CN107674388B - Halogen-free resin composition and glue film prepared therefrom, cover film and copper-clad plate - Google Patents
Halogen-free resin composition and glue film prepared therefrom, cover film and copper-clad plate Download PDFInfo
- Publication number
- CN107674388B CN107674388B CN201710816560.8A CN201710816560A CN107674388B CN 107674388 B CN107674388 B CN 107674388B CN 201710816560 A CN201710816560 A CN 201710816560A CN 107674388 B CN107674388 B CN 107674388B
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- China
- Prior art keywords
- halogen
- resin composition
- weight
- range
- free resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000011342 resin composition Substances 0.000 title claims abstract description 81
- 239000013039 cover film Substances 0.000 title claims abstract description 63
- 239000010408 film Substances 0.000 title claims abstract description 36
- 239000003292 glue Substances 0.000 title claims abstract description 31
- 239000003822 epoxy resin Substances 0.000 claims abstract description 56
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 56
- -1 nitrogenous epoxide Chemical class 0.000 claims abstract description 38
- 239000004645 polyester resin Substances 0.000 claims abstract description 28
- 229920001225 polyester resin Polymers 0.000 claims abstract description 28
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 26
- 239000003063 flame retardant Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 150000002367 halogens Chemical class 0.000 claims abstract description 10
- 239000012790 adhesive layer Substances 0.000 claims description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 38
- 229920005989 resin Polymers 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 30
- 239000010410 layer Substances 0.000 claims description 27
- 229920001721 polyimide Polymers 0.000 claims description 24
- 239000004642 Polyimide Substances 0.000 claims description 23
- 239000011889 copper foil Substances 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 14
- 239000012948 isocyanate Substances 0.000 claims description 13
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 12
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 150000002513 isocyanates Chemical class 0.000 claims description 10
- 239000004843 novolac epoxy resin Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 8
- 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 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 150000002924 oxiranes Chemical class 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- QMQZIXCNLUPEIN-UHFFFAOYSA-N 1h-imidazole-2-carbonitrile Chemical compound N#CC1=NC=CN1 QMQZIXCNLUPEIN-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 3
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 claims description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 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 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims 1
- 125000002619 bicyclic group Chemical group 0.000 claims 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical group NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims 1
- 125000005496 phosphonium group Chemical group 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 32
- 238000000034 method Methods 0.000 description 23
- 230000001070 adhesive effect Effects 0.000 description 18
- 229910052802 copper Inorganic materials 0.000 description 18
- 239000010949 copper Substances 0.000 description 18
- 239000000853 adhesive Substances 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 10
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000010030 laminating Methods 0.000 description 9
- 238000009987 spinning Methods 0.000 description 9
- 238000005476 soldering Methods 0.000 description 8
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 3
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 241001232787 Epiphragma Species 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 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 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002927 oxygen compounds Chemical class 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- XGJTVHAGMWPDKV-UHFFFAOYSA-N 2-(aminomethyl)cyclohexan-1-one Chemical class NCC1CCCCC1=O XGJTVHAGMWPDKV-UHFFFAOYSA-N 0.000 description 1
- UXJMXERXJQAWSP-UHFFFAOYSA-N 2-pentylcyclohexan-1-one Chemical compound CCCCCC1CCCCC1=O UXJMXERXJQAWSP-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
-
- 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
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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
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
-
- 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
- C09J2467/00—Presence of polyester
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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
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
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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)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Polyurethanes Or Polyureas (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a kind of halogen-free resin composition and glue film prepared therefrom, cover film and copper-clad plate.The halogen-free resin composition includes: 60 to 100 parts by weight contain carboxyl polyester resin；The polyfunctional epoxy resin of 5 to 30 parts by weight；The nitrogenous epoxide of 0.5 to 10 parts by weight；The fire retardant of 10 to 40 parts by weight；With the solvent of 40 to 100 parts by weight.Have the advantages that Halogen, high temperature resistant, ageing-resistant, flexibility is excellent and peel strength is high by using glue film, cover film and copper-clad plate prepared by halogen-free resin composition according to the present invention.
Description
Technical field
The present invention relates to flexible print wiring board technical field more particularly to a kind of halogen-free resin composition and by its system
Standby glue film, cover film and copper-clad plate.
Background technique
Glue film, cover film and copper-clad plate are the basic materials for making flexible print wiring board, with electronic information technology
Development, requirement of the market to its performance is higher and higher, especially heat resistance, ageing-resistant performance, flame retardant property and adhesive property.
Adhesive used in more typical glue film, cover film and three-layer process flexibility coat copper plate is using epoxy resin/nitrile rubber as main component
And curing agent of arranging in pairs or groups, fire retardant and other adjuvant components, peel strength is generally lower, heat resistance and ageing-resistant performance compared with
Difference.Come to improve heat resistance, Chinese patent CN101323773B and Chinese patent application publication number CN102199413A with span
Imide prepolymer modified epoxy/nitrile rubber system；Chinese patent application publication number CN104531030A does not use fourth
Nitrile rubber, but with phenolic resin modified flexible epoxy system；Chinese patent CN103834343B is solidified more with Flexible Curing Agent
Functional epoxy resins.The above method can be improved the heat resistance of copper-clad plate product, but the flexility of product has larger damage
It loses.
Japan Patent JP2009-96940A, Chinese patent application publication number CN105482442A etc. use polyurethane resin
Based on resin, collocation epoxy resin, other resins and the fire retardant such as phenolic resin are prepared for cover film and copper-clad plate, product
Flexibility and peel strength it is preferable.Chinese patent CN102822304B resin based on polyurethane, collocation polyester resin,
Epoxy resin, adhesive wet-hot aging performance obtained, low-temperature bending performance and mobility are preferable.But polyurethane is by carbamate
The influence of structure, heat resistance and ageing-resistant performance are poor, and the peel strength after wicking is lower.
Therefore, a kind of new resin combination is developed in urgent expectation at present, by using prepared by the resin combination
Glue film, cover film and copper-clad plate have excellent flexibility, heat resistance, resistance to ag(e)ing and peel strength.
Summary of the invention
From technical problem described above, it is an object of the present invention to provide one kind with containing carboxyl polyester resin,
Polyfunctional epoxy resin, nitrogenous epoxide halogen-free resin composition as main component, and prepare glue film by it, cover
Epiphragma and copper-clad plate.The present inventor passes through thoroughgoing and painstaking research, completes the present invention.
