TWI823894B - 接著劑組合物、熱硬化性接著片材及印刷配線板 - Google Patents
接著劑組合物、熱硬化性接著片材及印刷配線板 Download PDFInfo
- Publication number
- TWI823894B TWI823894B TW108104102A TW108104102A TWI823894B TW I823894 B TWI823894 B TW I823894B TW 108104102 A TW108104102 A TW 108104102A TW 108104102 A TW108104102 A TW 108104102A TW I823894 B TWI823894 B TW I823894B
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- Taiwan
- Prior art keywords
- adhesive composition
- mass
- parts
- epoxy resin
- polyphenylene ether
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims abstract description 75
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 74
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 46
- 239000003822 epoxy resin Substances 0.000 claims abstract description 46
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 46
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 39
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 36
- 229920001971 elastomer Polymers 0.000 claims abstract description 24
- 239000000806 elastomer Substances 0.000 claims abstract description 24
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 32
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 18
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 18
- 239000012790 adhesive layer Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 238000005452 bending Methods 0.000 abstract description 27
- -1 vinylbenzyl Chemical group 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 239000011889 copper foil Substances 0.000 description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000005856 abnormality Effects 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 229920006132 styrene block copolymer Polymers 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000004849 latent hardener Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000009661 fatigue test Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- 239000004727 Noryl Substances 0.000 description 1
- 229920001207 Noryl Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
-
- 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
-
- 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
- C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
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- C09J125/04—Homopolymers or copolymers of styrene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
- C08L65/02—Polyphenylenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
- C09J165/02—Polyphenylenes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C09J171/12—Polyphenylene oxides
-
- 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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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Abstract
本發明提供一種介電常數及介電損耗正切低、且耐彎曲性良好之接著劑組合物。
接著劑組合物中,相對於該接著劑組合物之合計100質量份,含有苯乙烯系彈性體75~90質量份、末端具有聚合性基之改性聚苯醚樹脂3~25質量份,及環氧樹脂及環氧樹脂硬化劑合計10質量份以下。
Description
本發明係關於一種接著劑組合物、熱硬化性接著片材及印刷配線板。本申請案係以2018年2月5日於日本提出申請之日本專利申請號特願2018-018177為基礎要求優先權者,藉由參考該申請而援引於本申請。
由於資訊通信之高速、大容量化,流經印刷配線板之信號之高頻化傾向加速。為了應對此情況,對剛性基板或柔性印刷配線板(FPC)之構成材料(例如接著劑組合物)要求低介電常數、低介電損耗正切等低介電特性(例如,參考專利文獻1、2)。
然而,聚苯醚雖作為具有低介電特性之基板用材料優點亦較多,但存在熔點(軟化點)非常高、常溫下具有較硬之性質故而耐彎曲性變差之難點。例如,如專利文獻2所記載之樹脂組合物,若相對於樹脂整體以聚苯醚構成3~5成左右,則存在耐彎曲性變差之傾向。
[先前技術文獻]
[專利文獻]
專利文獻1:日本專利特開2017-57346號公報
專利文獻2:日本專利特開2016-79354號公報
[發明所欲解決之問題]
本發明係鑒於此種先前之實際情況而揭示者,提供一種介電常數及介電損耗正切較低且耐彎曲性良好之接著劑組合物、熱硬化性接著片材及印刷配線板。
[解決問題之技術手段]
本發明之接著劑組合物中,相對於該接著劑組合物之合計100質量份,含有苯乙烯系彈性體75~90質量份、末端具有聚合性基之改性聚苯醚樹脂3~25質量份、及環氧樹脂及環氧樹脂硬化劑合計10質量份以下。
