KR20220169914A - Adhesive agent, adhesive sheet and flexible copper clad laminate - Google Patents
Adhesive agent, adhesive sheet and flexible copper clad laminate Download PDFInfo
- Publication number
- KR20220169914A KR20220169914A KR1020220073976A KR20220073976A KR20220169914A KR 20220169914 A KR20220169914 A KR 20220169914A KR 1020220073976 A KR1020220073976 A KR 1020220073976A KR 20220073976 A KR20220073976 A KR 20220073976A KR 20220169914 A KR20220169914 A KR 20220169914A
- Authority
- KR
- South Korea
- Prior art keywords
- adhesive
- resin
- weight
- fccl
- copper foil
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims abstract description 113
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 113
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052802 copper Inorganic materials 0.000 title description 10
- 239000010949 copper Substances 0.000 title description 10
- 229920001721 polyimide Polymers 0.000 claims abstract description 99
- 239000011889 copper foil Substances 0.000 claims abstract description 60
- 239000003822 epoxy resin Substances 0.000 claims abstract description 50
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 48
- 239000004642 Polyimide Substances 0.000 claims abstract description 46
- 239000013034 phenoxy resin Substances 0.000 claims abstract description 32
- 229920006287 phenoxy resin Polymers 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 230000009477 glass transition Effects 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims description 49
- 239000012790 adhesive layer Substances 0.000 claims description 47
- 239000009719 polyimide resin Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- VNAFWALXWOAPCK-UHFFFAOYSA-N 1-phenyl-2,3-dihydro-1h-indene Chemical group C1CC2=CC=CC=C2C1C1=CC=CC=C1 VNAFWALXWOAPCK-UHFFFAOYSA-N 0.000 claims description 13
- 238000010030 laminating Methods 0.000 claims description 11
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000006157 aromatic diamine group Chemical group 0.000 claims 1
- 230000003746 surface roughness Effects 0.000 claims 1
- 238000003475 lamination Methods 0.000 abstract description 19
- 238000005266 casting Methods 0.000 abstract description 15
- 230000037303 wrinkles Effects 0.000 abstract description 9
- 239000004848 polyfunctional curative Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 73
- 239000011347 resin Substances 0.000 description 73
- 239000010410 layer Substances 0.000 description 49
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 239000000203 mixture Substances 0.000 description 25
- 238000001723 curing Methods 0.000 description 24
- 239000010408 film Substances 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 20
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 15
- 239000002966 varnish Substances 0.000 description 15
- 150000004984 aromatic diamines Chemical group 0.000 description 14
- 239000004593 Epoxy Substances 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 229920003986 novolac Polymers 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 10
- 239000011162 core material Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
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- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 150000004982 aromatic amines Chemical class 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 8
- 229920006259 thermoplastic polyimide Polymers 0.000 description 8
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- 238000012661 block copolymerization Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
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- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
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- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 4
- 239000002313 adhesive film Substances 0.000 description 4
- -1 aromatic tetracarboxylic acid Chemical class 0.000 description 4
- 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 4
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- 125000004427 diamine group Chemical group 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000006358 imidation reaction Methods 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 4
- 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 3
- GDGWSSXWLLHGGV-UHFFFAOYSA-N 3-(4-aminophenyl)-1,1,3-trimethyl-2h-inden-5-amine Chemical compound C12=CC(N)=CC=C2C(C)(C)CC1(C)C1=CC=C(N)C=C1 GDGWSSXWLLHGGV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 3
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical group C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
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- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
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- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
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- 239000003431 cross linking reagent Substances 0.000 description 1
- CURBACXRQKTCKZ-UHFFFAOYSA-N cyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)C(C(O)=O)C1C(O)=O CURBACXRQKTCKZ-UHFFFAOYSA-N 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VXWFEQQIKVSOMK-UHFFFAOYSA-N oxalic acid;pyridine Chemical compound C1=CC=NC=C1.OC(=O)C(O)=O VXWFEQQIKVSOMK-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 230000037330 wrinkle prevention Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
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- 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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- 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
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- 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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- 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
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
- B32B2379/08—Polyimides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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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
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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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
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
본 발명은 플렉서블 프린트 배선판 등에 사용되는 플렉서블 동장 적층판(FCCL:Flexible Copper Clad Laminate), 그것을 제조하기 위한 접착제 및 접착 시트에 관한 것이다.The present invention relates to a flexible copper clad laminate (FCCL) used for a flexible printed wiring board and the like, an adhesive and an adhesive sheet for manufacturing the same.
최근, 일렉트로닉스 제품의 경량화, 소형화, 고밀도화에 따라, 각종 프린트 배선판의 수요가 늘고 있지만, 그중에서도, 플렉서블 프린트 배선판의 수요가 특히 늘고 있다. 주된 플렉서블 프린트 배선판 재료에는 플렉서블 동장 적층판, 커버레이 필름, 층간 절연 재료(본딩 시트)가 있다. 이 중 플렉서블 프린트 배선판용 플렉서블 동장 적층판은 일반적으로 각종 절연 재료에 의해 형성되며, 폴리이미드 필름 등의 유연성을 갖는 절연성 필름을 기재로 하여, 이 기재의 표면에 각종 접착 재료를 통해 금속박을 가열·압착하여 첩합하는 방법에 의해 제조된다.BACKGROUND ART In recent years, demand for various types of printed wiring boards is increasing along with weight reduction, miniaturization, and high density of electronic products, but, among them, demand for flexible printed wiring boards is particularly increasing. Main flexible printed wiring board materials include flexible copper-clad laminates, coverlay films, and interlayer insulating materials (bonding sheets). Among them, a flexible copper-clad laminate for a flexible printed wiring board is generally formed of various insulating materials, using an insulating film having flexibility such as a polyimide film as a base material, and heating and pressing a metal foil on the surface of the base material through various adhesive materials. It is manufactured by a bonding method.
동박과 폴리이미드 필름의 접착제로서 에폭시 수지 또는 아크릴 수지 등의 열경화성 수지를 사용한 플렉서블 동장 적층판(이하, 「3층 FCCL」이라고도 함)이 있다. 이들 열경화성 접착제는 비교적 저온에서의 접착이 가능하다는 이점이 있지만, 내열성, 내약품성, 전기적 신뢰성, 치수 안정성, 박육화 등의 요구 특성이 엄격해짐에 따라, 3층 FCCL로는 대응이 곤란해지고 있다. 그리하여 폴리이미드 필름에 직접 금속층을 형성하거나, 접착층에 열가소성 폴리이미드를 사용한 플렉서블 동장 적층판(이하, 「2층 FCCL」이라고도 함)이 늘고 있다. 이 2층 FCCL은 3층 FCCL보다 특히 내열성, 치수 안정성 및 전기적 신뢰성이 우수하며, 박육화에도 공헌할 수 있다.There is a flexible copper-clad laminate (hereinafter also referred to as "three-layer FCCL") using a thermosetting resin such as an epoxy resin or an acrylic resin as an adhesive between copper foil and a polyimide film. These thermosetting adhesives have the advantage of being able to bond at a relatively low temperature, but as the required properties such as heat resistance, chemical resistance, electrical reliability, dimensional stability, and thinning become stricter, it is difficult to cope with 3-layer FCCL. Therefore, flexible copper-clad laminates (hereinafter also referred to as "two-layer FCCL") in which a metal layer is directly formed on a polyimide film or a thermoplastic polyimide is used for an adhesive layer are increasing. This two-layer FCCL is superior in heat resistance, dimensional stability and electrical reliability in particular to that of the three-layer FCCL, and can also contribute to thinning.
2층 FCCL에는 라미네이트법, 캐스팅법, 및 스퍼터링법의 3종의 제조 방법이 있으며, 각각 장단점을 갖고 있다.There are three types of manufacturing methods for the two-layer FCCL: the lamination method, the casting method, and the sputtering method, and each has advantages and disadvantages.
라미네이트법 2층 FCCL은 폴리이미드 필름의 편면 또는 양면에 열가소성 폴리이미드(TPI) 접착층을 형성한 접착 시트와 도전성 금속박을 첩합하는 프로세스를 이용하기 때문에, 3종의 방법 중에서는 생산성이 높다(특허문헌 1, 3∼5). 일반적으로 2층 FCCL에는 무연 솔더에 대응한 높은 솔더 내열성, 및 고밀도 실장에 대응한 치수 안정성이 요구된다. 그러나 라미네이트법 2층 FCCL은 접착제에 고융점의 열가소성 폴리이미드(TPI)를 사용하기 때문에, 라미네이트 공정이 300℃ 이상의 고온 또한 고압이 될 수 밖에 없고, 이것이 에칭 후 및 가열 후의 치수 안정성을 악화시키고 있었다. 치수 안정성을 높이기 위해 다양한 개량이 이루어지고 있지만 치수 안정성은 아직 불충분하다. 또한, 동박 끊어짐, 주름 방지 등의 관점에서 내열 보호 필름의 병용이 필수가 되어, 비용 측면에서도 과제가 남아 있었다.Since the laminated two-layer FCCL uses a process of bonding an adhesive sheet in which a thermoplastic polyimide (TPI) adhesive layer is formed on one or both sides of a polyimide film and a conductive metal foil, productivity is high among the three methods (patent literature 1, 3-5). In general, high solder heat resistance corresponding to lead-free solder and dimensional stability corresponding to high-density mounting are required for two-layer FCCL. However, since the laminated two-layer FCCL uses high-melting-point thermoplastic polyimide (TPI) as an adhesive, the lamination process inevitably requires a high temperature of 300 ° C. or higher and a high pressure, which deteriorates the dimensional stability after etching and heating. . Various improvements have been made to increase dimensional stability, but dimensional stability is still insufficient. Moreover, from the viewpoint of copper foil breakage, wrinkle prevention, etc., the combined use of a heat-resistant protective film has become essential, and a problem remains from the viewpoint of cost.
캐스팅법 2층 FCCL은 도전성 금속박에 폴리이미드 전구체를 캐스팅(도포)하고 가열하여 이미드화하는 프로세스를 이용하지만(특허문헌 6 및 7), 생산성이 떨어지고 장대(長大) 장치를 요한다는 본질적인 결점을 갖고 있다. 치수 안정성과 동박 접착력의 신뢰성을 높이기 위해, 저열팽창 폴리이미드와 동박의 접착성을 높인 고접착성 폴리이미드를 사용하여 경화 후의 열팽창 계수가 구리와 정합하는 임의의 두께비로 동박 상에 3층 도공하여 경화하는 방법이 개발되고, 또한, 플로팅 방식에 의한 편면 2층 FCCL의 광폭 연속 도공·경화 프로세스나 양면 2층 FCCL의 고속·광폭의 연속 라미네이트 프로세스도 개발되고 있다. 이러한 개량을 거듭한 결과, 현재는 캐스팅법 2층 FCCL은 3종의 방법 중에서 특성이 가장 안정적이지만, 생산성이 떨어지고 장대 장치를 요한다는 본질적인 결점을 극복하기까지는 이르지 못했다.The casting method 2-layer FCCL uses a process of imidizing by casting (coating) a polyimide precursor on a conductive metal foil and heating it (Patent Documents 6 and 7), but has an essential drawback that productivity is low and a long device is required. there is. In order to improve dimensional stability and reliability of copper foil adhesion, low thermal expansion polyimide and high adhesive polyimide with improved adhesion of copper foil are used, and three layers are coated on the copper foil at an arbitrary thickness ratio whose thermal expansion coefficient after curing matches that of copper. A method of curing has been developed, and a wide continuous coating and curing process of single-sided two-layer FCCL by a floating method and a high-speed and wide continuous lamination process of double-sided two-layer FCCL have also been developed. As a result of these improvements, currently, the casting method 2-layer FCCL has the most stable properties among the three methods, but it has not been able to overcome the essential drawback of low productivity and requiring a pole device.
스퍼터링법 2층 FCCL은 폴리이미드 필름 상에 도전성 금속을 스퍼터링으로 적층하는 프로세스이고, 도체층의 박막화가 용이하며, 금속과 필름의 계면이 평활하다는 특징으로부터, 파인 패턴 형성에 유리하다(특허문헌 2). 그러나 스퍼터링법은 진공 증착 설비가 필수여서 생산 비용이 높고 생산성도 나쁘기 때문에, FCCL의 가격도 3종의 방법 중에서 가장 고가이다.The sputtering method 2-layer FCCL is a process of laminating a conductive metal on a polyimide film by sputtering, and is advantageous for fine pattern formation due to the characteristics that thinning of the conductor layer is easy and the interface between the metal and the film is smooth (Patent Document 2 ). However, since the sputtering method requires a vacuum deposition facility, the production cost is high and the productivity is low, the price of FCCL is also the most expensive among the three methods.
한편, 페닐인단 구조를 포함하는 용제 가용성 폴리이미드 수지와 에폭시 수지를 포함하는 열경화성 수지 조성물로 이루어지는 필름을 다층 기판의 층간 절연 재료나 접착제로서 사용하는 방법이 보고되어 있다(특허문헌 8 및 9). 특허문헌 8에서는 FR-4 등의 리지드 기판을 코어 재료로 한 빌드업 다층 기판용의 층간 절연 재료로서 열경화성 수지 조성물이 사용되고 있다. 또한, 특허문헌 9에서는 코어 재료인 플렉서블 동장판에 동박을 겹쳐 빌드업 다층 프린트 배선판을 제작할 때에, 플렉서블 동장판의 표면의 구리와 동박을 접합시키기 위한 접착제로서 열경화성 수지 조성물이 사용되고 있으며, 열경화성 수지 조성물에는 유리 전이 온도(Tg)가 130℃ 이상인 페녹시 수지가 사용되고 있다. 그러나 특허문헌 9의 접착제는 FCCL을 구성하는 폴리이미드 필름 기재와 동박을 접착시키기 위한 재료가 아니다. 또한, 특허문헌 10에는 FCCL을 구성하는 폴리이미드 필름과 동박을 접착시키기 위한 접착제로서, 폴리이미드 수지와 가교제를 포함하는 접착제가 개시되어 있다. 그러나 특허문헌 10에는 접착제가 고연화점(20∼220℃), 저유전률 및 저유전정접을 나타내는 것은 개시되어 있지만, 치수 안정성에 관해서는 전혀 언급되어 있지 않다.On the other hand, a method of using a film made of a thermosetting resin composition containing a solvent-soluble polyimide resin containing a phenylindan structure and an epoxy resin as an interlayer insulating material or adhesive of a multi-layer board has been reported (Patent Documents 8 and 9). In Patent Literature 8, a thermosetting resin composition is used as an interlayer insulating material for a build-up multilayer substrate using a rigid substrate such as FR-4 as a core material. In addition, in Patent Document 9, when manufacturing a build-up multilayer printed wiring board by overlapping copper foil on a flexible copper clad board as a core material, a thermosetting resin composition is used as an adhesive for bonding copper and copper foil on the surface of a flexible copper clad board, and the thermosetting resin composition A phenoxy resin having a glass transition temperature (Tg) of 130° C. or higher is used. However, the adhesive of Patent Document 9 is not a material for adhering the polyimide film substrate constituting the FCCL and the copper foil. In addition, Patent Document 10 discloses an adhesive containing a polyimide resin and a crosslinking agent as an adhesive for adhering a polyimide film and copper foil constituting FCCL. However, Patent Literature 10 discloses that the adhesive exhibits a high softening point (20 to 220° C.), a low dielectric constant, and a low dielectric loss tangent, but does not mention dimensional stability at all.