According to an aspect of the invention, there is provided a kind of halogen-free resin composition, the halogen-free resin composition includes:
60 to 100 parts by weight contain carboxyl polyester resin；
The polyfunctional epoxy resin of 5 to 30 parts by weight；
The nitrogenous epoxide of 0.5 to 10 parts by weight；
The fire retardant of 10 to 40 parts by weight；With
The solvent of 40 to 100 parts by weight.
Certain preferred embodiments according to the present invention, the number-average molecular weight containing carboxyl polyester resin 5000 to
In the range of 50000, glass transition temperature in the range of -10 DEG C to 70 DEG C, and acid value 5mgKOH/g extremely
In the range of 50mgKOH/g.
Certain preferred embodiments according to the present invention, the epoxide equivalent of the polyfunctional epoxy resin is in 100 grams/equivalent
In the range of to 500 grams/equivalent and number-average molecular weight is less than or equal to 8000.
Certain preferred embodiments according to the present invention, the polyfunctional epoxy resin be selected from one of the following or
It is a variety of: phenol type novolac epoxy resin, o-cresol type novolac epoxy resin, bisphenol A-type novolac epoxy resin, dicyclopentadiene type
Epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin and tetrafunctional epoxy resin.
Certain preferred embodiments according to the present invention, the content of the polyfunctional epoxy resin is in 10 to 30 parts by weight
In range.
Certain preferred embodiments according to the present invention, the nitrogenous epoxide have glycidol amine structure.
Certain preferred embodiments according to the present invention, the epoxide equivalent of the nitrogenous epoxide is in 50 grams/equivalent
In the range of to 500 grams/equivalent and number-average molecular weight is less than or equal to 4000.
Certain preferred embodiments according to the present invention, the nitrogenous epoxide be selected from one of the following or
It is a variety of: the double amino first of four glycidyl group diaminodiphenyl-methane, triglycidyl group para-aminophenol, four glycidyl group
Pentylcyclohexanone and N, N, N ', N '-four glycidyl group m-xylene diamine.
Certain preferred embodiments according to the present invention, the model of the content of the nitrogenous epoxide in 1 to 5 parts by weight
In enclosing.
Certain preferred embodiments according to the present invention, the fire retardant are phosphonium flame retardant or nitrogenous flame ratardant.
Certain preferred embodiments according to the present invention, the halogen-free resin composition also include the solidification of 0 to 2 parts by weight
Promotor.
Certain preferred embodiments according to the present invention, the curing accelerator are selected from one of the following or more
Kind: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole, undecyl imidazole and cyanoimidazole.
Certain preferred embodiments according to the present invention, the halogen-free resin composition also include the amine of 0 to 2 parts by weight
Curing agent.
Certain preferred embodiments according to the present invention, the amine curing agent are selected from one of the following or more
Kind: dicyandiamide, 4,4 '-diaminodiphenylsulfones and 4,4 '-diaminodiphenyl ethers.
Certain preferred embodiments according to the present invention, the halogen-free resin composition also include the closing of 0 to 2 parts by weight
Type isocyanates.
Certain preferred embodiments according to the present invention, the blocked isocyanate be selected from one of the following or
It is a variety of: enclosed type toluene di-isocyanate(TDI), enclosed type hexamethylene diisocyanate and enclosed type isophorone diisocyanate.
Certain preferred embodiments according to the present invention, the solvent are selected from acetone, butanone, cyclohexanone, toluene, ethylene glycol
One of methyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate and dimethylformamide are a variety of.
According to another aspect of the present invention, a kind of glue film is provided, the glue film includes:
Release film；
Adhesive layer on the release film, the adhesive layer are formed by halogen-free resin composition as described above；With
Release paper.
Certain preferred embodiments according to the present invention, the thickness of the release film are described in the range of 50 to 150 μm
The thickness of adhesive layer is in the range of 5 to 45 μm, and the thickness of the release paper is in the range of 50 to 150 μm.
According to a further aspect of the invention, a kind of cover film is provided, the cover film includes:
Polyimide layer；
Adhesive layer on the polyimide layer, the adhesive layer are formed by halogen-free resin composition as described above；With
Release paper on the adhesive layer.
Certain preferred embodiments according to the present invention, the thickness of the polyimide layer in the range of 10 to 100 μm,
The thickness of the adhesive layer is in the range of 5 to 45 μm, and the thickness of the release paper is in the range of 50 to 150 μm.
According to a further aspect of the invention, a kind of copper-clad plate is provided, the copper-clad plate includes:
Polyimide layer；
Adhesive layer on the polyimide layer, the adhesive layer are formed by halogen-free resin composition as described above；With
Copper foil on the adhesive layer.
Certain preferred embodiments according to the present invention, the thickness of the polyimide layer in the range of 10 to 100 μm,
The thickness of the adhesive layer is in the range of 5 to 45 μm, and the thickness of the copper foil is in the range of 6 to 70 μm.
Compared with the prior art in this field, the present invention has the advantages that halogen-free resin composition according to the present invention
In can be reacted with polyfunctional epoxy resin and nitrogenous epoxide containing carboxyl polyester resin, the nitrogenous epoxide can
With promote polyfunctional epoxy resin autohemagglutination and its with reacting containing carboxyl polyester resin so that adhesive is capable of forming interpenetrating net
Network structure, cured product have excellent heat resistance, adhesive property and resistance to Ion transfer performance.Using the Halogen resin combination
Glue film, cover film and the copper-clad plate of object production have excellent heat resistance, ageing-resistant performance, flexility and higher removing
Intensity.Glue film and cover film after copper-clad plate product and fitting copper foil can be by the high temperature wickings that last 20 seconds at 360 DEG C
Test, peel strength conservation rate is high, fire-retardant after peel strength conservation rate is high after wicking 60 seconds at 288 DEG C, high temperature ageing is handled
Grade reaches the advantages that UL94-V0.
Specific embodiment
It should be appreciated that without departing from the scope or spirit of the present disclosure, those skilled in the art can be according to this
The introduction of specification imagines other various embodiments and can modify to it.Therefore, specific embodiment below is not
Restrictive meaning.
Unless otherwise specified, expression characteristic size, quantity and materialization used in specification and claims are special
All numbers of property be construed as to be modified by term " about " in all cases.Therefore, unless there are opposite
Illustrate, the numerical parameter otherwise listed in description above and the appended claims is approximation, those skilled in the art
Member can seek the required characteristic obtained using teachings disclosed herein, suitably change these approximations.With endpoint table
The use for the numberical range shown includes all numbers within the scope of this and any range within the scope of this, for example, 1 to 5 includes
1,1.1,1.3,1.5,2,2.75,3,3.80,4 and 5 etc..