本發明之熱硬化性接著片材於基材上形成有含有上述接著劑組合物之熱硬化性接著層。
本發明之印刷配線板經由上述接著劑組合物之硬化物,積層有具備基材與配線圖案之付配線樹脂基板之上述配線圖案側、與覆蓋層。
[發明之效果]
根據本發明,可提供一種介電常數及介電損耗正切較低、耐彎曲性良好之接著劑組合物。
以下,對本發明之實施形態進行說明。以下所說明之成分之重量平均分子量及數量平均分子量之值係指根據藉由凝膠滲透層析(GPC)法測定之標準聚苯乙烯換算之分子量算出之值。
<接著劑組合物>
本發明之接著劑組合物係熱硬化性之接著劑組合物,相對於該接著劑組合物之合計100質量份,含有苯乙烯系彈性體(成分A)75~90質量份、末端具有聚合性基之改性聚苯醚樹脂(成分B;以下,簡稱為改性聚苯醚樹脂)3~25質量份、及環氧樹脂(成分C)及環氧樹脂硬化劑(成分D)合計10質量份以下。藉由此種構成,可製成熱硬化後介電常數及介電損耗正切亦較低、熱硬化後耐彎曲性亦良好之接著劑組合物。此種接著劑組合物例如可較佳地用作柔性印刷配線板用之接著劑(層間接著劑)。
[苯乙烯系彈性體]
苯乙烯系彈性體係苯乙烯與烯烴(例如,丁二烯、異戊二烯等共軛二烯)之共聚物及/或其氫化物。苯乙烯系彈性體係以苯乙烯為硬鏈段、以共軛二烯為軟鏈段之嵌段共聚物。作為苯乙烯系彈性體之例,可列舉:苯乙烯/丁二烯/苯乙烯嵌段共聚物、苯乙烯/異戊二烯/苯乙烯嵌段共聚物、苯乙烯/乙烯/丁烯/苯乙烯嵌段共聚物、苯乙烯/乙烯/丙烯/苯乙烯嵌段共聚物、苯乙烯/丁二烯嵌段共聚物等。又,亦可使用藉由氫化消除共軛二烯成分之雙鍵而得之苯乙烯/乙烯/丁烯/苯乙烯嵌段共聚物、苯乙烯/乙烯/丙烯/苯乙烯嵌段共聚物、苯乙烯/丁二烯嵌段共聚物(亦稱為經氫化之苯乙烯系彈性體)等。
苯乙烯系彈性體之重量平均分子量較佳為100000以上,更佳為100000~150000,進而較佳為110000~150000。藉由製成此種構成,可使剝離強度(連接可靠性)、耐熱性更加良好。
苯乙烯系彈性體中之苯乙烯比率較佳為未達30%,更佳為5~30%,進而較佳為5~25%,特佳為10~20%。藉由製成此種構成,可使耐彎曲性更加良好,可使剝離強度(連接可靠性)、耐熱性更加良好。
作為苯乙烯系彈性體之具體例,可列舉:Tuftec H1221(Mw120000、苯乙烯比率10%)、Tuftec H1041(Mw90000、苯乙烯比率30%)、Tuftec H1043(Mw110000、苯乙烯比率67%,以上為旭化成公司製造)、HYBRAR 7125(Mw110000、苯乙烯比率20%、可樂麗公司製造)。該等中,就分子量或苯乙烯比率之觀點而言,較佳為Tuftec H1221、HYBRAR 7125。
接著劑組合物中之苯乙烯系彈性體之含量相對於成分A、成分B、成分C及成分D之合計100質量份,為75~90質量份,亦可為80~90質量份。若苯乙烯系彈性體之含量未達75質量份,則存在耐彎曲性變差之傾向。又,若苯乙烯系彈性體之含量超過90質量份,則相對而言其他成分(例如成分B)之含量變少,故而存在耐熱性變差之傾向。苯乙烯系彈性體可單獨使用1種,亦可併用2種以上。
[改性聚苯醚樹脂]
改性聚苯醚樹脂於分子中具有聚苯醚鏈,於末端具有聚合性基。改性聚苯醚樹脂較佳為於1個分子中作為聚合性基具有2個以上環氧基及乙烯性不飽和鍵之至少1種。尤其,就與上述苯乙烯系彈性體之相容性或接著劑組合物之介電特性之觀點而言,改性聚苯醚樹脂較佳為於兩末端具有環氧基及乙烯性不飽和鍵(例如,(甲基)丙烯醯基、乙烯基苄基)之至少1種。
再者,未經具有聚合性基之化合物改性之聚苯醚樹脂,即末端具有羥基之聚苯醚樹脂由於極性過強,故而有與上述苯乙烯系彈性體之相容性較差,無法使接著劑組合物成膜之虞,欠佳。
作為改性聚苯醚樹脂之一例的兩末端具有乙烯基苄基之改性聚苯醚樹脂例如藉由將使2官能基酚化合物與1官能基酚化合物氧化偶合而獲得之2官能基苯醚低聚物之末端酚性羥基進行乙烯基苄醚化而獲得。