2층 FCCL에서는 생산성의 관점에서는 라미네이트법 2층 FCCL이 가장 우수하고, 특성의 관점에서는 캐스팅법 2층 FCCL이 가장 우수하다. 그 때문에, 라미네이트법의 프로세스를 이용하여 캐스팅법 2층 FCCL 수준의 특성을 실현하는 것이 요구되고 있었다. 라미네이트법 2층 FCCL은 라미네이트 온도가 300℃ 이상으로 높기 때문에, 동박 끊어짐이나 주름 등과 같은 불량을 없애기 위해, 라미네이트 시에 폴리이미드 필름 등의 고내열 필름을 병용하고 있다. 또한, 고온 라미네이트 때문에 치수 안정성도 나빠질 수 밖에 없었다. 그 때문에, 이러한 불량이 생기지 않고 접착제층과 동박을 라미네이트할 수 있으며, 또한, 치수 안정성이 우수한 FCCL을 제공할 수 있는 접착제가 요구되고 있었다.In the two-layer FCCL, the laminated two-layer FCCL is the most excellent in terms of productivity, and the casting two-layer FCCL is the most excellent in terms of characteristics. For this reason, it has been desired to realize characteristics at the level of the two-layer FCCL of the casting method by using the process of the lamination method. Since the laminated two-layer FCCL has a high lamination temperature of 300° C. or more, a highly heat-resistant film such as a polyimide film is used in combination during lamination to eliminate defects such as copper foil breakage and wrinkles. In addition, dimensional stability was inevitably deteriorated due to high-temperature lamination. Therefore, there has been a demand for an adhesive capable of laminating the adhesive layer and the copper foil without causing such a defect and providing an FCCL having excellent dimensional stability.
본 발명은 이상의 사정을 감안하여 이루어진 것으로서, 그 목적은 캐스팅법 2층 FCCL 수준의 특성과 라미네이트법 2층 FCCL 이상의 생산성을 양립함과 아울러, 동박 끊어짐이나 주름 등의 불량이 없으며, 치수 안정성이 우수한 FCCL을 제공하는 플렉서블 동장 적층판용의 접착제를 개발하고, 그것을 사용하여 제조하는 접착 시트 및 라미네이트법 플렉서블 동장 적층판(이하, 「2. 2층 FCCL」이라고도 함)을 제공하는 것에 있다.The present invention has been made in view of the above circumstances, and its purpose is to achieve both the characteristics of the two-layer FCCL level of the casting method and the productivity of the two-layer FCCL or higher of the laminate method, as well as to have no defects such as copper foil breakage or wrinkles, and to have excellent dimensional stability. It is to develop an adhesive for flexible copper clad laminates that provides FCCL, and to provide adhesive sheets and laminated flexible copper clad laminates (hereinafter also referred to as "2. Two-layer FCCL") manufactured using the same.
본 발명자들은 예의 검토를 거듭한 결과, 라미네이트법 2층 FCCL에 있어서, 접착제인 열가소성 폴리이미드(TPI)를, 특정의 용제 가용성 폴리이미드, 유리 전이 온도(Tg)가 120℃ 이하인 페녹시 수지, 에폭시 수지, 및 에폭시 수지 경화제를 포함하는 폴리머 알로이의 열경화성 접착제로 변경함으로써, 라미네이트법 2층 FCCL의 특성 상의 개선점인 치수 안정성을 개량할 수 있고, 캐스팅법 2층 FCCL 수준의 특성을 달성할 수 있음과 아울러, 라미네이트 시에 동박 끊어짐이나 주름 등의 불량이 없어지는 것을 알아내어 본 발명을 완성했다.As a result of repeated intensive studies, the inventors of the present invention have found that, in a laminated two-layer FCCL, thermoplastic polyimide (TPI) as an adhesive is selected from a specific solvent-soluble polyimide, a phenoxy resin having a glass transition temperature (Tg) of 120° C. or less, and an epoxy resin. By changing to a thermosetting adhesive of a polymer alloy containing a resin and an epoxy resin curing agent, it is possible to improve dimensional stability, which is an improvement in the properties of a laminated two-layer FCCL, and to achieve properties comparable to those of a casting two-layer FCCL. In addition, it was found that defects such as copper foil breakage and wrinkles were eliminated during lamination, and the present invention was completed.
즉, 본 발명은 플렉서블 동장 적층판을 구성하는 폴리이미드 필름 기재와 동박을 접착시키기 위한 플렉서블 동장 적층판용 접착제로서, 하기 일반식[I]으로 표시되는 반복 단위를 갖는 용제 가용성 폴리이미드, 유리 전이 온도(Tg)가 120℃ 이하인 페녹시 수지, 에폭시 수지, 및 에폭시 수지 경화제를 함유하는 접착제를 제공한다.That is, the present invention is an adhesive for a flexible copper-clad laminate for bonding a copper foil to a polyimide film substrate constituting a flexible copper-clad laminate, wherein a solvent-soluble polyimide having a repeating unit represented by the following general formula [I], a glass transition temperature ( An adhesive containing a phenoxy resin having a Tg) of 120°C or less, an epoxy resin, and an epoxy resin curing agent.
(식 중, Z는 방향족 혹은 지환식의 테트라카르복실산 디무수물 잔기이고, Ar은 페닐인단 구조를 갖는 방향족 디아민 잔기이다)(Wherein, Z is an aromatic or alicyclic tetracarboxylic acid dianhydride residue, and Ar is an aromatic diamine residue having a phenylindan structure)
또한, 본 발명은 플렉서블 동장 적층판을 구성하는 폴리이미드 필름 기재의 편면 또는 양면에 동박을 접착시키기 위한 접착제층이 적층되어 이루어지는 플렉서블 동장 적층판용의 접착 시트로서, 상기 접착제층이 상기 본 발명의 접착제를 함유하는 접착 시트를 제공한다.In addition, the present invention is an adhesive sheet for a flexible copper-clad laminate in which an adhesive layer for bonding copper foil is laminated on one or both sides of a polyimide film base material constituting the flexible copper-clad laminate, wherein the adhesive layer comprises the adhesive of the present invention An adhesive sheet containing
또한, 본 발명은 폴리이미드 필름 기재의 편면 또는 양면에 접착제층 및 동박이 순차 적층되어 이루어지는 플렉서블 동장 적층판으로서, 상기 접착제층이 상기 본 발명의 접착제를 함유하는 플렉서블 동장 적층판을 제공한다.In addition, the present invention provides a flexible copper-clad laminate formed by sequentially laminating an adhesive layer and copper foil on one or both surfaces of a polyimide film substrate, wherein the adhesive layer contains the adhesive of the present invention.
또한, 본 발명은 상기 본 발명의 플렉서블 동장 적층판의 제조 방법으로서, 상기 본 발명의 접착 시트에 동박을 70∼120℃의 온도에서 라미네이트한 후에, 200℃ 이하의 온도에서 접착제층을 경화시키는 것을 포함하는 제조 방법을 제공한다.In addition, the present invention is a method for manufacturing the flexible copper-clad laminate of the present invention, comprising laminating a copper foil on the adhesive sheet of the present invention at a temperature of 70 to 120 ° C., and then curing the adhesive layer at a temperature of 200 ° C. or less. A manufacturing method is provided.
종래, 접착 시트의 접착제층과 동박을 고온에서 라미네이트하면 동박 끊어짐이나 주름과 같은 불량이 발생했으며, 특히 동박 두께가 18㎛ 이하와 같은 얇은 경우에 이러한 불량이 현저했다. 본 발명의 특정의 접착제를 사용하여 폴리이미드 필름 기재의 표면에 접착제층을 적층하여 접착 시트를 제작함으로써, 동박의 두께가 얇은 경우여도 접착 시트의 접착제층과 동박을 비교적 저온에서 라미네이트할 수 있고, 동박 끊어짐이나 주름 등의 불량이 없는 플렉서블 동장 적층판을 제공할 수 있다. 그 때문에, 치수 안정성 악화의 주요인 중 하나인 고온 고압에서의 라미네이트 공정을 거칠 필요가 없고, 또한, 열경화 온도도 200℃ 이하이므로, 플렉서블 동장 적층판의 치수 안정성을 크게 개선할 수 있다. 그 결과, 캐스팅법 2층 FCCL 수준의 특성과 라미네이트법 2층 FCCL 이상의 생산성을 양립하는 플렉서블 동장 적층판을 제공할 수 있다.Conventionally, when the adhesive layer of the adhesive sheet and the copper foil are laminated at a high temperature, defects such as copper foil breakage or wrinkles occur, and these defects are particularly noticeable when the copper foil thickness is as thin as 18 μm or less. By laminating an adhesive layer on the surface of a polyimide film substrate using the specific adhesive of the present invention to produce an adhesive sheet, the adhesive layer of the adhesive sheet and the copper foil can be laminated at a relatively low temperature even when the thickness of the copper foil is thin, It is possible to provide a flexible copper-clad laminate having no defects such as broken copper foil or wrinkles. Therefore, since there is no need to go through a lamination process at high temperature and high pressure, which is one of the main causes of deterioration in dimensional stability, and the thermal curing temperature is 200° C. or lower, the dimensional stability of the flexible copper-clad laminate can be greatly improved. As a result, it is possible to provide a flexible copper-clad laminate that achieves both the characteristics of a two-layer FCCL level by the casting method and productivity equal to or higher than that of a two-layer FCCL by the laminate method.
본 발명의 플렉서블 동장 적층판용 접착제는 플렉서블 동장 적층판을 구성하는 폴리이미드 필름 기재와 동박을 접착시키기 위한 접착제이며, 하기 일반식[I]으로 표시되는 반복 단위를 갖는 용제 가용성 폴리이미드, Tg가 120℃ 이하인 페녹시 수지, 에폭시 수지, 및 에폭시 수지 경화제를 함유한다.The adhesive for a flexible copper-clad laminate of the present invention is an adhesive for adhering a polyimide film base material and copper foil constituting a flexible copper-clad laminate, and is a solvent-soluble polyimide having a repeating unit represented by the following general formula [I], Tg is 120 ° C. The following phenoxy resins, epoxy resins, and epoxy resin curing agents are contained.
상기 일반식 중, Z는 방향족 혹은 지환식의 테트라카르복실산 디무수물 잔기이고, Ar은 페닐인단 구조를 갖는 방향족 디아민 잔기이다.In the above general formula, Z is an aromatic or alicyclic tetracarboxylic acid dianhydride residue, and Ar is an aromatic diamine residue having a phenylindan structure.
(용제 가용성 폴리이미드)(solvent soluble polyimide)
본 발명에 있어서의 용제 가용성 폴리이미드가 갖는 상기 일반식[I]으로 표시되는 반복 단위에 있어서, Z로 표시되는 방향족 테트라카르복실산 디무수물 잔기를 폴리이미드에 도입하기 위한 방향족 테트라카르복실산 디무수물로서는 특별히 제한은 없지만, 벤조페논테트라카르복실산 디무수물 또는 비페닐테트라카르복실산 디무수물이 바람직하다.In the repeating unit represented by the general formula [I] of the solvent-soluble polyimide in the present invention, an aromatic tetracarboxylic acid di-anhydride residue represented by Z is introduced into the polyimide. The anhydride is not particularly limited, but benzophenonetetracarboxylic di-anhydride or biphenyltetracarboxylic di-anhydride is preferred.
Z로 표시되는 지환식 테트라카르복실산 디무수물 잔기를 폴리이미드에 도입하기 위한 지환식 테트라카르복실산 디무수물로서는, 비시클로[2.2.2]옥토-7-엔-2,3,5,6-테트라카르복실산 디무수물, 노르보르난-2-스피로-α-시클로알카논-α'-스피로-2''-노르보르난-5,5'',6,6''-테트라카르복실산 디무수물, 1,2,3,4-시클로부탄테트라카르복실산 디무수물, 1,2,3,4-시클로펜탄테트라카르복실산 디무수물, 1,2,4,5-시클로헥산테트라카르복실산 디무수물, 2,3,5-트리카르복시시클로펜틸아세트산 디무수물, 3,5,6-트리카르복시노르보르난-2-아세트산 디무수물, 2,3,4,5-테트라히드로푸란테트라카르복실산 디무수물, 1,3,3a,4,5,9b-헥사히드로-5-(테트라히드로-2,5-디옥소-3-푸라닐)-나프트[1,2-c]-푸란-1,3-디온, 1,3,3a,4,5,9b-헥사히드로-5-메틸-5-(테트라히드로-2,5-디옥소-3-푸라닐)-나프트[1,2-c]-푸란-1,3-디온, 1,3,3a,4,5,9b-헥사히드로-8-메틸-5-(테트라히드로-2,5-디옥소-3-푸라닐)-나프트[1,2-c]-푸란-1,3-디온, 5-(2,5-디옥소테트라히드로푸랄)-3-메틸-3-시클로헥센-1,2-디카르복실산 디무수물, 비시클로[2,2,2]-옥토-7-엔-2,3,5,6-테트라카르복실산 디무수물, 비시클로[2,2,1]-헵탄-2,3,5,6-테트라카르복실산 디무수물 및 데카하이드로디메타노나프탈렌-2,3,6,7-테트라카르복실산 디무수물 등을 들 수 있다.As the alicyclic tetracarboxylic dianhydride for introducing the alicyclic tetracarboxylic dianhydride residue represented by Z into the polyimide, bicyclo[2.2.2]octo-7-ene-2,3,5,6 -Tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cycloalkanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic Acid di-anhydride, 1,2,3,4-cyclobutanetetracarboxylic di-anhydride, 1,2,3,4-cyclopentanetetracarboxylic di-anhydride, 1,2,4,5-cyclohexanetetracar boxylic acid di-anhydride, 2,3,5-tricarboxycyclopentylacetic acid di-anhydride, 3,5,6-tricarboxynorbornane-2-acetic acid di-anhydride, 2,3,4,5-tetrahydrofurantetracar Boxylic di-anhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphth[1,2-c]-furan -1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphth[1, 2-c] -furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -Naphth[1,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofural)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid Di-anhydride, bicyclo[2,2,2]-octo-7-ene-2,3,5,6-tetracarboxylic acid di-anhydride, bicyclo[2,2,1]-heptane-2,3, 5,6-tetracarboxylic acid dianhydride and decahydrodimethanonaphthalene-2,3,6,7-tetracarboxylic acid dianhydride, etc. are mentioned.