According to an aspect of the invention, there is provided a kind of halogen-free resin composition, the halogen-free resin composition includes:
60 to 100 parts by weight contain carboxyl polyester resin；
The polyfunctional epoxy resin of 5 to 30 parts by weight；
The nitrogenous epoxide of 0.5 to 10 parts by weight；
The fire retardant of 10 to 40 parts by weight；With
The solvent of 40 to 100 parts by weight.
Technical solution as above according to the present invention, the halogen-free resin composition of the invention, which uses, contains carboxyl polyester resin
, can be with polyfunctional epoxy resin co-dissolve in organic solvent as matrix resin, and can react to each other, with multifunctional ring
Oxygen resin forms interpenetrating cross-linked network structure；Nitrogenous epoxide can promote polyfunctional epoxy resin autohemagglutination and its with contain
The crosslinking of carboxyl polyester resin forms greater number and a greater variety of crosslinking points, improves the performance of cured product (for example, logical
Crossing has Halogen, high temperature resistant, resistance to old using glue film, cover film and the copper-clad plate of halogen-free resin composition according to the present invention preparation
Change, the advantage that flexibility is excellent and peel strength is high).
Specifically, the number-average molecular weight containing carboxyl polyester resin is in the range of 5000 to 50000, glass transition
Temperature is in the range of -10 DEG C to 70 DEG C, and acid value is in the range of 5mgKOH/g to 50mgKOH/g.Contain carboxyl when described
When the acid value of polyester resin is lower than 5mgKOH/g, the crosslink density after halogen-free resin composition solidifies is low, poor mechanical property；Work as institute
When stating the acid value containing carboxyl polyester resin higher than 50mgKOH/g, it is low that halogen-free resin composition is fully cured rear flexibility, to route
Fillibility it is poor.The content containing carboxyl polyester resin is 60 to 100 parts by weight, preferably 70 to 100 parts by weight.Dosage is too
More, the crosslink density that will lead to the resin combination is lower, heat resistance decline；Dosage is very little, will lead to the resin combination
The flexibility of object declines, and is increased with the cover film glue overflow amount of its production, and usability is bad.The institute that can be used in the present invention
Stating the specific example containing carboxyl polyester resin includes the BX-39SS provided by Japanese Dongyang spinning company, and number-average molecular weight is
16000, glass transition temperature is 15 DEG C, acid value 17mgKOH/g, and solid content is 40 weight %.
Specifically, the epoxide equivalent of the polyfunctional epoxy resin used in the present invention is in 100 grams/equivalent to 500
Gram/equivalent in the range of and number-average molecular weight be less than or equal to 8000.Preferably, the number of the polyfunctional epoxy resin is divided equally
Son amount is less than or equal to 6000.Preferably, the number-average molecular weight of the polyfunctional epoxy resin is greater than or equal to 400.Preferably,
The polyfunctional epoxy resin is selected from one of the following or a variety of: phenol type novolac epoxy resin, o-cresol type phenolic aldehyde
Epoxy resin, bisphenol A-type novolac epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin
And tetrafunctional epoxy resin.The solidification crosslink density of resin combination can be improved in the polyfunctional epoxy resin, and then improves
The heat resistance and resistance to ag(e)ing of the glue film, cover film and the copper-clad plate that are formed by the resin combination.Preferably, described multifunctional
Epoxy resin is the o-cresol type novolac epoxy resin that molecular weight is less than or equal to 6000.Preferably, the multi-functional epoxy tree
The content of rouge is in the range of 10 to 30 parts by weight.When the dosage of the polyfunctional epoxy resin is very little, cause by the tree
Glue film, cover film and the crosslink density of copper-clad plate that oil/fat composition is formed are lower；When the polyfunctional epoxy resin dosage too
When more, cause the flexibility of the glue film, cover film and the copper-clad plate that are formed by the resin combination poor.Preferably, described more
The content of functional epoxy resins is in the range of 10 to 20 parts by weight.The polyfunctional epoxy resin that can be used in the present invention
Specific example includes the o-cresol type novolac epoxy resin KEC-2185A75 provided by Cologne company, South Korea, and epoxide equivalent is
214g/eq, number-average molecular weight 1100, and solid content are 75 weight %.
According to the technique and scheme of the present invention, nitrogenous epoxide is added in the halogen-free resin composition, it is described to contain
Azo-cycle oxygen compound can promote polyfunctional epoxy resin and oneself of reacting containing carboxyl polyester resin and polyfunctional epoxy resin
Poly- reaction, can be heated at a lower temperature by the short time, resin combination of the invention is made to reach semi-cured state.
Preferably, the nitrogenous epoxide has glycidol amine structure.Preferably, the epoxy of the nitrogenous epoxide is worked as
Amount is in the range of 80 grams/equivalent to 300 grams/equivalent and number-average molecular weight is in the range of being less than or equal to 2000.It is described
Nitrogenous epoxide is selected from one of the following or a variety of: four glycidyl group diaminodiphenyl-methane, three are shunk
The double aminomethyl cyclohexanones of glyceryl para-aminophenol, four glycidyl group and N, N, N ', N '-four glycidyl group meta-xylene
Diamines.Most preferably, the nitrogenous epoxide is triglycidyl group para-aminophenol.The nitrogenous epoxide
Content is 0.5 to 10 parts by weight.When being less than 0.5 parts by weight with the amount of the nitrogenous epoxide, facilitation effect is poor,
The long period is needed to reach semi-solid preparation state；When being greater than 10 parts by weight with the amount of the nitrogenous epoxide, rigidity is excessively high, glues
Knot property reduces, and cross-linking reaction is readily facilitated in preservation, and glue storage characteristics are deteriorated.Preferably, the nitrogenous epoxide
Content be 1 to 5 parts by weight.The specific example of the nitrogenous epoxide includes three shrinks provided by Shanghai Hua Yi company
Glyceryl para-aminophenol AFG-90, epoxide equivalent is 105 grams/equivalent and number-average molecular weight is 277.Preferably, described
The content of nitrogenous epoxide is in the range of 1 to 5 parts by weight.