改性聚苯醚樹脂之重量平均分子量(或數量平均分子量)就與上述苯乙烯系彈性體之相容性、或經由接著劑組合物之硬化物將具備基材與配線圖案之付配線樹脂基板之配線圖案側與覆蓋層熱硬化(壓製)時之階差追隨性等觀點而言,較佳為1000~3000。
作為改性聚苯醚樹脂之具體例,可使用:OPE-2St(兩末端具有乙烯基苄基之改性聚苯醚樹脂)、OPE-2Gly(兩末端具有環氧基之改性聚苯醚樹脂)、OPE-2EA(兩末端具有丙烯醯基之改性聚苯醚樹脂,以上為三菱瓦斯化學公司製造)、Noryl SA9000(兩末端具有甲基丙烯醯基之改性聚苯醚樹脂、SABIC公司製造)等。
接著劑組合物中之改性聚苯醚樹脂之含量相對於成分A、成分B、成分C及成分D之合計100質量份,為3~25質量份,較佳為5~20質量份。若改性聚苯醚樹脂之含量超過25質量份,則存在耐彎曲性變差之傾向。又,藉由將改性聚苯醚樹脂之含量設為5質量份以上,可使耐熱性更加良好。聚苯醚樹脂可單獨使用1種,亦可併用2種以上。
[環氧樹脂]
環氧樹脂例如可列舉:具有萘骨架之環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、酚系酚醛清漆型環氧樹脂、脂環式環氧樹脂、矽氧烷型環氧樹脂、聯苯型環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、乙內醯脲型環氧樹脂等。尤其,環氧樹脂就膜之成形性之觀點而言,較佳為具有萘骨架之環氧樹脂、雙酚A型環氧樹脂或雙酚F型環氧樹脂,即於常溫下為液狀者。環氧樹脂可單獨使用1種,亦可併用2種以上。
[環氧樹脂硬化劑]
環氧樹脂硬化劑係促進上述環氧樹脂之硬化反應之觸媒。作為環氧樹脂硬化劑,例如可使用:咪唑系、酚系、胺系、酸酐系、有機過氧化物系等。尤其,環氧樹脂硬化劑就接著劑組合物之常溫下之保存性(壽命)之觀點而言,較佳為具有潛在性之硬化劑,更佳為經膠囊化而具有潛在性之咪唑系硬化劑。由於常溫下之保存性良好,可使接著劑組合物之供給或使用之管理更加簡便。具體而言,作為環氧樹脂硬化劑,可使用以潛在性咪唑改性體為核且以聚胺基甲酸酯覆蓋其表面而成之微膠囊型潛在性硬化劑。作為市售品,例如可使用Novacure 3941(旭化成E-MATERIALS公司製造)。環氧樹脂硬化劑可單獨使用1種,亦可併用2種以上。
接著劑組合物中之環氧樹脂及環氧樹脂硬化劑之含量之合計相對於成分A、成分B、成分C及成分D之合計100質量份,為10質量份以下,較佳為5質量份以下。若環氧樹脂及環氧樹脂硬化劑之含量之合計超過10質量份,則存在介電特性變差之傾向。
[其他成分]
接著劑組合物於無損本發明之效果之範圍內,進而可含有除上述成分A~成分D以外之其他成分。作為其他成分,可列舉:有機溶劑、矽烷偶合劑、流動性調整用之填料等。有機溶劑未特別限制,但例如可列舉:醇系溶劑、酮系溶劑、醚系溶劑、芳香族系溶劑、酯系溶劑等。該等中,就溶解性之觀點而言,較佳為芳香族系溶劑、酯系溶劑。有機溶劑可單獨使用1種,亦可併用2種以上。
<熱硬化性接著片材>
本發明之熱硬化性接著片材於基材上形成有含有上述接著劑組合物之熱硬化性接著層,為膜形狀。熱硬化性接著片材例如藉由以溶劑稀釋上述接著劑組合物,並以乾燥後之厚度成為10~60 μm之方式藉由棒式塗佈機、輥式塗佈機等塗佈於基材之至少一面,於50~130℃左右之溫度下進行乾燥而獲得。基材例如可使用視需要對聚對苯二甲酸乙二酯膜、聚醯亞胺膜等基材以聚矽氧等進行剝離處理而得之剝離基材。
構成熱硬化性接著片材之熱硬化性接著層之厚度可根據目的適宜地設定,但作為一例,可設為1~100 μm,亦可設為1~30μm。
構成熱硬化性接著片材之熱硬化性接著層含有如上述熱硬化後介電常數及介電損耗正切亦較低、熱硬化後耐彎曲性亦良好之接著劑組合物,故而例如可用於柔性印刷配線板之層間接著劑或接著固定柔性印刷配線板之端子部與用於其襯底之連接用基材之用途。又,熱硬化性接著片材熱硬化後之剝離強度或耐熱性、常溫下之保存性亦良好。
<印刷配線板>
