◎: No cracks were observed ○: Cracks were observed, but the layer (copper layer) under the protective layer was not exposed from the cracks ×: Cracks were observed, and the cracks were observed under the protective layer layer (copper layer) exposed
評価基準は以下の通りである。結果を表１に示す。
◎：クラックが観察されなかった
○：クラックが観察されたが、クラック箇所から保護層の下の層（銅層）は露出しなかった
×：クラックが観察され、クラック箇所から保護層の下の層（銅層）が露出した The above operations (iv) to (v) were repeated 10 times, and the protective layer of the electromagnetic wave shielding film according to each example and each comparative example was visually observed to evaluate the bending resistance.
Evaluation criteria are as follows. Table 1 shows the results.
◎: No cracks were observed ○: Cracks were observed, but the layer (copper layer) under the protective layer was not exposed from the cracks ×: Cracks were observed, and the cracks were observed under the protective layer layer (copper layer) exposed
（ブロッキング試験）
図６は、ブロッキング試験を模式的に示す図である。
以下の方法で、保護層の耐ブロッキング性を評価した。 (Blocking test)
FIG. 6 is a diagram schematically showing a blocking test.
The blocking resistance of the protective layer was evaluated by the following method.
図６は、ブロッキング試験を模式的に示す図である。
以下の方法で、保護層の耐ブロッキング性を評価した。 (Blocking test)
FIG. 6 is a diagram schematically showing a blocking test.
The blocking resistance of the protective layer was evaluated by the following method.
まず、厚み５０μｍ、縦寸法４０ｍｍ、横寸法４０ｍｍのポリエチレンテレフタレートフィルム８０の上面に、各実施例及び各比較例に係る保護層用組成物を塗工し、電気オーブンを用い、１００℃で２分間加熱し、厚さ５μｍの保護層を作製することにより、ブロッキング試験用試験体８１を作製した。
First, the upper surface of a polyethylene terephthalate film 80 having a thickness of 50 μm, a vertical dimension of 40 mm, and a horizontal dimension of 40 mm was coated with the protective layer composition according to each example and each comparative example, and was heated at 100° C. for 2 minutes using an electric oven. A specimen 81 for blocking test was produced by heating and producing a protective layer having a thickness of 5 μm.
次に、図６に示すように、アルミニウム板９１の上に、保護層２０が下に位置し、ポリエチレンテレフタレートフィルム８０が上に位置するように、ブロッキング試験用試験体８１を２枚重ね、その上にアルミニウム板９２を配置した。
そして、アルミニウム板９１及びアルミニウム板９２の上下から２ｋｇの圧力をかけ、常温で３日間その状態を維持した。
その後、ブロッキング試験用試験体８１を取り出し、ブロッキングが生じているかを観察し、耐ブロッキング性を評価した。
評価基準は以下の通りである。結果を表１に示す。
〇：ブロッキング試験用試験体８１が容易に剥がれ、ブロッキングが生じていなかった。
×：一方のブロッキング試験用試験体８１の保護層２０と、もう一方のブロッキング試験用試験体８１のポリエチレンテレフタレートフィルム８０とがくっついており、各ブロッキング試験用試験体８１が剥がれにくく、ブロッキングが生じていた。 Next, as shown in FIG. 6, twospecimens 81 for blocking test are stacked on the aluminum plate 91 so that the protective layer 20 is positioned below and the polyethylene terephthalate film 80 is positioned above. An aluminum plate 92 was placed on top.
Then, a pressure of 2 kg was applied from above and below thealuminum plate 91 and the aluminum plate 92, and this state was maintained at room temperature for 3 days.
After that, the blockingtest specimen 81 was taken out, and whether or not blocking occurred was observed to evaluate the blocking resistance.
Evaluation criteria are as follows. Table 1 shows the results.