Ar로 표시되는 페닐인단 구조를 갖는 방향족 디아민 잔기에 있어서의 페닐인단 구조란, 하기의 인단 골격에 치환기를 갖고 있어도 되는 페닐기가 치환한 구조이며, 치환기로서는, 할로겐 원자 또는 탄소수 1∼5, 바람직하게는 탄소수 1∼3의 알킬기를 들 수 있다. 페닐인단 구조를 갖는 방향족 디아민 잔기(Ar)로서는 하기의 인단 골격의 1자리 또는 2자리에 치환기를 갖고 있어도 되는 페닐기가 치환한 구조를 포함하는 디아민 잔기가 바람직하고, 그중에서도, 하기 일반식[II]로 표시되는 디아민 잔기인 것이 바람직하다.The phenylindane structure in an aromatic diamine residue having a phenylindan structure represented by Ar is a structure in which the following indan skeleton is substituted with a phenyl group which may have a substituent, and the substituent is a halogen atom or 1 to 5 carbon atoms, preferably includes an alkyl group having 1 to 3 carbon atoms. As the aromatic diamine residue (Ar) having a phenylindan structure, a diamine residue containing a structure in which a phenyl group which may have a substituent at one or two positions of the following indan skeleton is substituted, and among these, the following general formula [II] It is preferably a diamine residue represented by
일반식[II] 중, R1, R2 및 R3은 각각 독립적으로 수소 원자 또는 탄소수 1∼5의 알킬기를 나타내고, 바람직하게는 탄소수 1∼3의 알킬기를 나타낸다. 또한, R4의 각각 및 R5의 각각은 독립적으로 수소 원자 또는 탄소수 1∼5의 알킬기를 나타내고, 바람직하게는 탄소수 1∼3의 알킬기를 나타낸다.In formula [II], R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. In addition, each of R 4 and each of R 5 independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and preferably represents an alkyl group having 1 to 3 carbon atoms.
페닐인단 구조를 갖는 방향족 디아민 잔기(Ar)를 폴리이미드에 도입하기 위한 방향족 디아민으로서는, 5-아미노-1-(4'-아미노페닐)-1,3,3-트리메틸인단, 6-아미노-1-(4'-아미노페닐)-1,3,3-트리메틸인단, 5-아미노-6-메틸-1-(3'-아미노-4'-메틸페닐)-1,3,3-트리메틸인단, 5-아미노-1-(4'-아미노-Ph', Ph'-디클로로-페닐)-Ph, Ph-디클로로-1,3,3-트리메틸인단, 6-아미노-1-(4'-아미노-Ph', Ph'-디클로로-페닐)-Ph, Ph-디클로로-1,3,3-트리메틸인단, 4-아미노-6-메틸-1-(3'-아미노-4'-메틸-페닐)-1,3,3-트리메틸인단, Ph-아미노-1-(Ph'-아미노-2',4'-디메틸페닐)-1,3,3,4,6-펜타메틸인단 등을 들 수 있다. 상기 예시 화합물 중의 Ph 및 Ph'는 페닐인단 구조 중의 페닐환 중의 불특정한 위치를 나타낸다.As the aromatic diamine for introducing the aromatic diamine residue (Ar) having a phenylindan structure into the polyimide, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1 -(4'-aminophenyl)-1,3,3-trimethylindane, 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindane, 5 -Amino-1-(4'-amino-Ph', Ph'-dichloro-phenyl)-Ph, Ph-dichloro-1,3,3-trimethylindane, 6-amino-1-(4'-amino-Ph ', Ph'-dichloro-phenyl)-Ph, Ph-dichloro-1,3,3-trimethylindane, 4-amino-6-methyl-1-(3'-amino-4'-methyl-phenyl)-1 ,3,3-trimethylindane, Ph-amino-1-(Ph'-amino-2',4'-dimethylphenyl)-1,3,3,4,6-pentamethylindane, and the like. Ph and Ph' in the above exemplary compounds represent unspecified positions in the phenyl ring in the phenyl indane structure.
용제 가용성 폴리이미드를 구성하는 페닐인단 구조를 갖는 방향족 디아민 성분(Ar 성분)의 함유량은 용제 가용성 폴리이미드와 에폭시 수지의 상용성을 높이는 관점에서, 전체 디아민 성분의 50mol% 이상, 바람직하게는 60mol% 이상, 보다 바람직하게는 70mol% 이상, 더욱 바람직하게는 80mol% 이상, 특히는 90mol% 이상이 바람직하다.The content of the aromatic diamine component (Ar component) having a phenylindan structure constituting the solvent-soluble polyimide is 50 mol% or more, preferably 60 mol% of the total diamine components, from the viewpoint of enhancing compatibility between the solvent-soluble polyimide and the epoxy resin. or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and particularly preferably 90 mol% or more.
용제 가용성 폴리이미드는 상기 일반식[I]으로 표시되는 반복 단위 이외의 다른 반복 단위를 갖는 블록 로크 공중합체여도 되고, 다른 방향족 디아민 잔기, 지방족 디아민 잔기 또는 지환식 디아민 잔기, 혹은 디아미노폴리실록산을 주쇄 중에 갖는 디아민 잔기를 갖는 반복 단위를 갖고 있어도 된다. 디아미노폴리실록산을 주쇄 중에 갖는 디아민 잔기를 폴리이미드에 도입하기 위한 디아민으로서는, α,ω-비스(2-아미노에틸)폴리디메틸실록산, α,ω-비스(3-아미노프로필)폴리디메틸실록산, α,ω-비스(4-아미노페닐)폴리디메틸실록산, α,ω-비스(4-아미노-3-메틸페닐)폴리디메틸실록산, α,ω-비스(3-아미노프로필)폴리디페닐실록산, α,ω-비스(4-아미노부틸)폴리디메틸실록산 등을 들 수 있다.The solvent-soluble polyimide may be a block copolymer having a repeating unit other than the repeating unit represented by the above general formula [I], and other aromatic diamine residues, aliphatic diamine residues or alicyclic diamine residues, or diaminopolysiloxane as a main chain You may have a repeating unit which has a diamine residue in the inside. As the diamine for introducing the diamine residue having the diaminopolysiloxane in the main chain into the polyimide, α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α ,ω-bis(4-aminophenyl)polydimethylsiloxane, α,ω-bis(4-amino-3-methylphenyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydiphenylsiloxane, α, (omega)-bis (4-aminobutyl) polydimethylsiloxane etc. are mentioned.
상기 일반식[I]으로 표시되는 반복 단위를 갖는 용제 가용성 폴리이미드는 방향족 혹은 지환식의 테트라카르복실산 디무수물과 페닐인단 구조를 갖는 방향족 디아민을 탈수 축합 반응시킴으로써 얻어진다.The solvent-soluble polyimide having a repeating unit represented by the general formula [I] is obtained by subjecting an aromatic or alicyclic tetracarboxylic dianhydride and an aromatic diamine having a phenylindan structure to a dehydration condensation reaction.
용제 가용성 폴리이미드의 합성 방법은 공지의 방법을 이용하면 되고, 특별히 제한되지 않지만, 상술한 테트라카르복실산 디무수물과 방향족 디아민을 거의 같은 양을 사용하여, 유기 극성 용매 중, 촉매 및 탈수제의 존재 하 160∼200℃에서 수시간 반응시킴으로써, 용제 가용성의 폴리이미드를 합성할 수 있다. 유기 극성 용매로서는, N-메틸피롤리돈(NMP), γ-부티로락톤, N,N'-디메틸아세트아미드, N,N'-디메틸포름아미드, 디메틸술폭시드, 테트라메틸요소, 테트라히드로티오펜-1,1-옥시드 등이 사용된다.The method for synthesizing the solvent-soluble polyimide may be a known method, and is not particularly limited, but the above-mentioned tetracarboxylic dianhydride and aromatic diamine are used in approximately equal amounts, in an organic polar solvent, in the presence of a catalyst and a dehydrating agent. A solvent-soluble polyimide can be synthesized by reacting at 160 to 200°C for several hours. As the organic polar solvent, N-methylpyrrolidone (NMP), γ-butyrolactone, N,N'-dimethylacetamide, N,N'-dimethylformamide, dimethylsulfoxide, tetramethylurea, tetrahydrothiocyanate Ophen-1,1-oxide and the like are used.
용제 가용성 폴리이미드는 블록 공중합체인 것이 바람직하고, 블록 공중합체는 블록 공중합 반응을 행함으로써 합성할 수 있다. 예를 들면, 2단계의 축차 첨가 반응에 의해 제조할 수 있고, 제 1 단계에서 테트라카르복실산 디무수물과 방향족 디아민으로부터 폴리이미드올리고머를 합성하고, 이어서 제 2 단계에서 테트라카르복실산 디무수물 및/또는 방향족 디아민을 더 첨가하여 중축합시켜서 블록 공중합 폴리이미드로 할 수 있다.The solvent-soluble polyimide is preferably a block copolymer, and the block copolymer can be synthesized by performing a block copolymerization reaction. For example, it can be produced by a two-step sequential addition reaction, in which a polyimide oligomer is synthesized from tetracarboxylic dianhydride and aromatic diamine in the first step, and then in the second step, tetracarboxylic dianhydride and It can be set as block copolymerization polyimide by polycondensing by adding/or aromatic diamine further.
블록 공중합 반응의 촉매로서는, 락톤의 평형 반응을 이용한 2성분계의 산-염기 촉매를 사용함으로써, 탈수 이미드화 반응을 촉진할 수 있다. 구체적으로는, γ-발레로락톤과 피리딘 또는 N-메틸모르폴린의 2성분계 촉매를 사용한다. 하기 식에 나타내는 바와 같이, 이미드화가 진행됨에 따라 물이 생성되고, 생성된 물이 락톤의 평형에 관여해서 산-염기 촉매가 되어 촉매작용을 나타낸다.As a catalyst for the block copolymerization reaction, the dehydration imidation reaction can be promoted by using a two-component acid-base catalyst using an equilibrium reaction of lactone. Specifically, a two-component catalyst of γ-valerolactone and pyridine or N-methylmorpholine is used. As shown in the following formula, water is generated as the imidation proceeds, and the generated water becomes an acid-base catalyst by being involved in the equilibrium of lactones and exhibits a catalytic action.
이미드화 반응에 의해 생성되는 물은 극성 용매 중에 공존하는 톨루엔 또는 크실렌 등의 탈수제와 공비에 의해 계외로 제거된다. 반응이 완결되면 용액 중의 물이 제거되고, 산-염기 촉매는 γ-발레로락톤과 피리딘 또는 N-메틸모르폴린이 되어 계외로 제거된다. 이와 같이 하여 고순도의 폴리이미드 용액을 얻을 수 있다.The water produced by the imidation reaction is removed out of the system by azeotropy with a dehydrating agent such as toluene or xylene coexisting in the polar solvent. When the reaction is completed, water in the solution is removed, and the acid-base catalyst becomes γ-valerolactone and pyridine or N-methylmorpholine and is removed out of the system. In this way, a high-purity polyimide solution can be obtained.
다른 2성분계 촉매로서는, 옥살산 또는 말론산과 피리딘 또는 N-메틸모르폴린을 사용할 수 있다. 160∼200℃의 반응 용액 중에서 옥살산염 또는 말론산염은 산 촉매로서 이미드화 반응을 촉진한다. 생성된 폴리이미드 용매 중에는 촉매량의 옥살산 또는 말론산이 잔류한다. 이 폴리이미드 용액을 기재에 도포한 후에 200℃ 이상으로 가열하고, 탈용매를 행하여 제막을 할 때에, 폴리이미드 중에 잔존하는 옥살산 또는 말론산은 하기 식에 나타내는 바와 같이 열분해하여 가스로서 계외로 제거된다.As another two-component catalyst, oxalic acid or malonic acid and pyridine or N-methylmorpholine can be used. In the reaction solution at 160 to 200°C, oxalate or malonate promotes the imidation reaction as an acid catalyst. A catalytic amount of oxalic acid or malonic acid remains in the resulting polyimide solvent. After applying this polyimide solution to a substrate, it is heated to 200° C. or higher, and solvent removal is performed to form a film. When forming a film, oxalic acid or malonic acid remaining in the polyimide is thermally decomposed as shown in the following formula and is removed from the system as a gas.
이상의 방법에 의해, 고순도의 용제 가용성 폴리이미드를 얻을 수 있다. 옥살산-피리딘계 촉매는 발레로락톤-피리딘계 촉매에 비해 활성이 강하고, 단시간에 고분자량의 폴리이미드를 생성할 수 있다.By the above method, a high-purity solvent-soluble polyimide can be obtained. The oxalic acid-pyridine-based catalyst is more active than the valerolactone-pyridine-based catalyst and can produce high molecular weight polyimide in a short time.
합성된 용제 가용성 폴리이미드의 분자량은 폴리스티렌 환산의 중량 평균 분자량(Mw)으로서 1만∼40만이 바람직하다. 용제 가용성 폴리이미드의 분자량이 이 범위 내이면 양호한 용제 가용성, 막 물성 및 절연성을 달성할 수 있기 때문에 바람직하다.The molecular weight of the synthesized solvent-soluble polyimide is preferably from 10,000 to 400,000 as a weight average molecular weight (Mw) in terms of polystyrene. When the molecular weight of the solvent-soluble polyimide is within this range, it is preferable because good solvent solubility, film properties and insulating properties can be achieved.
본 발명에 있어서의 「용제 가용성」이라는 용어는 폴리이미드의 합성에 있어서 사용하는 유기 극성 용제와, 후술하는 접착제 조성물에 사용하는 용제에 대하여 사용하는 용어이며, 이들 용제를 사용하여 폴리이미드가 20중량% 고형분의 용액을 제작 가능한 것을 의미한다. 용제로서는, NMP, γ-부티로락톤, DMF, DMAC 등을 들 수 있다. 합성된 폴리이미드는 상기 유기 극성 용제 또는 후술하는 접착제 조성물에 사용하는 용제에, 예를 들면 고형분이 10∼30중량%가 되도록 용해시킨 용액의 상태로 사용할 수 있다.The term "solvent solubility" in the present invention is a term used for the organic polar solvent used in the synthesis of polyimide and the solvent used for the adhesive composition described later, and polyimide is 20% by weight using these solvents. It means that a solution of % solid content can be produced. Examples of the solvent include NMP, γ-butyrolactone, DMF, and DMAC. The synthesized polyimide can be used in the form of a solution dissolved in the organic polar solvent or a solvent used for an adhesive composition described later, for example, in a solid content of 10 to 30% by weight.
또한, 본 발명의 용제 가용성 폴리이미드는 완전히 이미드화한 폴리이미드이기 때문에, 접착제를 폴리이미드 필름 기재에 도포한 후에 이미드화를 위한 고온에서의 열 처리를 필요로 하지 않는다. 따라서, 접착제를 폴리이미드 필름 기재에 도포한 후에 이미드화를 위한 고온에서의 열 처리(300℃ 이상)를 요하는 폴리아믹산(폴리이미드 전구체)에 비해 치수 안정성이 높은 플렉서블 동장 적층판을 제공할 수 있다는 이점이 있다.In addition, since the solvent-soluble polyimide of the present invention is a fully imidized polyimide, it does not require heat treatment at high temperature for imidization after applying the adhesive to the polyimide film substrate. Therefore, it is possible to provide a flexible copper-clad laminate having higher dimensional stability compared to polyamic acid (polyimide precursor), which requires heat treatment at high temperature (300 ° C. or more) for imidization after applying the adhesive to the polyimide film substrate. There is an advantage.