Fire retardant is added in the halogen-free resin composition, after making solidification in technical solution according to the present invention
Resin combination reach halogen-free flameproof；When it is used to prepare cover film, the additive amount of fire retardant other than influencing flame retarding efficiency,
Also have an impact to glue overflow amount, peel strength, Storage period.To the no spy of the specific type for the fire retardant that can be used in the present invention
It does not limit, as long as it can provide flame retardant effect and not influence the effect in the halogen-free resin composition between each component
And influence the engineering properties of the cover film formed by the halogen-free resin composition.Preferably, the fire retardant be containing
Phosphorus fire retardant or nitrogenous flame ratardant.The specific example of phosphonium flame retardant include the OP-930 that is manufactured by German Clariant Corporation and
The OP-935 and SPB-100 manufactured by Japanese Otsuka Kagaku K.K..In the phosphonium flame retardant, it is preferable to use fire-retardant effect
Rate is higher, the lesser OP-935 of partial size.In addition, the specific example of nitrogenous flame ratardant includes the MC- manufactured by Mitsubishi gas
The 5S and HT-209 manufactured by Tai Xing chemical company., it is preferable to use the preferable MC- of dispersibility in the nitrogenous flame ratardant
5S.According to the technique and scheme of the present invention, the halogen-free resin composition includes the fire retardant of 10 to 40 parts by weight.
Crosslink density for the adhesive further increased, the halogen-free resin composition can optionally include
One of curing accelerator, amine curing agent and blocked isocyanate are a variety of.Preferably, the curing accelerator is selected from
One of the following is a variety of: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole, undecyl imidazole and
Cyanoimidazole.Halogen-free resin composition also includes the curing accelerator of 0 to 2 parts by weight.Preferably, the amine curing agent is selected from
One of the following is a variety of: dicyandiamide, 4,4 '-diaminodiphenylsulfones and 4,4 '-diaminodiphenyl ethers.The Halogen tree
Oil/fat composition also includes the amine curing agent of 0 to 2 parts by weight.Preferably, the blocked isocyanate is in the following
It is one or more: enclosed type toluene di-isocyanate(TDI), enclosed type hexamethylene diisocyanate and enclosed type isophorone two
Isocyanates.The halogen-free resin composition also includes the blocked isocyanate of 0 to 2 parts by weight.
Solvent is added in halogen-free resin composition according to the present invention, to dissolve each component, and adjusts resin group
The solid content of object is closed, to adjust the viscosity of prepared resin adhesive liquid.Concrete kind to the solvent that can be used in the present invention
Type is not particularly limited, as long as it can dissolve or disperse each component and do not influence effect of the invention.Preferably,
The solvent is selected from acetone, butanone, cyclohexanone, toluene, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate and two
One of methylformamide is a variety of.
According to another aspect of the present invention, a kind of glue film is provided, the glue film includes:
Release film；
Adhesive layer on the release film, the adhesive layer are formed by halogen-free resin composition as described above；With
Release paper.
Preferably, for the thickness of the release film in the range of 50 to 150 μm, the thickness of the adhesive layer is at 5 to 45 μm
In the range of, and the thickness of the release paper is in the range of 50 to 150 μm.
The production method of the glue film include the following steps: by the halogen-free resin composition be coated on the release film from
On type face, the release film for being coated with the halogen-free resin composition is then placed in 120~160 DEG C of high-temperature test chamber bakings 2
~6 minutes progress semi-solid preparations, then release paper is laminating on the adhesive layer of semi-solid preparation.
According to a further aspect of the invention, a kind of cover film is provided, the cover film includes:
Polyimide layer；
Adhesive layer on the polyimide layer, the adhesive layer are formed by halogen-free resin composition as described above；With
Release paper on the adhesive layer.
Preferably, the thickness of the polyimide layer is in the range of 10 to 100 μm, the thickness of the adhesive layer 5 to
In the range of 45 μm, and the thickness of the release paper is in the range of 50 to 150 μm.
The production method of the cover film includes the following steps: the halogen-free resin composition being coated on the polyimides
On the surface of film, the polyimides for being coated with resin combination is then placed on 120~160 DEG C of high-temperature test chamber bakings
2~6 minutes progress semi-solid preparations, then release paper is laminating on the adhesive layer of semi-solid preparation.
According to a further aspect of the invention, a kind of copper-clad plate is provided, the copper-clad plate includes:
Polyimide layer；
Adhesive layer on the polyimide layer, the adhesive layer are formed by halogen-free resin composition as described above；With
Copper foil on the adhesive layer.
Preferably, the thickness of the polyimide layer is in the range of 10 to 100 μm, the thickness of the adhesive layer 5 to
In the range of 45 μm, and the thickness of the copper foil is in the range of 6 to 70 μm.
Preferably, the copper-clad plate is three-layer process single sided board or dual platen.By taking single sided board as an example, three-layer process single-side coated copper plate
It include: polyimide layer；Adhesive layer on the side of the polyimide layer, the adhesive layer is by Halogen resin as described above
Composition is formed；With the copper foil on the adhesive layer.Preferably, range of the thickness of the polyimide layer at 10 to 100 μm
Interior, the thickness of the adhesive layer is in the range of 5 to 45 μm, and the thickness of the copper foil is in the range of 6 to 70 μm.This three
Layer method single-side coated copper plate the production method is as follows: the halogen-free resin composition is coated on wherein the one of the polyimide film
On a side, which is placed in 120~160 DEG C of high-temperature test chambers and is toasted 2~6 minutes
Semi-solid preparation is carried out, then copper foil is laminating on the adhesive layer of semi-solid preparation, it will be after this semi-solid preparation state composition carries out by design program
Solidification.
The present invention is described in more detail below with reference to embodiment.It may be noted that these descriptions and embodiment are all
In order to be easy to understand the present invention, rather than limitation of the present invention.Protection scope of the present invention is with appended claims
It is quasi-.
Embodiment
In the present invention, unless otherwise noted, used reagent is commercial products, is directly used without further
Purification process.In addition, mentioned " part " is " parts by weight ".
Test method
In this disclosure, to each of the cover film obtained in following example 1-8 and comparative example 1-8 or copper-clad plate
Performance (covering the resistance to soldering dip temperature of type, the limit, peel strength, anti-flammability and resistance to dip solderability) is tested.Specific test side
Method is described as follows.
Cover type
Covering type can qualitatively reflect cover film obtained in following example 1-4 and comparative example 1-4 to printing electricity
The filling capacity of route on the plate of road.Type is covered to measure in particular by following method
The cover film obtained in the following examples and comparative examples is fitted in into measurement circuit respectively, it is fast with EWEDO-KY04C
For press at 180 DEG C, 100Kgf presses 80s fastly, using 50 times or more of amplification sem observation, whether there is starved, gas between inspection route
It steeps, fill other defects that are bad, pressing not firm or influence to use.