◯: Thespecimen 81 for blocking test was easily peeled off, and no blocking occurred.
x: Theprotective layer 20 of one blocking test specimen 81 and the polyethylene terephthalate film 80 of the other blocking test specimen 81 are stuck together, and each blocking test specimen 81 is difficult to peel off, causing blocking. was
そして、アルミニウム板９１及びアルミニウム板９２の上下から２ｋｇの圧力をかけ、常温で３日間その状態を維持した。
その後、ブロッキング試験用試験体８１を取り出し、ブロッキングが生じているかを観察し、耐ブロッキング性を評価した。
評価基準は以下の通りである。結果を表１に示す。
〇：ブロッキング試験用試験体８１が容易に剥がれ、ブロッキングが生じていなかった。
×：一方のブロッキング試験用試験体８１の保護層２０と、もう一方のブロッキング試験用試験体８１のポリエチレンテレフタレートフィルム８０とがくっついており、各ブロッキング試験用試験体８１が剥がれにくく、ブロッキングが生じていた。 Next, as shown in FIG. 6, two
Then, a pressure of 2 kg was applied from above and below the
After that, the blocking
Evaluation criteria are as follows. Table 1 shows the results.
◯: The
x: The
表１に示すように、保護層に含まれるウレタン樹脂の酸価が２０００～４０００ｇ／ｅｑであると、耐屈曲性が良好になることが判明した。
また、保護層に含まれるウレタン樹脂のＴｇが０℃以上であると、ブロッキングが生じにくくなることが判明した。
また、保護層に平均粒径が１０μｍ以下の非導電性フィラーが、保護層の全体重量に対し、１０～４０重量％含まれると、耐湿性及び耐屈曲性が向上することが判明した。 As shown in Table 1, it was found that when the acid value of the urethane resin contained in the protective layer was 2000 to 4000 g/eq, the flex resistance was improved.
Further, it was found that when the Tg of the urethane resin contained in the protective layer is 0° C. or higher, blocking hardly occurs.
It was also found that when the protective layer contains 10 to 40% by weight of a non-conductive filler having an average particle size of 10 μm or less relative to the total weight of the protective layer, the moisture resistance and flex resistance are improved.
また、保護層に含まれるウレタン樹脂のＴｇが０℃以上であると、ブロッキングが生じにくくなることが判明した。
また、保護層に平均粒径が１０μｍ以下の非導電性フィラーが、保護層の全体重量に対し、１０～４０重量％含まれると、耐湿性及び耐屈曲性が向上することが判明した。 As shown in Table 1, it was found that when the acid value of the urethane resin contained in the protective layer was 2000 to 4000 g/eq, the flex resistance was improved.
Further, it was found that when the Tg of the urethane resin contained in the protective layer is 0° C. or higher, blocking hardly occurs.
It was also found that when the protective layer contains 10 to 40% by weight of a non-conductive filler having an average particle size of 10 μm or less relative to the total weight of the protective layer, the moisture resistance and flex resistance are improved.