(에폭시 수지)(epoxy resin)
본 발명에 있어서의 에폭시 수지는 특별히 한정되지 않지만, 바람직하게는 2개 이상의 글리시딜기를 갖는 강직 구조의 에폭시 수지가 적합하다. 에폭시 수지의 분자량(Mw)은 통상 200∼2,000이고, 바람직하게는 280∼1,000이다. 특히 바람직하게는 비페닐형 에폭시 수지, 나프탈렌형 에폭시 수지, 디시클로펜타디엔형 에폭시 수지, 비스페놀A형 에폭시 수지 등이며, 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.Although the epoxy resin in this invention is not specifically limited, Preferably, the epoxy resin of the rigid structure which has 2 or more glycidyl groups is suitable. The molecular weight (Mw) of the epoxy resin is usually 200 to 2,000, preferably 280 to 1,000. Particularly preferred are biphenyl-type epoxy resins, naphthalene-type epoxy resins, dicyclopentadiene-type epoxy resins, and bisphenol A-type epoxy resins, which may be used alone or in combination of two or more.
본 발명에 있어서의 에폭시 수지란, 용제 가용성 폴리이미드와 상용하는 에폭시 수지이며, 용제 가용성 폴리이미드의 특성을 변화시킬 수 있는 수지이다. 에폭시 수지와 용제 가용성 폴리이미드 수지는 상용하기 때문에, 에폭시 수지와 용제 가용성 폴리이미드를 혼합함으로써 상용계의 폴리머 알로이가 생성된다.The epoxy resin in the present invention is an epoxy resin compatible with solvent-soluble polyimide, and is a resin capable of changing the characteristics of solvent-soluble polyimide. Since the epoxy resin and the solvent-soluble polyimide resin are compatible, a compatible polymer alloy is produced by mixing the epoxy resin and the solvent-soluble polyimide.
(에폭시 수지 경화제)(epoxy resin curing agent)
본 발명에 있어서의 경화제로서는 에폭시 수지를 경화시키는 것이면 특별히 한정되지 않지만, 노볼락페놀 수지나 나프탈렌 구조와 아랄킬 구조를 갖는 수지를 들 수 있다. 노볼락페놀 수지로서는, 페놀노볼락 수지, 크레졸노볼락 수지, 트리아진 변성 노볼락 수지인 벤조구아나민 변성 비스페놀A형 노볼락 수지, 벤조구아나민 변성 크레졸노볼락형 페놀 수지, 벤조구아나민 변성 페놀노볼락형 페놀 수지, 멜라민 변성 비스페놀A형 노볼락 수지, 멜라민 변성 크레졸노볼락형 페놀 수지, 멜라민 변성 페놀노볼락형 페놀 수지 등을 들 수 있다. 나프탈렌 구조와 아랄킬 구조를 갖는 수지로서, 1-나프톨아랄킬 수지, 2-나프톨아랄킬 수지, 1,6-나프탈렌디올아랄킬 수지 등을 예시할 수 있다.The curing agent in the present invention is not particularly limited as long as it cures an epoxy resin, and examples thereof include a novolac phenol resin and a resin having a naphthalene structure and an aralkyl structure. As the novolak phenol resin, phenol novolac resin, cresol novolak resin, triazine-modified novolac resin, benzoguanamine-modified bisphenol A type novolac resin, benzoguanamine-modified cresol novolac-type phenol resin, benzoguanamine-modified phenol Novolac-type phenolic resins, melamine-modified bisphenol A-type novolac resins, melamine-modified cresol novolac-type phenolic resins, and melamine-modified phenol novolac-type phenolic resins. Examples of the resin having a naphthalene structure and an aralkyl structure include 1-naphthol aralkyl resin, 2-naphthol aralkyl resin, and 1,6-naphthalenediol aralkyl resin.
에폭시 수지에 대한 상기 경화제의 사용량은 수산기 당량으로서 0.5당량 이상, 1.2당량 이하로 하는 것이 좋다. 경화제의 사용량이 0.5당량 미만에서는 적정한 Tg가 얻어지지 않는 경우가 있으므로, 0.5당량 이상이 바람직하지만, 0.6당량 이상이 더욱 바람직하다. 또한, 경화제의 사용량이 1.2당량을 초과하면 수지의 흡수 특성이 저하되는 경우가 있으므로, 1.2당량 이하가 바람직하지만, 1.0당량 이하가 더욱 바람직하다.The amount of the curing agent used for the epoxy resin is preferably 0.5 equivalent or more and 1.2 equivalent or less in terms of hydroxyl equivalent. If the amount of the curing agent used is less than 0.5 equivalent, appropriate Tg may not be obtained, so 0.5 equivalent or more is preferable, but 0.6 equivalent or more is more preferable. In addition, when the amount of the curing agent used exceeds 1.2 equivalents, the water absorption properties of the resin may deteriorate. Therefore, 1.2 equivalents or less is preferable, but 1.0 equivalents or less is more preferable.
경화제로서 방향족 아민계 수지도 적합하게 사용할 수 있다. 방향족 아민계 수지로서는 에폭시 수지의 경화를 진행할 수 있으면 특별히 한정되지 않지만, 4,4'-디아미노디페닐술폰, 4,4'-비스(4-아미노페녹시)비페닐, 2,2-비스[4-(4-아미노페녹시)페닐]프로판, 1,3-비스(4-아미노페녹시)벤젠, 1,4-비스(4-아미노페녹시)벤젠, 트리메틸렌비스(4-아미노벤조에이트), 폴리테트라메틸렌옥시드-디-p-아미노벤조에이트, 3,3'-디메틸-4,4'-디아미노비페닐, 2,2'-디메틸-4,4'-디아미노비페닐, 4,4'-디아미노디페닐에테르, 3,4'-디아미노디페닐에테르, 비스[4-(4-아미노페녹시)페닐]술폰, 비스[4-(3아미노페녹시)페닐]술폰, 9,9'-비스(4-아미노페닐)플루오렌, 2,2-비스[4-(4-아미노페녹시)페닐]헥사플루오로프로판 등을 예시할 수 있고, 단독으로 또는 2종 이상 조합하여 사용할 수 있다.As a curing agent, an aromatic amine-based resin can also be suitably used. The aromatic amine resin is not particularly limited as long as it can cure the epoxy resin, but 4,4'-diaminodiphenylsulfone, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis [4-(4-aminophenoxy)phenyl]propane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, trimethylenebis(4-aminobenzo 8), polytetramethylene oxide-di-p-aminobenzoate, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl , 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3aminophenoxy)phenyl] sulfone, 9,9'-bis(4-aminophenyl)fluorene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, etc. can be exemplified, either alone or in combination of two. The above can be used in combination.
방향족 아민계 수지의 사용량은 한정되지 않지만, 에폭시 수지의 몰수를 1로 했을 때의 방향족 아민 화합물의 사용량은 0.3∼1.5몰이 최적이다. 방향족 아민계 수지의 사용량(합계 몰수)을 0.3 이상으로 함으로써, 적정한 열팽창 계수를 갖는 접착제층을 용이하게 얻을 수 있다. 이 관점에서, 방향족 아민계 수지의 사용량(합계 몰수)은 0.4 이상이 더욱 바람직하다. 또한, 방향족 아민계 수지의 사용량(합계 몰수)을 1.5 이하로 함으로써도, 적정한 열팽창 계수를 갖는 접착제층을 용이하게 얻을 수 있다. 이 관점에서, 방향족 아민계 수지의 사용량은 1.2 이하가 더욱 바람직하다.Although the amount of aromatic amine-based resin used is not limited, the amount of aromatic amine compound used when the number of moles of the epoxy resin is set to 1 is optimal at 0.3 to 1.5 moles. By setting the amount of aromatic amine-based resin (total number of moles) to be 0.3 or more, an adhesive layer having an appropriate thermal expansion coefficient can be easily obtained. From this point of view, the amount of aromatic amine-based resin used (total number of moles) is more preferably 0.4 or more. Moreover, the adhesive layer which has an appropriate thermal expansion coefficient can be obtained easily also by making the usage-amount (total number of moles) of aromatic amine-type resin into 1.5 or less. From this point of view, the amount of aromatic amine-based resin used is more preferably 1.2 or less.
(페녹시 수지)(phenoxy resin)
본 발명에 있어서의 페녹시 수지는 유리 전이 온도(Tg)가 120℃ 이하인 페녹시 수지이며, 구체적으로는 분자량(Mw)이 10,000 이상인 것이 적합하고, 수지 골격으로서는 접착성도 가미하여 BPA형, BPA/BPF형, BPA/BPS형, BP/BPS형 등이 적합하다. 시판품으로 말하면, 예를 들면 JER1256(중량 평균 분자량(이하, Mw라고 함) 48,000, 유리 전이 온도(이하, Tg라고 함) 95℃, 미쓰비시 카가쿠사제), PKHJ(Mw 57,000, Tg 98℃, GabrielPhenoxies 사제), PKHH(Mw 52,000, Tg 92℃, GabrielPhenoxies사제), PKFE(Mw 60,000, Tg 98℃, GabrielPhenoxies사제), FX-310(Mw 45,000, Tg 110℃, 닛테츠 에폭시 세이조사제) 등을 들 수 있다.The phenoxy resin in the present invention is a phenoxy resin having a glass transition temperature (Tg) of 120° C. or less, and specifically, those having a molecular weight (Mw) of 10,000 or more are suitable. BPF type, BPA/BPS type, BP/BPS type, etc. are suitable. As for commercial products, for example, JER1256 (weight average molecular weight (hereinafter referred to as Mw) 48,000, glass transition temperature (hereinafter referred to as Tg) 95 ° C., manufactured by Mitsubishi Chemical Corporation), PKHJ (Mw 57,000, Tg 98 ° C., GabrielPhenoxies manufactured), PKHH (Mw 52,000, Tg 92°C, manufactured by GabrielPhenoxies), PKFE (Mw 60,000, Tg 98°C, manufactured by GabrielPhenoxies), FX-310 (Mw 45,000, Tg 110°C, manufactured by Nippon-Tsu Epoxy Seisei), etc. can
유리 전이 온도(Tg)가 120℃ 이하인 페녹시 수지를 병용함으로써, 용제 가용성 폴리이미드 수지와 마찬가지로, 접착제로 형성된 접착제층에 가요성과 접착성을 부여함과 아울러, 접착제층과 동박을 비교적 저온에서 첩합할 수 있다. 페녹시 수지의 Tg는 접착제층과 동박을 라미네이트할 때에 동박 끊어짐이나 주름 등의 불량을 방지함과 아울러, 접착제로 제작되는 접착층의 Tg를 후술하는 최적 범위로 하기 때문에, 바람직하게는 80∼115℃이고, 더욱 바람직하게는 85∼113℃이며, 가장 바람직하게는 90∼110℃이다. 페녹시 수지의 Tg는 IPC-TM-650-2.4.24.3에 준거하여 측정할 수 있다.By using a phenoxy resin having a glass transition temperature (Tg) of 120 ° C. or less in combination, flexibility and adhesiveness are imparted to the adhesive layer formed of the adhesive, as in the case of the solvent-soluble polyimide resin, and the adhesive layer and the copper foil are bonded at a relatively low temperature. can be combined The Tg of the phenoxy resin is preferably 80 to 115 ° C. to prevent defects such as copper foil breakage and wrinkles when laminating the adhesive layer and the copper foil, and to set the Tg of the adhesive layer made of the adhesive to the optimum range described later. , more preferably 85 to 113 ° C, most preferably 90 to 110 ° C. Tg of a phenoxy resin can be measured based on IPC-TM-650-2.4.24.3.
접착제 조성물 중의 용제 가용성 폴리이미드 수지(고형분)와 페녹시 수지의 중량비는 통상 1:1.2∼12.0, 바람직하게는 1:1.3∼10.0, 보다 바람직하게는 1:1.4∼9.5, 더욱 바람직하게는 1:1.5∼9.0이다.The weight ratio of the solvent-soluble polyimide resin (solid content) and the phenoxy resin in the adhesive composition is usually 1:1.2 to 12.0, preferably 1:1.3 to 10.0, more preferably 1:1.4 to 9.5, still more preferably 1: 1.5 to 9.0.
접착제 조성물 중의 용제 가용성 폴리이미드 수지, 페녹시 수지, 에폭시 수지 및 에폭시 수지 경화제의 합계 함유량에 대한 용제 가용성 폴리이미드 수지 및 페녹시 수지의 합계 함유량(중량%)은 통상 10∼50중량%이다. 용제 가용성 폴리이미드 수지와 페녹시 수지의 합계 함유량은 10중량% 미만에서는 접착제 조성물로 형성되는 접착제층의 접착 강도와 가요성이 낮은 경우가 있기 때문에, 에폭시 수지 및 에폭시 수지 경화제를 포함한 합계 중량에 대하여 15중량% 이상이 바람직하고, 20중량% 이상이 더욱 바람직하다. 또한, 용제 가용성 폴리이미드 수지와 페녹시 수지의 합계 함유량은 50중량%를 초과하면 필름으로서의 파단 강도가 저하되는 경우가 있기 때문에, 에폭시 수지 및 에폭시 수지 경화제를 포함한 합계 중량에 대하여 45중량% 이하가 바람직하고, 40중량% 이하가 더욱 바람직하다.The total content (% by weight) of the solvent-soluble polyimide resin, the phenoxy resin, the epoxy resin and the epoxy resin curing agent in the adhesive composition is usually 10 to 50% by weight. If the total content of the solvent-soluble polyimide resin and the phenoxy resin is less than 10% by weight, the adhesive strength and flexibility of the adhesive layer formed from the adhesive composition may be low, so relative to the total weight including the epoxy resin and the epoxy resin curing agent 15% by weight or more is preferred, and 20% by weight or more is more preferred. In addition, since the breaking strength as a film may decrease when the total content of the solvent-soluble polyimide resin and the phenoxy resin exceeds 50% by weight, 45% by weight or less relative to the total weight including the epoxy resin and the epoxy resin curing agent It is preferred, and 40% by weight or less is more preferred.
본 발명의 접착제는 상기 용제 가용성 폴리이미드, 에폭시 수지, 경화제 및 페녹시 수지 이외에도, 경화 촉진제, 난연제 등을 포함하는 접착제 조성물이어도 된다.The adhesive of the present invention may be an adhesive composition containing a curing accelerator, a flame retardant and the like in addition to the above solvent-soluble polyimide, epoxy resin, curing agent and phenoxy resin.
(경화 촉진제)(curing accelerator)
본 발명의 접착제에는 필요에 따라 경화 촉진제를 병용할 수 있다. 경화 촉진제로서는 각종 이미다졸류 등의 일반적인 것을 사용할 수 있다. 주로 반응 속도나 포트 라이프의 관점에서 선택할 수 있다.A curing accelerator may be used in combination with the adhesive of the present invention, if necessary. As the curing accelerator, common ones such as various imidazoles can be used. You can choose mainly from the viewpoint of reaction speed or pot life.