Measurement circuit include 100mm ± 10mm long straight line, semicircle and right angle figure, route copper thickness be 25 μm, line width and
Line-spacing is 100 μm.
From measurement result it is found that when there is no starved, bubble, other defects that filling is bad, pressure is not firm or influence uses
When, it is as qualified, it is otherwise, as unqualified.
The resistance to soldering dip temperature of the limit
The resistance to soldering dip temperature of the limit is for qualitatively reflecting cover film obtained in embodiment 1-8 and comparative example 1-8 or covering
The heat resistance of copper sheet.The resistance to soldering dip temperature of the limit is measured in particular by following method:
Cover film: the release paper of the cover film obtained in the following examples and comparative examples is removed, and by the covering
The smooth surface of the adhesive layer and the copper foil having a size of 5cm × 5cm of layer is laminating, with the fast press of EWEDO-KY04C in 180 DEG C, 100Kgf
Fast pressure is placed in 170 DEG C of common Homothermal Proof Box and solidifies 1 hour, obtain the copper foil for being pasted with cover film after 1 minute.It prepares more
A sample is impregnated into 20s in the tin liquor of 280+10n DEG C (n=1,2,3,4,5,6,7 and 8) respectively, takes out, has seen whether point
Layer, melting or foaming phenomena, the maximum temperature that qualification passes through are the resistance to soldering dip temperature of the limit.
Copper-clad plate: the copper-clad plate obtained in the following examples and comparative examples is cut into 5cm × 5cm after 170 DEG C of solidification 2h
Sample, according to cover film wicking method method test.
Peel strength
The release paper of each of the cover film that following example 1-4 and comparative example 1-4 are obtained is removed, and respectively will
The adhesive layer of the cover film with having a size of 20cm (length) × smooth surface of the copper foil of 20cm (width) × 18 μm (thickness) is laminating, use
It is small to be placed in 170 DEG C of common Homothermal Proof Box solidifications 1 after 180 DEG C, 100Kgf press 1 minute fastly for the fast press of EWEDO-KY04C
When, it is pasted with the copper foil of the cover film corresponding to embodiment 1-4 and comparative example 1-4 respectively.
According to IPC-TM-650 2.4.9 method, test is pasted with respectively according to what above method obtained corresponding to embodiment
The peel strength for the copper-clad plate that the copper foil and following example 5-8 and comparative example 5-8 of the cover film of 1-4 and comparative example 1-4 obtain.
Test result is shown below in table 1-4.Wherein, " peel strength (A state) " indicates the prepared copper foil for being pasted with cover film
Or the peel strength that copper-clad plate measures when without any processing；" peel strength (288 DEG C of wicking 20s) " refers to will be prepared
The peel strength that cover film or copper-clad plate measure after impregnating 20 seconds in 288 DEG C of tin liquor；" peel strength (288 DEG C of wickings
60s) " refer to the peel strength measured after impregnating prepared cover film or copper-clad plate 60 seconds in 288 DEG C of tin liquor；" stripping
From intensity (170 DEG C of aging 10h) " refer to the stripping for measuring prepared cover film or copper-clad plate after aging 10 hours at 170 DEG C
From intensity.
Anti-flammability
The cover film obtained in following example 1-8 and comparative example 1-8 is tested according to UL94 vertical combustion or covers copper
The anti-flammability of plate.The wherein cover film that embodiment 1-4 and comparative example 1-4 are obtained will be bonded solid that 18 μm of rolled copper foils of moral and consolidate
It is tested after change.
Embodiment 1
By the neighbour containing carboxyl polyester resin (BX-39SS provided by Japanese Dongyang spinning company), 8 parts by weight of 90 parts by weight
The triglycidyl group p-aminophenyl of first phenol-type epoxy resin (KEC-2185A75 provided by Cologne company, South Korea), 2 parts by weight
Phenol (AFG-90 provided by Shanghai Hua Yi company), the nitrogenous flame ratardants of 25 parts by weight (are provided by Mitsubishi gas company
MC-5S) and the butanone of 50 parts by weight (MEK) solvent is mixed and stirred for, to obtain halogen-free resin composition (resin adhesive liquid).
Using coating machine by the resin adhesive liquid coated in Kapton (the Taimide TL- with a thickness of 12.5 μm
012, Taiwan, which reaches, to step) on, gluing (dry glue) is controlled with a thickness of 15 μm, is then toasted 2 minutes in 140 DEG C of high-temperature test chamber,
To form the adhesive layer of part crosslinking curing on Kapton, then by release paper, (50 μm of thickness, SUMITOMO CHEMICAL is chemical
Company), obtained flexible printed-circuit board cover film laminating with the adhesive layer.
Embodiment 2
By 70 parts by weight containing carboxyl polyester resin (BX-39SS provided by Japanese Dongyang spinning company), 25 parts by weight
O-cresol type epoxy resin (KEC-2185A75 provided by Cologne company, South Korea), the triglycidyl groups of 5 parts by weight are to amino
Phenol (AFG-90 provided by Shanghai Hua Yi company), the nitrogenous flame ratardants of 25 parts by weight (are provided by Mitsubishi gas company
MC-5S) and butanone (MEK) solvent of 75 parts by weight be mixed and stirred for, to obtain halogen-free resin composition (resin adhesive liquid).
Flexible printed-circuit board cover film is prepared in a manner similar to example 1.
Embodiment 3
By 80 parts by weight containing carboxyl polyester resin (BX-39SS provided by Japanese Dongyang spinning company), 17 parts by weight
O-cresol type epoxy resin (KEC-2185A75 provided by Cologne company, South Korea), the triglycidyl groups of 3 parts by weight are to amino
Phenol (AFG-90 provided by Shanghai Hua Yi company), the nitrogenous flame ratardants of 15 parts by weight (are provided by Mitsubishi gas company
MC-5S) and butanone (MEK) solvent of 45 parts by weight be mixed and stirred for, to obtain halogen-free resin composition (resin adhesive liquid).
Flexible printed-circuit board cover film is prepared in a manner similar to example 1.