本發明之印刷配線板經由上述接著劑組合物(熱硬化性接著層)之硬化物積層有具備基材與配線圖案之付配線之基材之配線圖案側與覆蓋層。印刷配線板例如藉由於付配線之基材之配線圖案側與覆蓋層之間配置熱硬化性接著片材之熱硬化性接著層並進行熱壓接,而使付配線之基材與覆蓋層一體化而獲得。
付配線之基材與上述接著劑組合物相同,高頻區域之電特性優異,例如,較佳為於頻率1~10 GHz之區域,介電常數及介電損耗正切較低。作為基材之具體例,可列舉以液晶聚合物(LCP:Liquid Crystal Polymer)、聚四氟乙烯、聚醯亞胺及聚萘二甲酸乙二酯之任一者為主成分之基材。該等基材中,較佳為以液晶聚合物為主成分之基材(液晶聚合物膜)。由於液晶聚合物與聚醯亞胺相比,吸濕率非常低,難以被使用環境左右。
對使用本發明之接著劑組合物之印刷配線板之構成例進行說明。圖1所示之印刷配線板1係具備液晶聚合物膜2與銅箔(壓延銅箔)3之付配線之基材(銅箔積層板:CCL)之銅箔3側與液晶聚合物膜4經由含有上述接著劑組合物(熱硬化性接著層)之硬化物層5而積層。
又,印刷配線板例如可為如圖2所示之多層結構。圖2所示之印刷配線板6係具備聚醯亞胺層7(厚度25 μm)、銅箔8(厚度18 μm)及鍍銅層9(厚度10 μm)之付配線之基材之鍍銅層9側與覆蓋層10(厚度25 μm)經由含有上述接著劑組合物(熱硬化性接著層)之硬化物層5(厚度35 μm)而積層(合計厚度201 μm)。
[實施例]
以下,對本發明之實施例進行說明。再者,本發明未限定於該等實施例。
<成分A>
Tuftec H1221:氫化苯乙烯系熱塑性彈性體(Mw120000、苯乙烯比率10%)、旭化成公司製造
HYBRAR 7125:氫化苯乙烯系熱塑性彈性體(Mw110000、苯乙烯比率20%)、可樂麗公司製造
Tuftec H1041:氫化苯乙烯系熱塑性彈性體(Mw90000、苯乙烯比率30%)、旭化成公司製造
Tuftec H1043:氫化苯乙烯系熱塑性彈性體(Mw110000、苯乙烯比率67%)、旭化成公司製造
<成分B>
OPE-2St2200:兩末端具有乙烯基苄基之改性聚苯醚樹脂(Mn=2200)、三菱瓦斯化學公司製造
SA9000:兩末端具有甲基丙烯醯基之改性聚苯醚樹脂(Mw1700)、SABIC公司製造
SA120:兩末端具有羥基之聚苯醚樹脂、SABIC公司製造
S201A:兩末端具有羥基之聚苯醚樹脂、旭化成公司製造
<成分C>
4032D:萘型環氧樹脂、DIC公司製造
JER828:環氧樹脂、三菱化學公司製造
YD014:雙酚A型環氧樹脂、新日鐵住金化學公司製造
<成分D>
Novacure 3941:以咪唑改性體為核且以聚胺基甲酸酯覆蓋其表面而成之微膠囊型潛在性硬化劑、旭化成E-MATERIALS公司製造
2E4MZ:2-乙基-4-甲基咪唑(無潛在性之咪唑)
[熱硬化性接著劑組合物之製備]
以成為表1所示之質量之方式稱量表1所示之各成分,均勻地混合於含有甲苯及乙酸乙酯之有機溶劑中,藉此製備熱硬化性接著劑組合物(熱硬化性接著層形成用塗料)。
[熱硬化性片材之製作]
將所獲得之熱硬化性接著劑組合物塗佈於經剝離處理之聚對苯二甲酸乙二酯膜,於50~130℃之乾燥爐中進行乾燥,藉此製作具有聚對苯二甲酸乙二酯膜與厚度25 μm之熱硬化性接著層的熱硬化性接著片材。
[評價]
<熱硬化性接著層形成用塗料之塗佈性(膜之狀態)之評價>
製作上述熱硬化性片材時,對熱硬化性接著劑組合物之塗佈性按照以下之基準進行評價。結果示於表1。
A:接著劑組合物之相容性良好,能夠以膜狀態進行後述之評價
B:接著劑組合物之相容性較差,無法以膜狀態進行後述之評價
<介電常數>
將實施例及比較例所製作之熱硬化性接著片材彼此層壓,製作厚度1 mm之試片後,將該試片以160℃、1.0 MPa之條件熱硬化1小時,製作評價用試片。對該評價用試片使用介電常數測定裝置(AET公司製造)求得測定溫度23℃、測定頻率10 GHz下之介電常數。結果示於表1。
A:介電常數未達2.3
B:介電常數為2.3以上且未達2.4