(난연제)(flame retardant)
본 발명의 접착제에는 필요에 따라 난연성의 부여를 위해 난연제를 첨가할 수 있다. 할로겐 프리의 난연제로서, 축합형 인산 에스테르류, 포스파젠류, 폴리인산염류, HCA(9,10-디히드로-9-옥사-10-포스파페난트렌-10-옥사이드)유도체 등을 사용할 수 있다.A flame retardant may be added to the adhesive of the present invention to impart flame retardancy, if necessary. As the halogen-free flame retardant, condensed phosphoric acid esters, phosphazenes, polyphosphates, HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) derivatives, etc. can be used. .
에폭시 수지, 경화제, 용제 가용성 폴리이미드 및 페녹시 수지와 함께, 필요에 따라 상기의 각 수지 성분을 혼합하여 얻어진 혼합물에 용제를 첨가하고, 수지 고형분 20∼60중량%의 수지 바니시를 조제함으로써 접착제(조성물)를 제작할 수 있다.An adhesive ( composition) can be prepared.
본 발명의 접착제 조성물에 사용 가능한 용제는 특별히 한정되지 않지만, NMP, γ-부티로락톤, 벤조산 메틸, 디에틸렌글리콜모노메틸에테르아세테이트나 디에틸렌글리콜모노메틸에테르아세테이트 등의 고비점 용제와 시클로헥사논이나 MEK(메틸에틸케톤) 등의 중·저비점 용제를 조합하는 것이 바람직하다.The solvent that can be used in the adhesive composition of the present invention is not particularly limited, but a high boiling point solvent such as NMP, γ-butyrolactone, methyl benzoate, diethylene glycol monomethyl ether acetate or diethylene glycol monomethyl ether acetate and cyclohexanone or MEK (methyl ethyl ketone), etc. It is preferable to combine a low boiling point solvent.
(접착제 필름의 인장 탄성률 및 Tg)(Tensile modulus and Tg of adhesive film)
본 발명의 접착제(조성물)는 접착제로 제작한 반경화 상태의 필름을 180℃에서 90분간 가열 경화시켜서 얻어진 필름의 인장 탄성률이 1∼10.0GPa가 되고, Tg(유리 전이 온도)가 120∼190℃가 되는 접착제이다.The adhesive (composition) of the present invention heat-hardens a semi-cured film made of the adhesive at 180°C for 90 minutes, and the obtained film has a tensile modulus of 1 to 10.0 GPa and a Tg (glass transition temperature) of 120 to 190°C. It is an adhesive that becomes
인장 탄성률과 Tg를 측정하는 필름은 이하와 같이 하여 제작한다. 즉, 상기와 같이 하여 조제한 수지 바니시를 18㎛ 전해 동박의 샤이니면에 바 코터로 도포하고, 150℃의 온도에서 건조하여 반경화 상태(B 상태)의 접착제 부착 동박(접착제 두께:약 21㎛)을 제조한다. 용제의 휘발분은 0.6wt%로 조정한다. 이 접착제 부착 동박의 접착 시트면에 18㎛ 전해 동박 샤이니면을 중첩시키고, 진공 프레스에 투입하여 180℃×90분, 1MPa로 가열·가압(진공도 5torr) 성형한다. 이어서 동박을 전체면 에칭하여 얻어진 약 20㎛의 접착 필름에 대해 인장 탄성률과 Tg를 측정한다. 인장 탄성률은 IPC-TM-650-2.4.18.3에 준거하여 측정하고, Tg는 IPC-TM-650-2.4.24.3에 준거하여 측정했다.The film for measuring the tensile modulus and Tg is produced as follows. That is, the resin varnish prepared as described above is applied to the shiny side of the 18 μm electrodeposited copper foil with a bar coater, dried at a temperature of 150 ° C. to manufacture The volatile content of the solvent is adjusted to 0.6 wt%. An 18 μm electrodeposited copper foil shiny surface is superimposed on the adhesive sheet surface of this copper foil with adhesive, and put into a vacuum press to heat and press at 1 MPa at 180° C. for 90 minutes (vacuum degree: 5 torr). Subsequently, the tensile modulus and Tg of the adhesive film of about 20 μm obtained by etching the entire surface of the copper foil are measured. Tensile modulus was measured based on IPC-TM-650-2.4.18.3, and Tg was measured based on IPC-TM-650-2.4.24.3.
여기에서, 인장 탄성률은 주로 FCCL의 치수 안정성에 관계하지만, 동시에 프린트 배선판의 휨이나 굴곡짐 등에도 관계한다. 휨은 코어 재료로서 사용하는 폴리이미드 필름과 접착제층 사이의 특히 인장 탄성률이나 열팽창 계수의 미스매치로 인해 발생한다. 이러한 미스매치는 양면 대칭 구조의 접착 시트에서도 생기기 때문에, 인장 탄성률 및 열팽창 계수는 폴리이미드 필름과 접착제층 사이에서 동등한 값으로 하는 것이 바람직하지만, 이것을 실현하는 것은 용제 가용성 폴리이미드 수지에 있어서는 매우 어려운 과제였다. 그 해결책으로서 접착제층의 인장 탄성률을 코어 폴리이미드 필름 기재의 인장 탄성률 미만으로 하는 것이 유효하다. 접착제층의 인장 탄성률이 코어 폴리이미드 필름 기재의 인장 탄성률 이상이 되면, 코어 폴리이미드 필름 기재의 열변형이 커져 가열 후의 치수 변화율이 커진다. 또한, 접착제층의 인장 탄성률이 1GPa 미만이 되면 FCCL의 굴곡짐이 발생하기 쉽다. 인장 탄성률은 그중에서도 1.1∼5.0GPa, 더욱이는 1.2∼3.0GPa, 특히는 1.2∼2.5GPa의 범위 내인 것이 바람직하다.Here, the tensile elastic modulus is mainly related to the dimensional stability of FCCL, but at the same time it is also related to warpage and bending of the printed wiring board. Warpage occurs due to a mismatch between the polyimide film used as the core material and the adhesive layer, particularly in tensile modulus or thermal expansion coefficient. Since such a mismatch occurs even in an adhesive sheet having a double-sided symmetrical structure, it is desirable to set the tensile modulus and thermal expansion coefficient to equal values between the polyimide film and the adhesive layer, but realizing this is a very difficult problem for solvent-soluble polyimide resins. was As a solution to this, it is effective to make the tensile modulus of elasticity of the adhesive layer less than the tensile modulus of elasticity of the core polyimide film substrate. When the tensile modulus of elasticity of the adhesive layer is greater than or equal to the tensile modulus of elasticity of the core polyimide film base material, the thermal strain of the core polyimide film base material increases and the rate of dimensional change after heating increases. Further, when the tensile modulus of elasticity of the adhesive layer is less than 1 GPa, bending of the FCCL is likely to occur. The tensile modulus of elasticity is preferably within the range of 1.1 to 5.0 GPa, more preferably 1.2 to 3.0 GPa, and particularly 1.2 to 2.5 GPa.
또한, 접착제로 제작한 필름의 Tg(유리 전이 온도)는 그중에서도 125∼185℃, 더욱이는 130∼180℃인 것이 바람직하다.In addition, the Tg (glass transition temperature) of the film produced with the adhesive is preferably 125 to 185°C, more preferably 130 to 180°C.
(접착 시트)(adhesive sheet)
본 발명의 접착제(조성물)를 폴리이미드 필름 기재의 편면 또는 양면에 반경화 상태(B 상태)에 B 스테이지화함으로써, 라미네이트법 2. 2층 FCCL용 접착 시트를 얻을 수 있다. 구체적으로는, 상술한 바와 같이 본 발명의 접착제(조성물)를 NMP/MEK 등의 바람직한 혼합 유기 용제로 희석하여 조제한 수지 바니시를, 코어 재료인 폴리이미드 필름 기재의 편면 또는 양면에 그라비어 코터나 박막용 다이 코터 등을 이용하여 도공한다. 본 발명에서는 치수 안정성을 캐스팅법 2층 FCCL과 동등하게 하기 위해, 접착제층의 도공 두께, 도공 온도 및 열경화 온도를 이하의 특정의 범위로 하는 것이 바람직하다.Laminate method 2. A two-layer FCCL adhesive sheet can be obtained by B-staging the adhesive (composition) of the present invention to a semi-cured state (B state) on one or both surfaces of a polyimide film substrate. Specifically, as described above, a resin varnish prepared by diluting the adhesive (composition) of the present invention with a suitable mixed organic solvent such as NMP/MEK is applied to one or both sides of a polyimide film substrate as a core material for a gravure coater or thin film. Coating is performed using a die coater or the like. In the present invention, in order to make the dimensional stability equal to that of the casting method 2-layer FCCL, it is preferable to set the coating thickness, coating temperature and heat curing temperature of the adhesive layer to the following specific ranges.
접착제층의 도공 두께는 적층하는 동박의 조화면(粗化面)을 매입하는 최저 두께 이상인 것이 필요하고, 구체적으로는 동박 표면의 표면 거칠기의 Rz(JIS B 0601-2001에 준거하여 측정) 이상의 두께가 바람직하다. 이 도공 두께는 특히 치수 안정성에도 영향을 끼치기 때문에, 이 조건에 추가로, 편측 접착층의 두께가 코어 폴리이미드 필름의 두께의 20% 이하, 바람직하게는 15% 이하, 더욱 바람직하게는 13% 이하로 하는 것이 바람직하다. 접착 시트의 접착제층의 두께는 상기 2개의 조건 범위를 함께 만족하는 것이 바람직하지만, 두께의 절대값으로서도 1.6∼4.0㎛, 더욱이는 2.0∼3.5㎛, 특히는 2.5∼2.9㎛인 것이 바람직하다. 접착제층의 두께를 이러한 범위로 함으로써, 접착제층과 코어 폴리이미드 필름 사이의 물성차(주로 인장 탄성률, 열팽창 계수)를 복합 필름으로서의 FCCL도 물성에 표면화시키지 않고, 접착 특성을 유지할 수 있다. 또한, 접착 시트의 접착제층의 두께는 접착 시트를 건조기로 180℃에서 90분간 가열 경화시킨 경우에, 1.5∼3.5㎛의 두께가 되는 것이 바람직하다.The coating thickness of the adhesive layer is required to be equal to or greater than the minimum thickness to embed the roughened surface of the copper foil to be laminated. is preferable Since this coating thickness particularly affects dimensional stability, in addition to this condition, the thickness of the adhesive layer on one side is 20% or less, preferably 15% or less, more preferably 13% or less of the thickness of the core polyimide film. It is desirable to do The thickness of the adhesive layer of the adhesive sheet preferably satisfies both of the above two conditional ranges, but the absolute value of the thickness is also preferably 1.6 to 4.0 μm, more preferably 2.0 to 3.5 μm, particularly 2.5 to 2.9 μm. By setting the thickness of the adhesive layer within this range, the difference in physical properties (mainly tensile modulus and thermal expansion coefficient) between the adhesive layer and the core polyimide film does not surface in the physical properties of FCCL as a composite film, and adhesive properties can be maintained. Further, the thickness of the adhesive layer of the adhesive sheet is preferably 1.5 to 3.5 μm when the adhesive sheet is heated and cured in a dryer at 180° C. for 90 minutes.
본 발명의 접착제(조성물)로 제작한 필름의 인장 탄성률과 Tg를 상기의 특정 범위 내로 하고, 또한 접착 시트의 접착제층의 두께를 1.6∼4.0㎛, 바람직하게는 1.8∼2.9㎛로 함으로써, 복합층 필름으로서의 FCCL의 치수 안정성을 코어 폴리이미드 필름의 치수 안정성과 거의 동등하게 할 수 있다. 이에 따라, 캐스팅법 2층 FCCL 수준의 특성과 라미네이트법 2층 FCCL 이상의 생산성이 우수한 접착 시트 및 라미네이트법 2. 2층 FCCL을 제공하는 것이 가능해졌다. 또한, 상기의 조건을 실현함으로써, 편면 2층 FCCL의 열팽창 계수의 불일치로 인한 휨의 발생을 막을 수 있기 때문에, 현재 많이 채용되고 있는 TPI 양측 대칭 구조에 의하지 않아도 휨을 억제하는 것이 가능해졌다.The composite layer is obtained by setting the tensile modulus and Tg of the film made of the adhesive (composition) of the present invention within the above-specified range, and setting the thickness of the adhesive layer of the adhesive sheet to 1.6 to 4.0 μm, preferably 1.8 to 2.9 μm. The dimensional stability of FCCL as a film can be made almost equal to that of the core polyimide film. Accordingly, it has become possible to provide an adhesive sheet and a laminated 2.2-layer FCCL having excellent properties comparable to those of the casting-method 2-layer FCCL and productivity higher than that of the laminated 2-layer FCCL. In addition, by realizing the above conditions, it is possible to prevent the occurrence of warpage due to the mismatch of thermal expansion coefficients of the single-sided, two-layer FCCL, so that warpage can be suppressed even without resorting to the TPI bilateral symmetrical structure that is currently widely used.
접착제층의 도공 온도(도공 후의 건조 온도를 포함함)도 FCCL에 열변형을 주는 요인이 되기 때문에, 도공 온도는 150℃ 이하가 바람직하다.Since the coating temperature of the adhesive layer (including the drying temperature after coating) also becomes a factor in giving the FCCL thermal deformation, the coating temperature is preferably 150°C or less.
(플렉서블 동장 적층(FCCL))(Flexible copper clad laminate (FCCL))
상기와 같이 하여 제작한 접착 시트의 접착제층의 표면에 동박을 라미네이트(첩합)한 후에 접착제층을 경화시킴으로써, 라미네이트법 2. 2층 플렉서블 동장 적층판(FCCL)을 제작할 수 있다. 접착 시트의 접착제층과 동박의 라미네이트는 라미네이터를 이용하여 70∼120℃, 바람직하게는 75∼115℃, 더욱 바람직하게는 80∼110℃에서 행할 수 있다. 이러한 비교적 저온에서 라미네이트를 행함으로써, 동박 끊어짐이나 주름 등의 불량이 없는 플렉서블 동장 적층판을 제작할 수 있다. 동박의 두께는 통상 1.5∼20㎛이고, 바람직하게는 5∼18㎛이다. 열변형의 최대 요인인 접착제층의 경화 온도는 200℃ 이하, 더욱이는 195℃ 이하, 특히는 190℃ 이하가 바람직하고, 150℃ 이상, 더욱이는 160℃ 이상이 바람직하다.Laminate method 2. A two-layer flexible copper clad laminate (FCCL) can be produced by laminating (bonding) copper foil on the surface of the adhesive layer of the adhesive sheet produced as described above and then curing the adhesive layer. The adhesive layer of the adhesive sheet and the copper foil can be laminated using a laminator at 70 to 120°C, preferably 75 to 115°C, and more preferably 80 to 110°C. By laminating at such a relatively low temperature, a flexible copper-clad laminate without defects such as copper foil breakage and wrinkles can be produced. The thickness of the copper foil is usually 1.5 to 20 μm, preferably 5 to 18 μm. The curing temperature of the adhesive layer, which is the largest factor of thermal deformation, is preferably 200°C or less, more preferably 195°C or less, particularly 190°C or less, and preferably 150°C or more, more preferably 160°C or more.