Embodiment 4
By 80 parts by weight containing carboxyl polyester resin (BX-39SS provided by Japanese Dongyang spinning company), 17 parts by weight
O-cresol type epoxy resin (KEC-2185A75 provided by Cologne company, South Korea), the triglycidyl groups of 3 parts by weight are to amino
Phenol (AFG-90 provided by Shanghai Hua Yi company), the nitrogenous flame ratardants of 15 parts by weight (are provided by German Clariant Corporation
OP-935) and the butanone of 45 parts by weight (MEK) solvent is mixed and stirred for, to obtain halogen-free resin composition (resin adhesive liquid).
Flexible printed-circuit board cover film is prepared in a manner similar to example 1.
Embodiment 5
Halogen-free resin composition obtained in above embodiments 1 is coated on to 12.5 μm of Kapton (Taimide
TL-012, Taiwan, which reaches, to step) on, gluing (dry glue) is controlled with a thickness of 15 μm.The polyamides for being coated with halogen-free resin composition is sub-
Amine film is placed in 140 DEG C of high-temperature test chambers and toasts 2 minutes progress semi-solid preparations, then will be having a size of 40cm (length) × 25cm (width) × 18
The rolled copper foil (BHY-22B-T provided by Japanese Kuang company) of μm (thickness) is laminating on the adhesive layer of semi-solid preparation, and 100 DEG C
Modeling is crossed, 180 DEG C/100kg pressure presses 60s fastly, and 170 DEG C solidify 2 hours, to prepare flexible printed-circuit board single-side coated copper plate.
Embodiment 6
Flexible printed-circuit board single-side coated copper plate is prepared in method same as Example 5, the difference is that using
Halogen-free resin composition obtained in embodiment 2.
Embodiment 7
Flexible printed-circuit board single-side coated copper plate is prepared in method same as Example 5, the difference is that using
Halogen-free resin composition obtained in embodiment 3.
Embodiment 8
Flexible printed-circuit board single-side coated copper plate is prepared in method same as Example 5, the difference is that using
Halogen-free resin composition obtained in embodiment 4.
Comparative example 1
By the polyester urethane resin of 75 parts by weight, (UR-3500 provided by Japanese Dongyang spinning company, acid value are
35mgKOH/g), the o-cresol type epoxy resin (KEC-2185A75 provided by Cologne company, South Korea) of 20 parts by weight, 5 weight
Part triglycidyl group para-aminophenol (AFG-90 provided by Shanghai Hua Yi company), the nitrogenous flame ratardants of 25 parts by weight
(MC-5S provided by Mitsubishi gas company) and butanone (MEK) solvent of 70 parts by weight are mixed and stirred for, to obtain nothing
Halogen resin combination (resin adhesive liquid).
Flexible printed-circuit board cover film is prepared in a manner similar to example 1.
Comparative example 2
By 75 parts by weight containing carboxyl polyester resin (BX-39SS provided by Japanese Dongyang spinning company), 20 parts by weight
O-cresol type epoxy resin (KEC-2185A75 provided by Cologne company, South Korea), the blocked isocyanates of 5 parts by weight (by
The B-1358A that German Degussa company provides), the nitrogenous flame ratardant (MC- provided by Mitsubishi gas company of 25 parts by weight
5S) and the butanone of 70 parts by weight (MEK) solvent is mixed and stirred for, to obtain halogen-free resin composition (resin adhesive liquid).
Flexible printed-circuit board cover film is prepared in a manner similar to example 1.
Comparative example 3
By 75 parts by weight containing carboxyl polyester resin (BX-39SS provided by Japanese Dongyang spinning company), 25 parts by weight
O-cresol type epoxy resin (KEC-2185A75 provided by Cologne company, South Korea), the nitrogenous flame ratardants of 25 parts by weight are (by Japan
Gas company, Mitsubishi provide MC-5S) and butanone (MEK) solvent of 65 parts by weight be mixed and stirred for, to obtain Halogen resin
Composition (resin adhesive liquid).
Flexible printed-circuit board cover film is prepared in a manner similar to example 1.
Comparative example 4
By 50 parts by weight containing carboxyl polyester resin (BX-39SS provided by Japanese Dongyang spinning company), 35 parts by weight
O-cresol type epoxy resin (KEC-2185A75 provided by Cologne company, South Korea), the triglycidyl groups of 15 parts by weight are to ammonia
Base phenol (AFG-90 provided by Shanghai Hua Yi company), (by Mitsubishi gas, company is mentioned for the nitrogenous flame ratardants of 25 parts by weight
The MC-5S of confession) and butanone (MEK) solvent of 100 parts by weight be mixed and stirred for, to obtain halogen-free resin composition (resin glue
Liquid).
Flexible printed-circuit board cover film is prepared in a manner similar to example 1.
Comparative example 5
Flexible printed-circuit board single-side coated copper plate is prepared in method same as Example 5, the difference is that using
Halogen-free resin composition obtained in comparative example 1.
Comparative example 6
Flexible printed-circuit board single-side coated copper plate is prepared in method same as Example 5, the difference is that using
Halogen-free resin composition obtained in comparative example 2.
Comparative example 7
Flexible printed-circuit board single-side coated copper plate is prepared in method same as Example 5, the difference is that using
Halogen-free resin composition obtained in comparative example 3.
Comparative example 8
Flexible printed-circuit board single-side coated copper plate is prepared in method same as Example 5, the difference is that using
Halogen-free resin composition obtained in comparative example 4.
According to aboveTest methodMeasurement method described in part, in above embodiments 1-8 and comparative example 1-8
Obtained cover film or the properties of copper-clad plate (cover the resistance to soldering dip temperature of type, the limit, peel strength, anti-flammability and resistance to immersed solder
Property) be tested.Wherein, the test result about flexible printed-circuit board cover film is shown below in table 1- table 2；It closes
It is shown below in table 3- table 4 in the test result of flexible printed-circuit board single-side coated copper plate.
The performance test results of flexible printed-circuit board cover film obtained in 1 embodiment 1-4 of table
The performance test results of flexible printed-circuit board cover film obtained in 2 comparative example 1-4 of table
Covering using halogen-free resin composition of the present invention preparation it can be seen from the measurement result of embodiment 1-4 in table 1
Epiphragma has excellent heat resistance, and the resistance to soldering dip temperature of the limit is more than 360 DEG C, and 288 DEG C of wicking 20s peel strength conservation rates are greater than
85%；When collocation nitrogenous flame ratardant, 288 DEG C of wicking 60s peel strength conservation rates are still greater than 85%, and the removing of part formulations is strong
Degree even increases, and the peel strength conservation rate after 170 DEG C of aging 10h is all larger than 80%.In addition, the glue overflow amount of cover film is suitable
In, type qualification is covered, laminating copper foil after-combustion reaches V0 grades.