C:介電常數為2.4以上且未達2.6
D:介電常數為2.6以上
<介電損耗正切>
以與上述介電常數之測定相同之方法對評價用試片求得介電損耗正切。結果示於表1。
A:介電損耗正切未達0.002
B:介電損耗正切為0.002以上且未達0.0035
C:介電損耗正切為0.0035以上且未達0.005
D:介電損耗正切為0.005以上
<剝離強度>
將所獲得之熱硬化性接著片材切割為規定大小之短條(2 cm×5 cm),用設定至100℃之貼合機將該切割之熱硬化性接著層暫貼於2 cm×7 cm×50 μm厚之液晶聚合物膜後,除去基材(聚對苯二甲酸乙二酯膜)使熱硬化性接著層露出。對露出之熱硬化性接著層,自上重疊相同大小之銅箔積層板(包含厚度12 μm之壓延銅箔與厚度50 μm之液晶聚合物膜之CCL)之壓延銅箔面(未進行表面粗糙化處理之面),以160℃、1.0 MPa之條件熱硬化1小時。藉此製作樣品。
對所獲得之樣品以剝離速度50 mm/min進行90度剝離試驗,測定剝離時所需之力(初始剝離強度及可靠性試驗後之剝離強度)。結果示於表1。
[初始(上述160℃、1.0 MPa之條件下之熱硬化後直接測定)]
A:剝離強度為8 N/cm以上
B:剝離強度為6 N/cm以上且未達8 N/cm
C:剝離強度為4 N/cm以上且未達6 N/cm
D:剝離強度未達4 N/cm
[可靠性試驗後(85℃、相對濕度85%、240小時(即,上述160℃、1.0 MPa之條件下之熱硬化後投入至85℃、相對濕度85%之環境240小時,取出3小時後進行測定))]
A:剝離強度為7 N/cm以上
B:剝離強度為5 N/cm以上且未達7 N/cm
C:剝離強度為3 N/cm以上且未達5 N/cm
D:剝離強度未達3 N/cm
<耐熱性>
使上述樣品經過最高溫度260℃-30秒之回焊步驟3次,確認經過後之樣品之外觀,按照下述基準評價是否產生剝離或鼓出。結果示於表1。
A:經過3次後亦無異常
B:經過2次無異常,於第3次產生剝離或鼓出等異常
C:經過1次無異常,於第2次產生剝離或鼓出等異常
D:於第1次產生剝離或鼓出等異常
<耐彎曲性>
將所獲得之熱硬化性接著片材切割為規定大小之短條(1.5 cm×12 cm),用設定至100℃之貼合機將該切割之熱硬化性接著層暫貼於1.5 cm×12 cm×50 μm厚之液晶聚合物膜後,除去基材(聚對苯二甲酸乙二酯膜)使熱硬化性接著層露出。對露出之熱硬化性接著層,重疊於MIT耐彎曲試驗用之FPC-TEG,以160℃、1.0 MPa之條件熱硬化1小時。MIT耐彎曲試驗用之TEG11之構成示於圖3。TEG11係由包括作為基材之液晶聚合物膜(厚度50 μm)與壓延銅箔(厚度12 μm)之CCL形成銅配線者。MIT耐彎曲試驗係將所製作之試片12安放於圖4所示之結構之MIT耐折疲勞試驗機13而進行。以彎折角度135°、彎折鉗角度R=0.38、試驗速度175 cpm之條件進行。確認直至銅配線斷裂為止之彎折次數。結果示於表1。
A:直至斷裂為止之彎折次數為1200次以上
B:直至斷裂為止之彎折次數為500次以上且未達1200次
C:直至斷裂為止之彎折次數為200次以上且未達500次
D:直至斷裂為止之彎折次數未達200次
<壽命評價>
將熱硬化性片材於常溫下保存4個月後,進行與上述剝離強度之評價相同之評價。確認與製作熱硬化性接著片材後即刻進行評價之剝離強度相比時之降低率。結果示於表1。
A:剝離強度之降低未達10%
B:剝離強度之降低為10%以上且未達30%
C:剝離強度之降低為30%以上
[表1]
根據表1所示之結果可知,相對於接著劑組合物之合計100質量份,含有苯乙烯系彈性體(成分A)75~90質量份、末端具有聚合性基之改性聚苯醚樹脂(成分B)3~25質量份、及環氧樹脂(成分C)及環氧樹脂硬化劑(成分D)合計10質量份以下之接著劑組合物於熱硬化後介電常數及介電損耗正切亦較低、耐彎曲性亦良好。
根據實驗例6之結果可知,若改性聚苯醚樹脂之含量超過25質量份,則耐彎曲性變差。