１ シールドプリント配線板
２ 試験用シールド基板
１０、１１０ 電磁波シールドフィルム
２０、１２０ 保護層
３０ 金属層
４０、１４０ 導電性接着剤層
５０ プリント配線板
５１ ベースフィルム
５２ プリント回路
５２ａ グランド回路
５２ｂ 金属パッド
５３ カバーレイ
５３ａ 開口部
５５ 試験基板
６０ 試験用プリント配線基板
６１ 積層体
７１、７３ ベーク板
７２ ガラスエポキシ板
７４ 標準分銅
８０ ポリエチレンテレフタレートフィルム
８１ ブロッキング試験用試験体
９１、９２ アルミニウム板
1 shield printedwiring board 2 test shield substrates 10, 110 electromagnetic shielding films 20, 120 protective layer 30 metal layers 40, 140 conductive adhesive layer 50 printed wiring board 51 base film 52 printed circuit 52a ground circuit 52b metal pad 53 cover Ray 53a Opening 55 Test board 60 Test printed wiring board 61 Laminate 71, 73 Bake plate 72 Glass epoxy plate 74 Standard weight 80 Polyethylene terephthalate film 81 Blocking test specimen 91, 92 Aluminum plate
２ 試験用シールド基板
１０、１１０ 電磁波シールドフィルム
２０、１２０ 保護層
３０ 金属層
４０、１４０ 導電性接着剤層
５０ プリント配線板
５１ ベースフィルム
５２ プリント回路
５２ａ グランド回路
５２ｂ 金属パッド
５３ カバーレイ
５３ａ 開口部
５５ 試験基板
６０ 試験用プリント配線基板
６１ 積層体
７１、７３ ベーク板
７２ ガラスエポキシ板
７４ 標準分銅
８０ ポリエチレンテレフタレートフィルム
８１ ブロッキング試験用試験体
９１、９２ アルミニウム板
1 shield printed
Claims (8)
- 保護層と、シールド層とが積層された電磁波シールドフィルムであって、
前記保護層は、酸価が２０００～４０００ｇ／ｅｑ、かつ、Ｔｇが０℃以上であるウレタン系樹脂と、平均粒径が１０μｍ以下である非導電性フィラーとを含み、
前記保護層の全体重量に対する前記非導電性フィラーの重量割合は、１０～４０重量％であることを特徴とする電磁波シールドフィルム。 An electromagnetic wave shielding film in which a protective layer and a shield layer are laminated,
The protective layer contains a urethane resin having an acid value of 2000 to 4000 g/eq and a Tg of 0° C. or higher, and a non-conductive filler having an average particle size of 10 μm or less,
An electromagnetic wave shielding film, wherein the weight ratio of the non-conductive filler with respect to the total weight of the protective layer is 10 to 40% by weight. - 前記保護層が、さらにエポキシ系樹脂を含む請求項１に記載の電磁波シールドフィルム。 The electromagnetic wave shielding film according to claim 1, wherein the protective layer further contains an epoxy resin.
- 前記ウレタン系樹脂と、前記エポキシ系樹脂との重量比が、ウレタン系樹脂／エポキシ系樹脂＝４～４９である請求項２に記載の電磁波シールドフィルム。 3. The electromagnetic wave shielding film according to claim 2, wherein the weight ratio of said urethane-based resin and said epoxy-based resin is urethane-based resin/epoxy-based resin=4-49.
- 前記ウレタン系樹脂のＴｇが、０～６０℃である請求項１～３のいずれかに記載の電磁波シールドフィルム。 The electromagnetic wave shielding film according to any one of claims 1 to 3, wherein the urethane resin has a Tg of 0 to 60°C.
- 前記ウレタン系樹脂の重量平均分子量は、１００，０００～２，０００，０００である請求項１～４のいずれかに記載の電磁波シールドフィルム。 The electromagnetic wave shielding film according to any one of claims 1 to 4, wherein the urethane resin has a weight average molecular weight of 100,000 to 2,000,000.
- 前記非導電性フィラーは、シリカ及び有機リン酸塩からなる群から選択される少なくとも１種である請求項１～５のいずれかに記載の電磁波シールドフィルム。 The electromagnetic wave shielding film according to any one of claims 1 to 5, wherein the non-conductive filler is at least one selected from the group consisting of silica and organic phosphates.
- 前記シールド層は、導電性接着剤層である請求項１～６のいずれかに記載の電磁波シールドフィルム。 The electromagnetic wave shielding film according to any one of claims 1 to 6, wherein the shield layer is a conductive adhesive layer.