Review the test result of the comparative example 1-4 in table 2, it can be seen that with polyurethane adhesive preparation in comparative example 1
The resistance to soldering dip temperature of the cover film limit is significantly lower than the cover film of invention resin composition preparation, and peel strength is prominent after wicking
Drop.Nitrogenous epoxide is replaced with isocyanates in comparative example 2, resin combination is promoted to solidify, cover film obtained, although
360 DEG C of wicking 20s are without foaming phenomena, but the peel strength after 288 DEG C of wickings can sharply decline, and illustrate that it integrates heat resistance not
It is good.Such as about the result of comparative example 3 it is found that if without nitrogenous epoxide as curing accelerator, adhesive reaches semi-solid preparation
The time of state is longer, and peel strength sharply declines after 288 DEG C of wickings.In addition, resin types and the present invention that comparative example 4 uses
It is identical, but the ratio of component is different, it can be found that its heat resistance is insufficient, it is poor to cover type.Therefore, resin combination of the invention
The collocation containing carboxyl polyester resin, polyfunctional epoxy resin and nitrogenous epoxide is not required nothing more than, also requires its each component
The cover film with excellent properties could be made in proportion.
The performance test results of flexible printed-circuit board single-side coated copper plate obtained in 3 embodiment 5-8 of table
The performance test results of flexible printed-circuit board single-side coated copper plate obtained in 4 comparative example 5-8 of table
The peel strength of flexible printed-circuit board single-side coated copper plate, resistance to immersed solder performance, resistance to it can be seen from table 3 and table 4
Ageing properties and the relationship of halogen-free resin composition formula and cover film are similar with the relationship of halogen-free resin composition formula, according to
Haveing excellent performance for copper-clad plate is obtained in the embodiment that the method for the invention is implemented.
In conclusion halogen-free resin composition of the invention includes carboxylic polyester resin, polyfunctional epoxy resin, contains
Azo-cycle oxygen compound, fire retardant and organic solvent, wherein can be reacted with polyfunctional epoxy resin containing carboxyl polyester resin, it is multifunctional
Self-polymeric reaction can occur for epoxy resin, and nitrogenous epoxide can promote the progress of above-mentioned reaction, promote to be formed mutual
Polymer network structure is worn, so that cured product has excellent heat resistance, ageing-resistant performance and adhesive property.
The cover film of invention resin composition production and copper-clad plate have excellent heat resistance, ageing-resistant performance, compared with
High peel strength, flame retardant rating reaches UL94-V0 grades after laminating copper foil, excellent combination property.
Although specific embodiment has been shown and described in the present invention, those skilled in the art be will be understood that, can
To replace shown and described specific embodiment with various substitutions and/or equivalent embodiments, without departing from this hair
Bright range.The application is intended to include any improvement or change to the specific embodiment discussed in the present invention.Therefore, this hair
It is bright to be limited solely by claim and its equivalent.
It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, can carry out a variety of modifications and
Change.Such modifications and changes are intended to fall within the scope of the present invention as defined in the appended claims.
Claims (23)
1. a kind of halogen-free resin composition, the halogen-free resin composition includes:
The acid value of 60 to 100 parts by weight contains carboxyl polyester resin in the range of 5mgKOH/g to 50mgKOH/g；
Polyfunctional epoxy resin of the epoxide equivalent of 5 to 30 parts by weight in the range of 100 grams/equivalent to 500 grams/equivalent；
Nitrogenous epoxide of the epoxide equivalent of 0.5 to 10 parts by weight in the range of 50 grams/equivalent to 500 grams/equivalent；
The fire retardant of 10 to 40 parts by weight；With
The solvent of 40 to 100 parts by weight.
2. halogen-free resin composition according to claim 1, wherein the number-average molecular weight containing carboxyl polyester resin exists
In the range of 5000 to 50000, and glass transition temperature is in the range of -10 DEG C to 70 DEG C.
3. halogen-free resin composition according to claim 1, wherein the number-average molecular weight of the polyfunctional epoxy resin is small
In or equal to 8000.
4. halogen-free resin composition according to claim 1, wherein the polyfunctional epoxy resin is in the following
It is one or more: it is phenol type novolac epoxy resin, o-cresol type novolac epoxy resin, bisphenol A-type novolac epoxy resin, bicyclic
Pentadiene type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin and tetrafunctional epoxy resin.
5. halogen-free resin composition according to claim 1, wherein the content of the polyfunctional epoxy resin is 10 to 30
In the range of parts by weight.
6. halogen-free resin composition according to claim 1, wherein the nitrogenous epoxide has glycidyl amine
Structure.
7. halogen-free resin composition according to claim 1, wherein the number-average molecular weight of the nitrogenous epoxide is small
In or equal to 4000.
8. halogen-free resin composition according to claim 1, the nitrogenous epoxide in the following one
Kind is a variety of: the double ammonia of four glycidyl group diaminodiphenyl-methane, triglycidyl group para-aminophenol, four glycidyl group
Ylmethyl cyclohexanone and N, N, N ', N '-four glycidyl group m-xylene diamine.
9. halogen-free resin composition according to claim 1, wherein the content of the nitrogenous epoxide is in 1 to 5 weight
In the range of amount part.
10. halogen-free resin composition according to claim 1, wherein the fire retardant is phosphonium flame retardant or nitrogenous fire-retardant
Agent.
11. halogen-free resin composition according to claim 1, the halogen-free resin composition also includes 0 to 2 parts by weight
Curing accelerator.
12. halogen-free resin composition according to claim 11, wherein the curing accelerator is in the following
It is one or more: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole, undecyl imidazole and cyanoimidazole.
13. halogen-free resin composition according to claim 1, wherein the halogen-free resin composition also includes 0 to 2 weight
The amine curing agent of part.
14. halogen-free resin composition according to claim 13, wherein the amine curing agent is in the following
It is one or more: dicyandiamide, 4,4 '-diaminodiphenylsulfones and 4,4 '-diaminodiphenyl ethers.
15. halogen-free resin composition according to claim 1, wherein the halogen-free resin composition also includes 0 to 2 weight
The blocked isocyanate of part.
16. halogen-free resin composition according to claim 15, wherein the blocked isocyanate is selected from the following
One of or it is a variety of: enclosed type toluene di-isocyanate(TDI), enclosed type hexamethylene diisocyanate and enclosed type isophorone
Diisocyanate.