이상과 같이 하여, 접착 시트 및 FCCL을 제작함으로써, 에칭 후 및 가열 후의 치수 변화율을 캐스팅법 2층 FCCL과 동등하게 할 수 있다.By producing the adhesive sheet and the FCCL as described above, the rate of dimensional change after etching and heating can be equal to that of the two-layer FCCL by the casting method.
종래의 라미네이트법 2층 FCCL의 에칭 및 가열 후에 있어서 치수 안정성이 악화되는 주요인 중 하나는 300℃ 이상의 고온 및 고압 하에서의 동박과의 라미네이트 공정에 있어서 변형이 발생하는 것에 있었다. 본 발명에서는 열경화성 수지인 특정의 용제 가용성 폴리이미드, Tg가 120℃ 이하인 페녹시 수지, 에폭시 수지 및 에폭시 수지 경화제를 포함하는 폴리머 알로이의 접착제를 사용함으로써, 동박 끊어짐이나 주름 등이 생기지 않는 비교적 저온에서의 동박 라미네이트와, 200℃ 이하에서의 열경화가 가능해지고, 각각의 공정에서 발생하는 변형을 감소시켜 치수 수축률을 크게 개선할 수 있다.One of the main causes of deterioration in dimensional stability after etching and heating of a conventional laminated two-layer FCCL was that deformation occurred in the lamination process with copper foil under high temperature and high pressure of 300 ° C. or higher. In the present invention, by using a polymer alloy adhesive containing a specific solvent-soluble polyimide, which is a thermosetting resin, a phenoxy resin having a Tg of 120° C. or less, an epoxy resin, and an epoxy resin curing agent, at a relatively low temperature without copper foil breakage or wrinkles. The copper foil laminate of and thermal curing at 200° C. or lower is possible, and the dimensional shrinkage rate can be greatly improved by reducing the strain generated in each process.
(실시예)(Example)
이하, 본 발명을 실시예에 의거하여 상세히 설명하지만, 본 발명은 다양한 다른 실시형태로 변형할 수 있는 것이며, 하기 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail based on examples, but the present invention can be modified into various other embodiments, and is not limited to the following examples.
1. 용제 가용성 폴리이미드 수지의 합성1. Synthesis of solvent-soluble polyimide resin
(합성 실시예 1)(Synthesis Example 1)
유리제의 세퍼러블 3구 플라스크에, 교반기, 질소 도입관, 및 수분 수용기를 구비한 냉각관을 부착했다. 3,3',4,4'-비페닐테트라카르복실산 디무수물(이하 BPDA라고 함) 58.84g(0.2몰), 5-아미노-1-(4'-아미노페닐)-1,3,3-트리메틸인단 26.64g (0.1몰)(페닐인단 구조 함유 방향족 디아민), 발레로락톤 1.5g(0.015몰), 피리딘 2.4g(0.03몰), NMP 200g, 톨루엔 30g을 투입하고, 실온에서 질소 분위기 하 200rpm으로 30분 교반한 후, 180℃로 승온하여 1시간 가열 교반했다. 반응 중, 톨루엔-물의 공비분을 제거했다.A cooling pipe provided with a stirrer, a nitrogen inlet pipe, and a water container was attached to a glass separable three-necked flask. 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (hereinafter referred to as BPDA) 58.84 g (0.2 mol), 5-amino-1- (4'-aminophenyl) -1,3,3 -Trimethylindan 26.64 g (0.1 mol) (phenylindan structure-containing aromatic diamine), valerolactone 1.5 g (0.015 mol), pyridine 2.4 g (0.03 mol), NMP 200 g, and toluene 30 g were added, and the mixture was stirred at room temperature under a nitrogen atmosphere. After stirring at 200 rpm for 30 minutes, the temperature was raised to 180°C and the mixture was heated and stirred for 1 hour. During the reaction, the toluene-water azeotrope was removed.
실온으로 냉각하여, BPDA 44.13g(0.15몰), 6-아미노-1-(4'-아미노페닐)-1,3,3-트리메틸인단 66,60g(0.25몰), NMP 360g, 톨루엔 90g을 첨가하고, 실온에서 30분 교반한 후, 180℃로 승온하여 1시간 가열 교반했다. 물-톨루엔의 공비의 환류물을 계외로 제거하면서, 180℃에서 2시간 30분 가열 교반하여 반응을 종료했다. 얻어진 생성물에 γ-부티로락톤을 첨가해 희석하고, 고형분 20중량%의 블록 공중합 폴리이미드 용액을 얻었다.After cooling to room temperature, 44.13 g (0.15 mol) of BPDA, 66,60 g (0.25 mol) of 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 360 g of NMP, and 90 g of toluene were added. After stirring at room temperature for 30 minutes, the temperature was raised to 180°C, followed by heating and stirring for 1 hour. The reaction was terminated by heating and stirring at 180°C for 2 hours and 30 minutes while removing the azeotropic reflux product of water and toluene out of the system. [gamma]-butyrolactone was added and diluted to the obtained product, and the block-copolymerization polyimide solution of 20 weight% of solid content was obtained.
(합성 실시예 2)(Synthesis Example 2)
유리제의 세퍼러블 3구 플라스크에, 교반기, 질소 도입관, 및 수분 수용기를 구비한 냉각관을 부착했다. 3,4,3',4'-벤조페논테트라카르복실산 디무수물(이하 BTDA라고 함) 64.45g(0.2몰), 5-아미노-1-(4'-아미노페닐)-1,3,3-트리메틸인단 26.64g(0.1몰)(페닐인단 구조 함유 방향족 디아민), 발레로락톤 1.5g(0.015몰), 피리딘 2.4g(0.03몰), NMP 200g, 톨루엔 30g을 투입하고, 실온에서 질소 분위기 하 200rpm으로 30분 교반한 후, 180℃로 승온하여 1시간 가열 교반했다. 반응 중, 톨루엔-물의 공비분을 제거했다.A cooling pipe provided with a stirrer, a nitrogen inlet pipe, and a water container was attached to a glass separable three-necked flask. 3,4,3',4'-benzophenonetetracarboxylic acid dianhydride (hereinafter referred to as BTDA) 64.45 g (0.2 mol), 5-amino-1- (4'-aminophenyl) -1,3,3 -Trimethylindan 26.64 g (0.1 mol) (a phenyl indan structure-containing aromatic diamine), valerolactone 1.5 g (0.015 mol), pyridine 2.4 g (0.03 mol), NMP 200 g, and toluene 30 g were added, and the mixture was stirred at room temperature under a nitrogen atmosphere. After stirring at 200 rpm for 30 minutes, the temperature was raised to 180°C and the mixture was heated and stirred for 1 hour. During the reaction, the toluene-water azeotrope was removed.
실온으로 냉각하여, BTDA 48.33g(0.15몰), 6-아미노-1-(4'-아미노페닐)-1,3,3-트리메틸인단 66,60g(0.25몰), NMP 360g, 톨루엔 90g을 첨가하고, 실온에서 30분 교반한 후, 180℃로 승온하여 1시간 가열 교반했다. 물-톨루엔의 공비의 환류물을 계외로 제거하면서, 180℃에서 2시간 30분 가열 교반하여 반응을 종료했다. 얻어진 생성물에 γ-부티로락톤을 첨가해 희석하고, 고형분 20중량%의 블록 공중합 폴리이미드 용액을 얻었다.After cooling to room temperature, 48.33 g (0.15 mol) of BTDA, 66,60 g (0.25 mol) of 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 360 g of NMP, and 90 g of toluene were added. After stirring at room temperature for 30 minutes, the temperature was raised to 180°C, followed by heating and stirring for 1 hour. The reaction was terminated by heating and stirring at 180°C for 2 hours and 30 minutes while removing the azeotropic reflux product of water and toluene out of the system. [gamma]-butyrolactone was added and diluted to the obtained product, and the block-copolymerization polyimide solution of 20 weight% of solid content was obtained.
(합성 실시예 3)(Synthesis Example 3)
유리제의 세퍼러블 3구 플라스크에, 교반기, 질소 도입관, 및 수분 수용기를 구비한 냉각관을 부착했다. 3,4,3',4'-벤조페논테트라카르복실산 디무수물(이하 BTDA라고 함) 64.45g(0.2몰), 4,4'-디아미노디페닐에테르 20.02g(0.1몰), 발레로락톤 1.5g(0.015몰), 피리딘 2.4g(0.03몰), NMP 200g, 톨루엔 30g을 투입하고, 실온에서 질소 분위기 하 200rpm으로 30분 교반한 후, 180℃로 승온하여 1시간 가열 교반했다. 반응 중, 톨루엔-물의 공비분을 제거했다.A cooling pipe provided with a stirrer, a nitrogen inlet pipe, and a water container was attached to a glass separable three-necked flask. 3,4,3',4'-benzophenonetetracarboxylic acid dianhydride (hereinafter referred to as BTDA) 64.45 g (0.2 mol), 4,4'-diaminodiphenyl ether 20.02 g (0.1 mol), Valero 1.5 g (0.015 mol) of lactone, 2.4 g (0.03 mol) of pyridine, 200 g of NMP, and 30 g of toluene were charged, and after stirring at room temperature at 200 rpm for 30 minutes under a nitrogen atmosphere, the mixture was heated to 180°C and heated and stirred for 1 hour. During the reaction, the toluene-water azeotrope was removed.
실온으로 냉각하여, BTDA 48.33g(0.15몰), 5-아미노-1-(4'-아미노페닐)-1,3,3-트리메틸인단 66.60g(0.25몰), NMP 360g, 톨루엔 90g을 첨가하고, 실온에서 30분 교반한 후, 180℃로 승온하여 1시간 가열 교반했다. 물-톨루엔의 공비의 환류물을 계외로 제거하면서, 180℃에서 2시간 30분 가열 교반하여 반응을 종료했다. 얻어진 생성물에 γ-부티로락톤을 첨가해 희석하고, 고형분 20중량%의 블록 공중합 폴리이미드 용액을 얻었다.After cooling to room temperature, 48.33 g (0.15 mol) of BTDA, 66.60 g (0.25 mol) of 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 360 g of NMP, and 90 g of toluene were added. , After stirring at room temperature for 30 minutes, the temperature was raised to 180°C and heating and stirring were performed for 1 hour. The reaction was terminated by heating and stirring at 180°C for 2 hours and 30 minutes while removing the azeotropic reflux product of water and toluene out of the system. [gamma]-butyrolactone was added and diluted to the obtained product, and the block-copolymerization polyimide solution of 20 weight% of solid content was obtained.
(합성 실시예 4)(Synthesis Example 4)
유리제의 세퍼러블 3구 플라스크에, 교반기, 질소 도입관, 및 수분 수용기를 구비한 냉각관을 부착했다. 3,4,3',4'-벤조페논테트라카르복실산 디무수물(이하 BTDA라고 함) 64.45g(0.2몰), 5-아미노-1-(4'-아미노페닐)-1,3,3-트리메틸인단 15.98g(0.06몰), 1,3-비스(3-아미노프로필)테트라메틸디실록산 9.94g(0.04몰), 발레로락톤 1.5g(0.015몰), 피리딘 2.4g(0.03몰), NMP 200g, 톨루엔 30g을 투입하고, 실온에서 30분간 교반한 후, 180℃로 승온하여 1시간 교반했다. 반응 중, 톨루엔-물의 공비분을 제거했다.A cooling pipe provided with a stirrer, a nitrogen inlet pipe, and a water container was attached to a glass separable three-necked flask. 3,4,3',4'-benzophenonetetracarboxylic acid dianhydride (hereinafter referred to as BTDA) 64.45 g (0.2 mol), 5-amino-1- (4'-aminophenyl) -1,3,3 -trimethylindane 15.98 g (0.06 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 9.94 g (0.04 mol), valerolactone 1.5 g (0.015 mol), pyridine 2.4 g (0.03 mol), 200 g of NMP and 30 g of toluene were introduced, and after stirring at room temperature for 30 minutes, the temperature was raised to 180°C and stirred for 1 hour. During the reaction, the toluene-water azeotrope was removed.
실온으로 냉각하여, BTDA 48.33g(0.15몰), 5-아미노-1-(4'-아미노페닐)-1,3,3-트리메틸인단 66.60g(0.25몰), NMP 360g, 톨루엔 90g을 첨가하고, 실온에서 30분 교반한 후, 180℃로 승온하여 1시간 가열 교반했다. 물-톨루엔의 공비의 환류물을 계외로 제거하면서, 180℃에서 2시간 30분 가열 교반하여 반응을 종료했다. 얻어진 생성물에 γ-부티로락톤을 첨가해 희석하고, 고형분 20중량%의 블록 공중합 폴리이미드 용액을 얻었다.After cooling to room temperature, 48.33 g (0.15 mol) of BTDA, 66.60 g (0.25 mol) of 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 360 g of NMP, and 90 g of toluene were added. , After stirring at room temperature for 30 minutes, the temperature was raised to 180°C and heating and stirring were performed for 1 hour. The reaction was terminated by heating and stirring at 180°C for 2 hours and 30 minutes while removing the azeotropic reflux product of water and toluene out of the system. [gamma]-butyrolactone was added and diluted to the obtained product, and the block-copolymerization polyimide solution of 20 weight% of solid content was obtained.
2. 접착제 조성물의 조제, 접착 시트 및 FCCL의 제작2. Preparation of adhesive composition, production of adhesive sheet and FCCL
(실시예 1)(Example 1)
347중량부의 디시클로펜타디엔형 에폭시 수지 「HP-7200H」(DIC사제, 에폭시 당량 283, 수지 고형분 80중량%), 183중량부의 멜라민 변성 크레졸노볼락 수지 「EXB-9854」(DIC사제, 수산기가 151, 수지 고형분 80중량%), 290중량부의 가용성 폴리이미드 수지(합성 실시예 1, 수지 고형분 20중량%), 91중량부의 페녹시 수지 「jER1256」(미쓰비시 케미컬사제, Mw≒48,000, Tg 95℃, 수지 고형분 100중량%), 57중량부의 포스파젠계 유도체 「FP-100」(후시미 세이야쿠쇼사제), 0.7중량부의 2-에틸-4메틸이미다졸로 이루어지는 혼합물에 용매로서 γ-부티로락톤/시클로헥사논 혼합 용제를 첨가하여 수지 고형분 40중량%의 수지 바니시를 조제했다.347 parts by weight of dicyclopentadiene type epoxy resin "HP-7200H" (manufactured by DIC, epoxy equivalent 283, resin solid content 80% by weight), 183 parts by weight of melamine-modified cresol novolac resin "EXB-9854" (manufactured by DIC, hydroxyl value) 151, resin solid content 80% by weight), 290 parts by weight of soluble polyimide resin (Synthesis Example 1, resin solid content 20% by weight), 91 parts by weight of phenoxy resin "jER1256" (manufactured by Mitsubishi Chemical Corporation, Mw ≈ 48,000, Tg 95 ° C. , Resin solid content 100% by weight), 57 parts by weight of a phosphazene derivative "FP-100" (manufactured by Fushimi Pharmaceutical Co., Ltd.), 0.7 parts by weight of a mixture consisting of 2-ethyl-4methylimidazole, γ-butyrolactone as a solvent /cyclohexanone mixed solvent was added to prepare a resin varnish having a resin solid content of 40% by weight.