- 前記シールド層は、金属層であり、
前記シールド層の前記保護層が積層されていない側の面には、さらに接着剤層が積層されている請求項１～６のいずれかに記載の電磁波シールドフィルム。
The shield layer is a metal layer,
The electromagnetic wave shielding film according to any one of claims 1 to 6, further comprising an adhesive layer laminated on the side of the shield layer on which the protective layer is not laminated.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020227028896A KR102558231B1 (en) | 2021-02-24 | 2022-02-22 | electromagnetic wave shielding film |
| CN202280004051.4A CN115486215B (en) | 2021-02-24 | 2022-02-22 | Electromagnetic wave shielding film |
| JP2022541965A JP7206441B1 (en) | 2021-02-24 | 2022-02-22 | electromagnetic wave shielding film |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-027524 | 2021-02-24 | ||
| JP2021027524 | 2021-02-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022181570A1 true WO2022181570A1 (en) | 2022-09-01 |
Family
ID=83048076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2022/007068 WO2022181570A1 (en) | 2021-02-24 | 2022-02-22 | Electromagentic wave shield film |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7206441B1 (en) |
| KR (1) | KR102558231B1 (en) |
| CN (1) | CN115486215B (en) |
| TW (1) | TW202234982A (en) |
| WO (1) | WO2022181570A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008140007A1 (en) * | 2007-05-09 | 2008-11-20 | Toray Industries, Inc. | Conductive board, electromagnetic shielding board for plasma display and method for manufacturing conductive board |
| WO2016088381A1 (en) * | 2014-12-05 | 2016-06-09 | タツタ電線株式会社 | Electromagnetic wave shielding film |
| WO2018047957A1 (en) * | 2016-09-09 | 2018-03-15 | タツタ電線株式会社 | Conductive adhesive composition |
| WO2019012590A1 (en) * | 2017-07-10 | 2019-01-17 | タツタ電線株式会社 | Electromagnetic wave shield film, and shielded printed wiring board equipped with same |
| WO2020218507A1 (en) * | 2019-04-24 | 2020-10-29 | 三菱ケミカル株式会社 | Thermoplastic polyurethane resin elastomer |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015129226A (en) * | 2014-01-08 | 2015-07-16 | 日東電工株式会社 | Film type adhesive, dicing tape with film type adhesive, method for manufacturing semiconductor device, and semiconductor device |
| JP6723146B2 (en) * | 2016-11-30 | 2020-07-15 | 三菱電機株式会社 | Driving equipment and driving equipment system |
| JP2019046871A (en) | 2017-08-30 | 2019-03-22 | タツタ電線株式会社 | Electromagnetic wave shield film, shield printed wiring board, and method for manufacturing shield printed wiring board |
| CN107880530B (en) * | 2017-12-25 | 2020-10-27 | 广东生益科技股份有限公司 | Halogen-free resin composition, cover film and preparation method thereof |
| TW201943330A (en) | 2018-03-29 | 2019-11-01 | 日商拓自達電線股份有限公司 | Resin composition for protective layer of electromagnetic wave-shielding film, electromagnetic wave-shielding film, and method for producing electromagnetic wave-shielding film |
| JP7070061B2 (en) * | 2018-05-11 | 2022-05-18 | Dic株式会社 | Conductive adhesive composition |
| KR20210014107A (en) * | 2018-05-29 | 2021-02-08 | 주식회사 쿠라레 | Reinforcing fiber and manufacturing method thereof, and molded article using the same |
| JP2020119964A (en) * | 2019-01-22 | 2020-08-06 | 東洋インキＳｃホールディングス株式会社 | Electromagnetic wave shield sheet-attached printed wiring board |
| JP6904464B2 (en) * | 2019-06-12 | 2021-07-14 | 東洋インキＳｃホールディングス株式会社 | Printed wiring board |
| TW202111001A (en) * | 2019-06-28 | 2021-03-16 | 日商東亞合成股份有限公司 | Resin composition, laminate having resin composition layer, laminate, and electromagnetic wave shielding film |
-
2021
- 2021-11-12 TW TW110142284A patent/TW202234982A/en unknown
-
2022
- 2022-02-22 JP JP2022541965A patent/JP7206441B1/en active Active
- 2022-02-22 WO PCT/JP2022/007068 patent/WO2022181570A1/en active Application Filing
- 2022-02-22 CN CN202280004051.4A patent/CN115486215B/en active Active