根據實驗例8之結果可知,若環氧樹脂及環氧樹脂硬化劑之合計量超過10質量份,則難以降低介電損耗正切。
根據實驗例11、12之結果可知,若使用末端具有羥基之聚苯醚樹脂,則膜狀態較差,或介電特性及耐彎曲性變差。再者,實驗例12中,由於膜之狀態變差,故而無法進行介電常數、介電損耗正切、剝離強度、耐熱性、耐彎曲性之評價。
根據實驗例之結果可知,藉由將改性聚苯醚樹脂之含量設為5~20質量份,介電常數及介電損耗正切較低,耐彎曲性良好,進而耐熱性亦良好。
根據實驗例之結果可知,藉由將苯乙烯系彈性體之質量平均分子量設為100000以上,可使剝離強度、耐熱性及耐彎曲性更加良好。
根據實驗例之結果可知,藉由將苯乙烯系彈性體之苯乙烯比率設為未達30%,可使介電特性、剝離強度、耐熱性及耐彎曲性更加良好。
根據實驗例之結果可知,藉由使用液狀之環氧樹脂,可使剝離強度、耐熱性及耐彎曲性更加良好。
根據實驗例之結果可知,藉由使用具有潛在性之環氧樹脂硬化劑,亦可使常溫下之保存性良好。
根據實驗例3、7、14之結果可知,雖於10 GHz下介電常數(Dk)為2.3以下、介電損耗正切(Df)未達0.002,顯示非常低之值,但對液晶聚合物膜與未實施表面粗糙化處理之壓延銅箔顯示8 N/cm以上之非常高之接著強度。
1‧‧‧印刷配線板
2‧‧‧液晶聚合物膜
3‧‧‧銅箔
4‧‧‧液晶聚合物膜
5‧‧‧含有接著劑組合物之硬化物層
6‧‧‧印刷配線板
7‧‧‧聚醯亞胺層
8‧‧‧銅箔
9‧‧‧鍍銅層
10‧‧‧覆蓋層
11‧‧‧TEG
12‧‧‧試片
13‧‧‧MIT耐折疲勞試驗機
14‧‧‧柱塞
15‧‧‧上部夾頭
16‧‧‧旋轉夾頭
17‧‧‧彎折齒輪齒
圖1係表示印刷配線板之構成例之剖視圖。
圖2係表示多層印刷配線板之構成例之剖視圖。
圖3係表示用於耐彎曲性試驗之TEG(Test Element Group,測試元件組)之構成例之俯視圖。
圖4係表示用於耐彎曲性試驗之測定裝置之立體圖。
1‧‧‧印刷配線板
2‧‧‧液晶聚合物膜
3‧‧‧銅箔
4‧‧‧液晶聚合物膜
5‧‧‧含有接著劑組合物之硬化物層
Claims (8)
- 一種接著劑組合物,其相對於該接著劑組合物之合計100質量份含有苯乙烯系彈性體75~90質量份、末端具有聚合性基之改性聚苯醚樹脂3~25質量份、環氧樹脂硬化劑1~3質量份、及環氧樹脂及環氧樹脂硬化劑合計10質量份以下,上述苯乙烯系彈性體之質量平均分子量為100000以上。
- 如請求項1之接著劑組合物,其中上述苯乙烯系彈性體之苯乙烯比率為5%以上且30%以下。
- 如請求項1或2之接著劑組合物,其含有上述改性聚苯醚樹脂5~20質量份。
- 如請求項1或2之接著劑組合物,其中上述改性聚苯醚樹脂於末端具有環氧基及乙烯性不飽和鍵之至少1種。
- 如請求項1或2之接著劑組合物,其中上述環氧樹脂硬化劑係具有潛在性之環氧樹脂硬化劑。
- 一種熱硬化性接著片材,其於基材上形成有含有如請求項1至5中任一項之接著劑組合物之熱硬化性接著層。
- 一種印刷配線板,其經由如請求項1至5中任一項之接著劑組合物之硬化物,積層有具備基材與配線圖案之付配線樹脂基板之上述配線圖案側與覆蓋層。
- 如請求項7之印刷配線板,其中上述基材係液晶聚合物膜。
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CN111742029A (zh) | 2020-10-02 |
KR102445337B1 (ko) | 2022-09-20 |
TW201936849A (zh) | 2019-09-16 |
WO2019151014A1 (ja) | 2019-08-08 |
EP3750966A4 (en) | 2021-12-01 |
US20210040360A1 (en) | 2021-02-11 |
CN111742029B (zh) | 2023-11-07 |
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