(실시예 2)(Example 2)
337중량부의 비페닐형 에폭시 수지 「NC-3000H」 (니혼 카야쿠사제, 에폭시 당량 275, 수지 고형분 80중량%), 202중량부의 멜라민 변성 페놀노볼락 수지 「LA-7054」(DIC사제, 수산기가 125, 수지 고형분 60중량%), 98중량부의 가용성 폴리이미드 수지(합성 실시예 2, 수지 고형분 20중량%), 170중량부의 페녹시 수지 「jER1256」(미쓰비시 케미컬사제, Mw≒48,000, Tg 95℃, 수지 고형분 100중량%), 57중량부의 포스파젠계 유도체 「FP-100」(후시미 세이야쿠쇼사제), 0.7중량부의 2-에틸-4메틸이미다졸로 이루어지는 혼합물에 용매로서 γ-부티로락톤/시클로헥사논 혼합 용제를 첨가하여 수지 고형분 40중량%의 수지 바니시를 조제했다.337 parts by weight of biphenyl type epoxy resin "NC-3000H" (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 275, resin solid content 80% by weight), 202 parts by weight of melamine-modified phenolic novolak resin "LA-7054" (manufactured by DIC Corporation, hydroxyl value) 125, resin solid content 60% by weight), 98 parts by weight soluble polyimide resin (Synthesis Example 2, resin solid content 20% by weight), 170 parts by weight phenoxy resin "jER1256" (manufactured by Mitsubishi Chemical Corporation, Mw ≒ 48,000, Tg 95 ° C. , Resin solid content 100% by weight), 57 parts by weight of a phosphazene derivative "FP-100" (manufactured by Fushimi Pharmaceutical Co., Ltd.), 0.7 parts by weight of a mixture consisting of 2-ethyl-4methylimidazole, γ-butyrolactone as a solvent /cyclohexanone mixed solvent was added to prepare a resin varnish having a resin solid content of 40% by weight.
(실시예 3)(Example 3)
349중량부의 나프톨아랄킬형 에폭시 수지 「ESN-165」(닛테츠 에폭시 세이조사제, 에폭시 당량 265, 수지 고형분 80중량%), 177중량부의 멜라민 변성 페놀노볼락 수지 「LA-7054」(DIC사제, 수산기가 125, 수지 고형분 60중량%), 290중량부의 가용성 폴리이미드 수지(합성 실시예 3, 수지 고형분 20중량%), 91중량부의 페녹시 수지 「jER1256」(미쓰비시 케미컬사제, Mw≒48,000, Tg 95℃, 수지 고형분 100중량%), 57중량부의 포스파젠계 유도체 「FP-100」(후시미 세이야쿠쇼사제), 0.7중량부의 2-에틸-4메틸이미다졸로 이루어지는 혼합물에 용매로서 γ-부티로락톤/시클로헥사논 혼합 용제를 첨가하여 수지 고형분 40중량%의 수지 바니시를 조제했다.349 parts by weight of naphthol aralkyl type epoxy resin "ESN-165" (Nittetsu Epoxy Seizo, made by epoxy equivalent 265, resin solid content 80% by weight), 177 parts by weight of melamine-modified phenolic novolac resin "LA-7054" (manufactured by DIC, Hydroxyl value 125, resin solid content 60% by weight), 290 parts by weight of soluble polyimide resin (Synthesis Example 3, resin solid content 20% by weight), 91 parts by weight of phenoxy resin “jER1256” (manufactured by Mitsubishi Chemical Corporation, Mw ≒ 48,000, Tg 95 ° C., 100% by weight of resin solid content), 57 parts by weight of a phosphazene derivative “FP-100” (manufactured by Fushimi Pharmaceutical Co., Ltd.), and 0.7 parts by weight of 2-ethyl-4methylimidazole, γ-buty as a solvent A resin varnish having a resin solid content of 40% by weight was prepared by adding a mixed solvent of rolactone/cyclohexanone.
(실시예 4)(Example 4)
337중량부의 비페닐형 에폭시 수지 「NC-3000H」(니혼 카야쿠사제, 에폭시 당량 275, 수지 고형분 80중량%), 202중량부의 멜라민 변성 페놀노볼락 수지 「LA-7054」(DIC사제, 수산기가 125, 수지 고형분 60중량%), 98중량부의 가용성 폴리이미드 수지(합성 실시예 1, 수지 고형분 20중량%), 170중량부의 페녹시 수지 「FX-310」(닛테츠 에폭시 세이조사제, Mw≒45,000, Tg 110℃, 수지 고형분 100중량%), 57중량부의 포스파젠계 유도체 「FP-100」(후시미 세이야쿠쇼사제), 0.7중량부의 2-에틸-4메틸이미다졸로 이루어지는 혼합물에 용매로서 γ-부티로락톤/시클로헥사논 혼합 용제를 첨가하여 수지 고형분 40중량%의 수지 바니시를 조제했다.337 parts by weight of biphenyl type epoxy resin "NC-3000H" (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 275, resin solid content 80% by weight), 202 parts by weight of melamine-modified phenolic novolac resin "LA-7054" (manufactured by DIC Corporation, hydroxyl value) 125, resin solid content 60% by weight), 98 parts by weight of soluble polyimide resin (Synthesis Example 1, resin solid content 20% by weight), 170 parts by weight of phenoxy resin "FX-310" (Nittetsu Epoxy Seizo, Mw ≒ 45,000, Tg 110 ° C., resin solid content 100% by weight), 57 parts by weight of a phosphazene derivative "FP-100" (manufactured by Fushimi Pharmaceutical Co., Ltd.), 0.7 parts by weight of 2-ethyl-4methylimidazole as a solvent. A mixed solvent of γ-butyrolactone/cyclohexanone was added to prepare a resin varnish having a resin solid content of 40% by weight.
(실시예 5)(Example 5)
372중량부의 디시클로펜타디엔형 에폭시 수지 「HP-7200H」(DIC사제, 에폭시 당량 283, 수지 고형분 80중량%), 128중량부의 방향족 아민 「엘라스머 250P」(쿠미아이 카가쿠 고교사제, MW=488, 수지 고형분 100중량%), 290중량부의 가용성 폴리이미드 수지(합성 실시예 4, 수지 고형분 20중량%), 91중량부의 페녹시 수지 「jER1256」(미쓰비시 케미컬사제, Mw≒48,000, Tg 95℃, 수지 고형분 100중량%), 57중량부의 포스파젠계 유도체 「FP-100」(후시미 세이야쿠쇼사제), 0.7중량부의 2-에틸-4메틸이미다졸로 이루어지는 혼합물에 용매로서 γ-부티로락톤/시클로헥사논 혼합 용제를 첨가하여 수지 고형분 40중량%의 수지 바니시를 조제했다.372 parts by weight of dicyclopentadiene type epoxy resin "HP-7200H" (manufactured by DIC Corporation, epoxy equivalent 283, resin solid content 80% by weight), 128 parts by weight of aromatic amine "Elasmer 250P" (manufactured by Kumiai Kagaku Kogyo Co., Ltd., MW= 488, resin solid content 100% by weight), 290 parts by weight of soluble polyimide resin (Synthesis Example 4, resin solid content 20% by weight), 91 parts by weight of phenoxy resin “jER1256” (manufactured by Mitsubishi Chemical Corporation, Mw ≒ 48,000, Tg 95 ° C. , Resin solid content 100% by weight), 57 parts by weight of a phosphazene derivative "FP-100" (manufactured by Fushimi Pharmaceutical Co., Ltd.), 0.7 parts by weight of a mixture consisting of 2-ethyl-4methylimidazole, γ-butyrolactone as a solvent /cyclohexanone mixed solvent was added to prepare a resin varnish having a resin solid content of 40% by weight.
(실시예 6)(Example 6)
372중량부의 디시클로펜타디엔형 에폭시 수지 「HP-7200H」(DIC사제, 에폭시 당량 283, 수지 고형분 80중량%), 128중량부의 방향족 아민 「엘라스머 250P」(쿠미아이 카가쿠 고교사제, MW=488, 수지 고형분 100중량%), 98중량부의 가용성 폴리이미드 수지(합성 실시예 3, 수지 고형분 20중량%), 170중량부의 페녹시 수지 「FX-310」(닛테츠 에폭시 세이조사제, Mw≒45,000, Tg 110℃, 수지 고형분 100중량%), 57중량부의 포스파젠계 유도체 「FP-100」(후시미 세이야쿠쇼사제), 0.7중량부의 2-에틸-4메틸이미다졸로 이루어지는 혼합물에 용매로서 γ-부티로락톤/시클로헥사논 혼합 용제를 첨가하여 수지 고형분 40중량%의 수지 바니시를 조제했다.372 parts by weight of dicyclopentadiene type epoxy resin "HP-7200H" (manufactured by DIC Corporation, epoxy equivalent 283, resin solid content 80% by weight), 128 parts by weight of aromatic amine "Elasmer 250P" (manufactured by Kumiai Kagaku Kogyo Co., Ltd., MW= 488, resin solid content 100% by weight), 98 parts by weight of soluble polyimide resin (Synthesis Example 3, resin solid content 20% by weight), 170 parts by weight of phenoxy resin "FX-310" (Nittetsu Epoxy Seizo, Mw ≒ 45,000, Tg 110 ° C., resin solid content 100% by weight), 57 parts by weight of a phosphazene derivative "FP-100" (manufactured by Fushimi Pharmaceutical Co., Ltd.), 0.7 parts by weight of 2-ethyl-4methylimidazole as a solvent. A mixed solvent of γ-butyrolactone/cyclohexanone was added to prepare a resin varnish having a resin solid content of 40% by weight.
상기 실시예 1∼6에서 조제한 수지 바니시를 고형분 20%까지 희석하고, 20㎛폴리이미드 필름(캡톤(등록상표) EN) 상에 그라비어 코터로 도포하고, 150℃의 온도에서 건조하여 양면 도공의 B 상태의 접착 시트(편측 막두께:2.8㎛)를 제조했다. 휘발분은 0.6wt%로 조정했다. 이 접착 시트에 12㎛의 Rz=1.8㎛의 동박을 라미네이터로 라미네이트 온도 110℃ 또는 100℃에서 양면에 첩합하고, 그 후 건조기로 180℃×90분 가열해 접착제층을 가열 경화시켜 양면 동박 FCCL을 제작했다. 마찬가지로, 상기 각 예의 수지 바니시를 고형분 20%까지 희석하고, 20㎛ 폴리이미드 필름(캡톤(등록상표) EN) 상에 그라비어 코터로 도포하고, 150℃의 온도에서 건조하여 편면 도공의 B 상태의 접착 시트(편측 막두께:2.8㎛)를 제조했다. 휘발분은 0.6wt%로 조정했다. 이 접착 시트에 12㎛의 Rz=1.8㎛의 동박을 라미네이터로 라미네이트 온도 110℃ 또는 100℃에서 편면에 첩합하고, 그 후 건조기로 180℃×90분 가열해접착제층을 가열 경화시켜 편면 동박 FCCL을 제작했다.The resin varnish prepared in Examples 1 to 6 was diluted to a solid content of 20%, applied with a gravure coater on a 20 μm polyimide film (Kapton (registered trademark) EN), and dried at a temperature of 150 ° C. B of double-sided coating An adhesive sheet (film thickness on one side: 2.8 μm) was prepared. Volatile content was adjusted to 0.6 wt%. To this adhesive sheet, 12 μm Rz = 1.8 μm copper foil was bonded to both sides with a laminator at a lamination temperature of 110 ° C or 100 ° C, and then heated with a dryer at 180 ° C for 90 minutes to heat-harden the adhesive layer to form a double-sided copper foil FCCL. made Similarly, the resin varnish of each of the above examples was diluted to a solid content of 20%, applied on a 20 μm polyimide film (Kapton (registered trademark) EN) with a gravure coater, and dried at a temperature of 150 ° C. A sheet (film thickness on one side: 2.8 μm) was prepared. Volatile content was adjusted to 0.6 wt%. To this adhesive sheet, a 12 μm Rz = 1.8 μm copper foil was bonded to one side with a laminator at a lamination temperature of 110 ° C or 100 ° C, and then heated with a dryer at 180 ° C for 90 minutes to heat and cure the adhesive layer to obtain single-sided copper foil FCCL. made
(비교예 1)(Comparative Example 1)
337중량부의 비페닐형 에폭시 수지 「NC-3000H」(니혼 카야쿠사제, 에폭시 당량 275, 수지 고형분 80중량%), 202중량부의 멜라민 변성 페놀노볼락 수지 「LA-7054」(DIC사제, 수산기가 125, 수지 고형분 60중량%), 190중량부의 페녹시 수지 「jER1256」(미쓰비시 케미컬사제, Mw≒48,000, Tg 95℃, 수지 고형분 100중량%), 57중량부의 포스파젠계 유도체 「FP-100」(후시미 세이야쿠쇼사제), 0.7중량부의 2-에틸-4메틸이미다졸로 이루어지는 혼합물에 용매로서 γ-부티로락톤/시클로헥사논 혼합 용제를 첨가하여 수지 고형분 40중량%의 수지 바니시를 조제했다.337 parts by weight of biphenyl type epoxy resin "NC-3000H" (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 275, resin solid content 80% by weight), 202 parts by weight of melamine-modified phenolic novolac resin "LA-7054" (manufactured by DIC Corporation, hydroxyl value) 125, resin solid content 60% by weight), 190 parts by weight of phenoxy resin "jER1256" (manufactured by Mitsubishi Chemical Corporation, Mw ≈ 48,000, Tg 95 ° C., resin solid content 100% by weight), 57 parts by weight phosphazene derivative "FP-100" (manufactured by Fushimi Seiyakusho Co., Ltd.), a mixed solvent of γ-butyrolactone/cyclohexanone as a solvent was added to a mixture consisting of 0.7 parts by weight of 2-ethyl-4methylimidazole to prepare a resin varnish having a resin solid content of 40% by weight. .