- 2022-02-22 KR KR1020227028896A patent/KR102558231B1/en active IP Right Grant
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008140007A1 (en) * | 2007-05-09 | 2008-11-20 | Toray Industries, Inc. | Conductive board, electromagnetic shielding board for plasma display and method for manufacturing conductive board |
| WO2016088381A1 (en) * | 2014-12-05 | 2016-06-09 | タツタ電線株式会社 | Electromagnetic wave shielding film |
| WO2018047957A1 (en) * | 2016-09-09 | 2018-03-15 | タツタ電線株式会社 | Conductive adhesive composition |
| WO2019012590A1 (en) * | 2017-07-10 | 2019-01-17 | タツタ電線株式会社 | Electromagnetic wave shield film, and shielded printed wiring board equipped with same |
| WO2020218507A1 (en) * | 2019-04-24 | 2020-10-29 | 三菱ケミカル株式会社 | Thermoplastic polyurethane resin elastomer |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102558231B1 (en) | 2023-07-20 |
| CN115486215A (en) | 2022-12-16 |
| JPWO2022181570A1 (en) | 2022-09-01 |
| TW202234982A (en) | 2022-09-01 |
| CN115486215B (en) | 2023-08-11 |
| JP7206441B1 (en) | 2023-01-17 |
| KR20220123474A (en) | 2022-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101956091B1 (en) | Electromagnetic wave shielding film | |
| CN105451529B (en) | Electromagnetic shielding film, flexible printing wiring board and their manufacturing method | |
| WO2020129985A1 (en) | Electronic component mounting substrate and electronic apparatus | |
| WO2019239710A1 (en) | Electromagnetic wave shielding sheet | |
| JP2006232985A (en) | Non-halogen adhesive composition, and coverlay film and adhesive sheet obtained using the same | |
| JP7232996B2 (en) | Electronic component mounting board and electronic equipment | |
| JP6468389B1 (en) | Laminated body, component mounting board, and method for manufacturing component mounting board | |
| JP2012097197A (en) | Flame-retardant adhesive composition and adhesive sheet and coverlay film using the same | |
| KR20190065158A (en) | Electromagnetic wave shield film | |
| JP2016111172A (en) | Composite electromagnetic wave suppressor | |
| JP2017092417A (en) | Electromagnetic wave shield film and electromagnetic wave shield film-attached printed wiring board | |
| JP7206441B1 (en) | electromagnetic wave shielding film | |
| JP2006169446A (en) | Adhesive composition and cover lay film | |
| WO2020095919A1 (en) | Electromagnetic shielding film, method for manufacturing electromagnetic shielding film, and method for manufacturing shielded printed wiring board | |
| JP2012097195A (en) | Flame-retardant adhesive composition and adhesive sheet and coverlay film using the same | |
| JP7056723B2 (en) | Parts set | |
| KR101970484B1 (en) | Conductive bonding sheet for fpc and fpc | |
| JP2000158589A (en) | Manufacture of metal foil clad laminated sheet | |
| JP2017092415A (en) | Electromagnetic wave shield film and electromagnetic wave shield film-attached printed wiring board | |
| JPS60243180A (en) | Adhesive and flexibile base for printed circuit | |
| CN115024029A (en) | Electromagnetic wave shielding film | |
| WO2023090334A1 (en) | Electromagnetic wave shield film | |
| JP2824149B2 (en) | Coverlay film | |
| KR100827756B1 (en) | Thermosetting adhesive agent and adhesive film using the same | |
| JP2021093501A (en) | Electronic component mounting substrate and electronic apparatus using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| ENP | Entry into the national phase |
Ref document number: 2022541965 Country of ref document: JP Kind code of ref document: A |
|
| ENP | Entry into the national phase |
Ref document number: 20227028896 Country of ref document: KR Kind code of ref document: A |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22759606 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 22759606 Country of ref document: EP Kind code of ref document: A1 |