17. halogen-free resin composition according to claim 1, wherein the solvent is selected from acetone, butanone, cyclohexanone, first
One of benzene, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate and dimethylformamide are a variety of.
18. a kind of glue film, the glue film include:
Release film；
Adhesive layer on the release film, the adhesive layer is as according to claim 1 to Halogen resin described in any one of 17
Composition is formed；With
Release paper.
19. glue film according to claim 18, wherein the thickness of the release film is in the range of 50 to 150 μm, it is described
The thickness of adhesive layer is in the range of 5 to 45 μm, and the thickness of the release paper is in the range of 50 to 150 μm.
20. a kind of cover film, the cover film include:
Polyimide layer；
Adhesive layer on the polyimide layer, the adhesive layer is as according to claim 1 to Halogen described in any one of 17
Resin combination is formed；With
Release paper on the adhesive layer.
21. cover film according to claim 20, wherein range of the thickness of the polyimide layer at 10 to 100 μm
Interior, the thickness of the adhesive layer is in the range of 5 to 45 μm, and the thickness of the release paper is in the range of 50 to 150 μm.
22. a kind of copper-clad plate, the copper-clad plate include:
Polyimide layer；
Adhesive layer on the polyimide layer, the adhesive layer is as according to claim 1 to Halogen described in any one of 17
Resin combination is formed；With
Copper foil on the adhesive layer.
23. copper-clad plate according to claim 22, wherein range of the thickness of the polyimide layer at 10 to 100 μm
Interior, the thickness of the adhesive layer is in the range of 5 to 45 μm, and the thickness of the copper foil is in the range of 6 to 70 μm.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710816560.8A CN107674388B (en) | 2017-09-12 | 2017-09-12 | Halogen-free resin composition and glue film prepared therefrom, cover film and copper-clad plate |
| TW107100844A TWI657110B (en) | 2017-09-12 | 2018-01-10 | Halogen-free resin composition and adhesive film, cover film and copper-clad board prepared therefrom |
| JP2018170921A JP6831356B2 (en) | 2017-09-12 | 2018-09-12 | Halogen-free resin composition and adhesive film, cover film, copper-clad plate produced by it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710816560.8A CN107674388B (en) | 2017-09-12 | 2017-09-12 | Halogen-free resin composition and glue film prepared therefrom, cover film and copper-clad plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107674388A CN107674388A (en) | 2018-02-09 |
| CN107674388B true CN107674388B (en) | 2019-10-08 |
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| CN201710816560.8A Expired - Fee Related CN107674388B (en) | 2017-09-12 | 2017-09-12 | Halogen-free resin composition and glue film prepared therefrom, cover film and copper-clad plate |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6831356B2 (en) |
| CN (1) | CN107674388B (en) |
| TW (1) | TWI657110B (en) |
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| CN109135647A (en) * | 2018-09-05 | 2019-01-04 | 广东生益科技股份有限公司 | A kind of halogen-free resin composition, cover film prepared therefrom, copper-clad plate and printed wiring board |
| CN109266284B (en) * | 2018-09-05 | 2021-06-04 | 广东生益科技股份有限公司 | Halogen-free resin composition, cover film prepared from same, copper-clad plate and printed circuit board |
| KR102220288B1 (en) * | 2018-11-28 | 2021-02-25 | 주식회사 케이씨씨 | Curable Coating Composition |
| CN110768482A (en) * | 2019-08-29 | 2020-02-07 | 襄阳航力机电技术发展有限公司 | Motor iron core bonding type manufacturing method |
| CN111040387B (en) * | 2019-12-28 | 2022-06-03 | 广东生益科技股份有限公司 | Halogen-free resin composition and flexible copper clad laminate comprising same |
| CN113999639A (en) * | 2021-11-17 | 2022-02-01 | 九江福莱克斯有限公司 | High-transparency temperature-resistant yellowing-resistant polyester adhesive and flexible covering film prepared from same |
| CN114133895B (en) * | 2021-12-29 | 2022-10-18 | 广东生益科技股份有限公司 | Transparent resin composition for copper-clad plate and copper-clad plate containing same |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL182319C (en) * | 1980-01-29 | Du Pont | COATING PREPARATION. | |
| JPH0718169A (en) * | 1993-06-30 | 1995-01-20 | Toyobo Co Ltd | Polyester resin composition |
| JP3482753B2 (en) * | 1994-11-28 | 2004-01-06 | 日産化学工業株式会社 | Resin composition for powder coating |
| JP2007070481A (en) * | 2005-09-07 | 2007-03-22 | Toyobo Co Ltd | Adhesive composition and flexible printed wiring board using the same |
| CN102264855B (en) * | 2008-12-26 | 2014-03-12 | 东洋纺织株式会社 | Resin composition for adhesive, adhesive comprising same, adhesive sheet, and printed wiring board including same as adhesive layer |
| JP5641251B2 (en) * | 2009-03-31 | 2014-12-17 | 日産化学工業株式会社 | Polyester composition for thermosetting film formation |
| JP2012056981A (en) * | 2010-09-06 | 2012-03-22 | Toray Ind Inc | Epoxy resin composition, epoxy resin cured product, prepreg, and fiber-reinforced composite material |
| JP2012111807A (en) * | 2010-11-22 | 2012-06-14 | Uniplus Electronics Co Ltd | Thermosetting resin composition and prepreg sheet or laminated board using the thermosetting resin composition |
| JP5304954B2 (en) * | 2011-05-31 | 2013-10-02 | 東洋紡株式会社 | Carboxyl group-containing polyimide |
| CN105492534B (en) * | 2013-09-26 | 2018-09-21 | 东洋纺株式会社 | Polyurethane resin composition and the adhesive composite, laminated body, printed wiring board for using it |
| JP6771885B2 (en) * | 2015-02-09 | 2020-10-21 | 東レ株式会社 | Epoxy resin compositions, prepregs and fiber reinforced composites |
| CN105482442A (en) * | 2015-12-31 | 2016-04-13 | 广东生益科技股份有限公司 | Halogen-free resin composition and cover film prepared from the same |
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| TW201811925A (en) | 2018-04-01 |
| TWI657110B (en) | 2019-04-21 |
| CN107674388A (en) | 2018-02-09 |
| JP6831356B2 (en) | 2021-02-17 |
| JP2019052303A (en) | 2019-04-04 |
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