(비교예 2)(Comparative Example 2)
347중량부의 디시클로펜타디엔형 에폭시 수지 「HP-7200H」(DIC사제, 에폭시 당량 283, 수지 고형분 80중량%), 183중량부의 멜라민 변성 크레졸노볼락 수지 「EXB-9854」(DIC사제, 수산기가 151, 수지 고형분 80중량%), 290중량부의 가용성 폴리이미드 수지(합성 실시예 1, 수지 고형분 20중량%), 303중량부의 페녹시 수지 ERF-001M30(닛테츠 에폭시 세이조사제, Tg 146℃, 수지 고형분 30중량%), 57중량부의 포스파젠계 유도체「FP-100」(후시미 세이야쿠쇼사제), 0.7중량부의 2-에틸-4메틸이미다졸로 이루어지는 혼합물에 용매로서 γ-부티로락톤/시클로헥사논 혼합 용제를 첨가하여 수지 고형분 40중량%의 수지 바니시를 조제했다.347 parts by weight of dicyclopentadiene type epoxy resin "HP-7200H" (manufactured by DIC, epoxy equivalent 283, resin solid content 80% by weight), 183 parts by weight of melamine-modified cresol novolac resin "EXB-9854" (manufactured by DIC, hydroxyl value) 151, resin solid content 80% by weight), 290 parts by weight of soluble polyimide resin (Synthesis Example 1, resin solid content 20% by weight), 303 parts by weight of phenoxy resin ERF-001M30 (Nittetsu Epoxy Seizo, Tg 146 ° C., 30% by weight of resin solid content), 57 parts by weight of a phosphazene-based derivative "FP-100" (manufactured by Fushimi Seiyakusho Co., Ltd.), and 0.7 parts by weight of 2-ethyl-4methylimidazole, γ-butyrolactone/ A resin varnish having a resin solid content of 40% by weight was prepared by adding a mixed solvent of cyclohexanone.
이 비교예 1∼2의 수지 바니시를 사용해 실시예 1∼6과 마찬가지로 하여 양면 동박 FCCL 및 편면 동박 FCCL을 제작했다.Double-sided copper-clad FCCL and single-sided copper-clad FCCL were produced in the same manner as in Examples 1 to 6 using the resin varnishes of Comparative Examples 1 to 2.
(비교예 3∼5)(Comparative Examples 3 to 5)
시판의 FCCL로서 이하의 것을 사용했다.As commercially available FCCLs, the following were used.
비교예 3:시판 캐스팅법 2층 FCCLComparative Example 3: Commercially available casting method 2-layer FCCL
비교예 4:시판 라미네이트법 2층 FCCLComparative Example 4: Commercially available lamination method 2-layer FCCL
비교예 5:시판 3층 FCCLComparative Example 5: Commercial 3-layer FCCL
(각종 특성의 평가)(Evaluation of various characteristics)
상기와 같이 제작한 양면 동박 FCCL을 사용하여 박리 강도, 땜납 내열성, 치수 안정성의 평가를 행하고, 양면 동박 FCCL을 전체면 에칭한 필름을 사용하여 Tg 및 C. T. E의 평가를 TMA법(열기계 분석법)에 의해 행했다. 시험 방법은 JIS C 6471에 준거했다.Peel strength, solder heat resistance, and dimensional stability were evaluated using the double-sided copper-clad FCCL produced as described above, and Tg and C.T.E were evaluated using a film obtained by etching the double-sided copper-clad FCCL on the entire surface by TMA method (thermo-mechanical analysis method). done by The test method was based on JIS C 6471.
또한, 상기와 같이 제작한 편면 동박 FCCL을 사용하여 휨의 평가를 행했다. 구체적으로는, 100mm×100mm로 절단한 샘플을 동박면을 위로 하여 경면반(鏡面盤)에 정치하고, 그 들뜸을 측정했다. 5mm 이하는 휨의 발생 없음으로 평가했다. 또한, 동박을 전체면 에칭하여 마찬가지로 들뜸을 측정했다.In addition, evaluation of warpage was performed using the single-sided copper-clad FCCL produced as described above. Specifically, a sample cut into 100 mm × 100 mm was placed with the copper foil face up on a mirror board, and the lifting was measured. 5 mm or less was evaluated as no occurrence of warpage. In addition, the entire surface of the copper foil was etched, and lifting was measured in the same way.
(접착제 필름의 인장 탄성률 및 Tg)(Tensile modulus and Tg of adhesive film)
실시예 1∼6 및 비교예 1에서 조제한 수지 바니시(접착제 조성물)로 제작한 필름의 인장 탄성률과 Tg를 이하의 방법으로 측정했다.The tensile modulus and Tg of the films produced from the resin varnish (adhesive composition) prepared in Examples 1 to 6 and Comparative Example 1 were measured by the following methods.
수지 바니시(접착제 조성물)를 18㎛ 전해 동박의 샤이니면에 바 코터로 도포하고, 150℃의 온도에서 건조하여 반경화 상태(B 상태)의 접착제 부착 동박(접착제 두께:약 21㎛)을 제조했다. 용제의 휘발분은 0.6wt%로 조정했다. 이 접착제 부착 동박의 접착 시트면에 18㎛ 전해 동박 샤이니면을 중첩시키고, 진공 프레스에 투입하여 180℃×90분, 1MPa로 가열·가압(진공도 5torr) 성형했다. 이어서 동박을 전체면 에칭하여 얻어진 약 20㎛의 접착 필름에 대해 인장 탄성률과 Tg를 측정했다. 인장 탄성률은 IPC-TM-650-2.4.18.3에 준거하여 측정하고, 폭 10mm의 스트립(strip) 형상 샘플을 척간 거리 50mm로 인장·압축 시험기에 세트해, 인장 속도 50mm/분으로 인장 강도를 측정하고, 인장 응력과 변형의 관계로부터 구했다. Tg는 IPC-TM-650-2.4.24.3에 준거하여 측정했다. IPC-TM-650-2.4.18.3과 IPC-TM-650-2.4.24.3은 「IPC-TM-650 TEST METHODS MANUAL」에 기재된 방법을 따랐다.A resin varnish (adhesive composition) was applied to the shiny side of an 18 μm electrolytic copper foil with a bar coater, and dried at a temperature of 150 ° C. to produce a semi-cured state (B state) copper foil with adhesive (adhesive thickness: about 21 μm). . The volatile content of the solvent was adjusted to 0.6 wt%. An 18 μm electrodeposited copper foil shiny surface was superimposed on the adhesive sheet surface of this copper foil with adhesive, put into a vacuum press, and molded by heating and pressing at 1 MPa at 180 ° C. for 90 minutes (vacuum degree 5 torr). Next, the tensile modulus and Tg of the adhesive film of about 20 µm obtained by etching the entire surface of the copper foil were measured. The tensile modulus of elasticity is measured in accordance with IPC-TM-650-2.4.18.3, a strip-shaped sample with a width of 10 mm is set in a tensile/compression tester with a distance between chucks of 50 mm, and tensile strength is measured at a tensile speed of 50 mm/min. and obtained from the relationship between tensile stress and strain. Tg was measured based on IPC-TM-650-2.4.24.3. IPC-TM-650-2.4.18.3 and IPC-TM-650-2.4.24.3 followed the method described in "IPC-TM-650 TEST METHODS MANUAL".
실시예 1∼6 및 비교예 1∼5의 FCCL의 구성 내용과 특성 평가 결과를 하기 표 1∼표 4에 나타낸다.Tables 1 to 4 show the composition and characteristic evaluation results of the FCCLs of Examples 1 to 6 and Comparative Examples 1 to 5.
표 1∼표 4의 결과로부터, 본 발명의 접착제를 사용하여 제작한 FCCL(실시예 1∼6)은 페녹시 변성 에폭시 수지를 사용하여 필름의 Tg가 120℃ 미만이 되는 접착제를 사용하여 제작한 FCCL(비교예 1)에 비해, 치수 안정성이 향상되고 편면판의 휨도 보이지 않는 것을 알 수 있다. 또한, 120℃를 넘는 Tg를 갖는 페녹시 수지를 사용한 접착제의 경우에는 100℃의 라미네이트 온도에서는 폴리이미드 필름과 동박이 붙지 않기 때문에 라미네이트할 수 없어, 125℃의 라미네이트 온도에서는 동박 끊어짐이 발생했다(비교예 2). 또한, 실시예 1∼6의 FCCL은 시판의 캐스팅법 2층 FCCL(비교예 3)과 비교하면, 라미네이트법의 프로세스로 제작되고 있음에도 불구하고, 캐스팅법 2층 FCCL 수준의 특성이 실현되는 것을 알 수 있다.From the results of Tables 1 to 4, the FCCLs (Examples 1 to 6) produced using the adhesive of the present invention were produced using an adhesive having a film Tg of less than 120 ° C using a phenoxy-modified epoxy resin. Compared to FCCL (Comparative Example 1), it can be seen that the dimensional stability is improved and warpage of the single-sided plate is not observed. In addition, in the case of an adhesive using a phenoxy resin having a Tg of more than 120 ° C., since the polyimide film and copper foil do not adhere at a lamination temperature of 100 ° C., lamination cannot be performed, and copper foil breaks at a lamination temperature of 125 ° C. ( Comparative Example 2). In addition, when the FCCLs of Examples 1 to 6 are compared with the commercially available 2-layer FCCL by casting method (Comparative Example 3), it can be seen that even though they are manufactured by the lamination process, the same characteristics as the 2-layer FCCL by casting method are realized. can
본 발명의 접착제 및 접착 시트를 사용함으로써, 캐스팅법 2층 FCCL 수준의 특성과 라미네이트법 2층 FCCL 이상의 생산성을 양립하는 플렉서블 동장 적층판(2. 2층 FCCL)을 제공할 수 있다.By using the adhesive and adhesive sheet of the present invention, it is possible to provide a flexible copper-clad laminate (2. 2-layer FCCL) that achieves both the properties of a casting-type two-layer FCCL level and productivity equal to or higher than that of a laminated two-layer FCCL.
Claims (14)
(식 중, Z는 방향족 혹은 지환식의 테트라카르복실산 디무수물 잔기이고, Ar은 페닐인단 구조를 갖는 방향족 디아민 잔기이다)An adhesive for a flexible copper-clad laminate for bonding a copper foil to a polyimide film substrate constituting the flexible copper-clad laminate, comprising a solvent-soluble polyimide having a repeating unit represented by the following general formula [I], a glass transition temperature (Tg) of 120 ° C. An adhesive containing the following phenoxy resins, epoxy resins and epoxy resin curing agents.
(Wherein, Z is an aromatic or alicyclic tetracarboxylic acid dianhydride residue, and Ar is an aromatic diamine residue having a phenylindan structure)
상기 접착제로 제작한 반경화 상태의 필름을 180℃에서 90분간 가열 경화시켜서 얻어진 필름의 인장 탄성률이 1∼10.0GPa가 되고, Tg가 120∼190℃가 되는 접착제.According to claim 1,
An adhesive having a tensile modulus of elasticity of 1 to 10.0 GPa and a Tg of 120 to 190 ° C.
상기 페녹시 수지의 유리 전이 온도(Tg)가 80∼115℃인 접착제.According to claim 1 or 2,
An adhesive having a glass transition temperature (Tg) of the phenoxy resin of 80 to 115 ° C.
상기 페녹시 수지의 유리 전이 온도(Tg)가 90∼110℃인 접착제.According to claim 3,
An adhesive having a glass transition temperature (Tg) of the phenoxy resin of 90 to 110 ° C.
상기 접착제에 포함되는 용제 가용성 폴리이미드 수지(고형분)와 페녹시 수지의 중량비가 1:1.2∼12.0인 접착제.According to any one of claims 1 to 4,
An adhesive in which the weight ratio of the solvent-soluble polyimide resin (solid content) and the phenoxy resin contained in the adhesive is 1:1.2 to 12.0.
상기 접착제에 포함되는 용제 가용성 폴리이미드 수지, 페녹시 수지, 에폭시 수지 및 에폭시 수지 경화제의 합계 함유량에 대한 용제 가용성 폴리이미드 수지 및 페녹시 수지의 합계 함유량이 10∼50중량%인 접착제.According to any one of claims 1 to 5,
An adhesive in which the total content of the solvent-soluble polyimide resin and the phenoxy resin is 10 to 50% by weight relative to the total content of the solvent-soluble polyimide resin, the phenoxy resin, the epoxy resin and the epoxy resin curing agent contained in the adhesive.
상기 접착제로 제작한 반경화 상태의 필름을 180℃에서 90분간 가열 경화시켜서 얻어진 필름의 인장 탄성률이 폴리이미드 필름 기재의 인장 탄성률 미만인 접착 시트.According to claim 7,
An adhesive sheet having a tensile modulus of elasticity of a film obtained by heating and curing a semi-cured film made of the adhesive at 180° C. for 90 minutes is less than the tensile modulus of elasticity of a polyimide film substrate.
상기 접착제층의 두께가 1.6∼4.0㎛인 접착 시트.According to claim 7 or 8,
An adhesive sheet having a thickness of the adhesive layer of 1.6 to 4.0 μm.
상기 접착 시트가, 상기 접착 시트를 180℃에서 90분간 가열 경화시킨 경우에 접착제층의 두께가 1.5∼3.5㎛가 되는 접착 시트인 접착 시트.According to any one of claims 7 to 9,
The adhesive sheet wherein the adhesive sheet is an adhesive sheet having an adhesive layer having a thickness of 1.5 to 3.5 μm when the adhesive sheet is heat-cured at 180° C. for 90 minutes.
상기 동박의 두께가 1.5∼18㎛인 플렉서블 동장 적층판.According to claim 11,
A flexible copper-clad laminate in which the thickness of the copper foil is 1.5 to 18 μm.
접착제층과 접하는 동박 표면의 표면 거칠기 Rz가 접착층의 두께 미만인 플렉서블 동장 적층판.According to claim 11 or 12,
A flexible copper-clad laminate in which the surface roughness Rz of the surface of the copper foil in contact with the adhesive layer is less than the thickness of the adhesive layer.
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JP2014198385A (en) | 2013-03-29 | 2014-10-23 | 新日鉄住金化学株式会社 | Method for manufacturing flexible copper-clad laminate sheet |
JP2016215651A (en) | 2016-07-19 | 2016-12-22 | 新日鉄住金化学株式会社 | Flexible copper-clad laminated sheet and flexible circuit board |
JP2019081379A (en) | 2019-02-20 | 2019-05-30 | 日鉄ケミカル&マテリアル株式会社 | Flexible copper-clad laminated sheet and flexible circuit board |
JP2019172989A (en) | 2018-03-28 | 2019-10-10 | 荒川化学工業株式会社 | Polyimide, adhesive, crosslinking agent, film-like adhesive, adhesive layer, adhesive sheet, copper foil with resin, copper clad laminate, printed wiring board and multilayer wiring sheet, and manufacturing method therefor |
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- 2022-06-16 TW TW111122321A patent/TW202311342A/en unknown
- 2022-06-17 CN CN202210684805.7A patent/CN115491154A/en active Pending
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JPH06232553A (en) | 1993-01-29 | 1994-08-19 | Hitachi Chem Co Ltd | Single-sided flexible copper plated board for lamination |
JP2002280684A (en) | 2001-03-16 | 2002-09-27 | Sumitomo Electric Printed Circuit Inc | Copper clad flexible circuit board and its manufacturing method |
JP2003071982A (en) | 2001-06-22 | 2003-03-12 | Ube Ind Ltd | Copper-clad sheet for protection against heat |
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