TWI657110B - Halogen-free resin composition and adhesive film, cover film and copper-clad board prepared therefrom - Google Patents
Halogen-free resin composition and adhesive film, cover film and copper-clad board prepared therefrom Download PDFInfo
- Publication number
- TWI657110B TWI657110B TW107100844A TW107100844A TWI657110B TW I657110 B TWI657110 B TW I657110B TW 107100844 A TW107100844 A TW 107100844A TW 107100844 A TW107100844 A TW 107100844A TW I657110 B TWI657110 B TW I657110B
- Authority
- TW
- Taiwan
- Prior art keywords
- halogen
- resin composition
- weight
- parts
- range
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 99
- 239000013039 cover film Substances 0.000 title claims abstract description 46
- 239000002313 adhesive film Substances 0.000 title claims abstract description 18
- 239000003822 epoxy resin Substances 0.000 claims abstract description 66
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 66
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000004593 Epoxy Substances 0.000 claims abstract description 43
- 239000003063 flame retardant Substances 0.000 claims abstract description 38
- 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 abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 239000004645 polyester resin Substances 0.000 claims abstract description 27
- 229920001225 polyester resin Polymers 0.000 claims abstract description 27
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 57
- 239000012790 adhesive layer Substances 0.000 claims description 45
- 239000010408 film Substances 0.000 claims description 30
- 229920001721 polyimide Polymers 0.000 claims description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 27
- 239000010410 layer Substances 0.000 claims description 27
- 239000004642 Polyimide Substances 0.000 claims description 23
- 239000011889 copper foil Substances 0.000 claims description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 9
- 150000002513 isocyanates Chemical class 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-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
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 4
- 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 claims description 3
- QMQZIXCNLUPEIN-UHFFFAOYSA-N 1h-imidazole-2-carbonitrile Chemical compound N#CC1=NC=CN1 QMQZIXCNLUPEIN-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- 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
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- SJPFBRJHYRBAGV-UHFFFAOYSA-N n-[[3-[[bis(oxiran-2-ylmethyl)amino]methyl]phenyl]methyl]-1-(oxiran-2-yl)-n-(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC=1C=C(CN(CC2OC2)CC2OC2)C=CC=1)CC1CO1 SJPFBRJHYRBAGV-UHFFFAOYSA-N 0.000 claims description 3
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical group NCC1CO1 AFEQENGXSMURHA-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
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-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 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 2
- -1 dimethyl methyl Chemical group 0.000 claims description 2
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 3
- 150000001409 amidines Chemical class 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 32
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 239000003292 glue Substances 0.000 description 16
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 239000010949 copper Substances 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000007654 immersion Methods 0.000 description 7
- 238000005476 soldering Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 description 5
- PJUQAFXJSAHTEG-UHFFFAOYSA-N 4-amino-2-(oxiran-2-ylmethyl)phenol Chemical compound NC1=CC=C(O)C(CC2OC2)=C1 PJUQAFXJSAHTEG-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 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 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical group [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 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 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- WXAIEIRYBSKHDP-UHFFFAOYSA-N 4-phenyl-n-(4-phenylphenyl)-n-[4-[4-(4-phenyl-n-(4-phenylphenyl)anilino)phenyl]phenyl]aniline Chemical compound C1=CC=CC=C1C1=CC=C(N(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 WXAIEIRYBSKHDP-UHFFFAOYSA-N 0.000 description 1
- UDZSKVZNBWFVIF-UHFFFAOYSA-N C1CC(CC(C1=O)CC2CO2)(CN)CN Chemical compound C1CC(CC(C1=O)CC2CO2)(CN)CN UDZSKVZNBWFVIF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GDULUEIMCZRBNK-UHFFFAOYSA-N NC(N)C(=O)C1CCCCC1 Chemical class NC(N)C(=O)C1CCCCC1 GDULUEIMCZRBNK-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HLPKYOCVWVMBMR-UHFFFAOYSA-N azane benzylbenzene Chemical compound N.N.C=1C=CC=CC=1CC1=CC=CC=C1 HLPKYOCVWVMBMR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000463 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
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesive Tapes (AREA)
- Polyurethanes Or Polyureas (AREA)
- Epoxy Resins (AREA)
Abstract
本發明提供一種無鹵樹脂組合物以及由其製備的膠膜、覆蓋膜和覆銅板。所述無鹵樹脂組合物包含：60至100重量份的含羧基聚酯樹脂；5至30重量份的多官能環氧樹脂；0.5至10重量份的含氮環氧化合物；10至40重量份的阻燃劑；和40至100重量份的溶劑。通過採用根據本發明的無鹵樹脂組合物製備的膠膜、覆蓋膜和覆銅板具有無鹵、耐高溫、耐老化、柔韌性優並且剝離強度高的優點。The invention provides a halogen-free resin composition, and an adhesive film, a cover film, and a copper-clad board prepared therefrom. The halogen-free resin composition includes: 60 to 100 parts by weight of a carboxyl-containing polyester resin; 5 to 30 parts by weight of a polyfunctional epoxy resin; 0.5 to 10 parts by weight of a nitrogen-containing epoxy compound; 10 to 40 parts by weight Flame retardant; and 40 to 100 parts by weight of a solvent. The adhesive film, cover film, and copper-clad board prepared by using the halogen-free resin composition according to the present invention have the advantages of being halogen-free, high temperature resistance, aging resistance, excellent flexibility, and high peel strength.
Description
本發明涉及撓性印刷電路板技術領域，尤其涉及一種無鹵樹脂組合物以及由其製備的膠膜、覆蓋膜和覆銅板。The invention relates to the technical field of flexible printed circuit boards, in particular to a halogen-free resin composition, and an adhesive film, a cover film and a copper-clad board prepared therefrom.
膠膜、覆蓋膜和覆銅板是製作撓性印刷電路板的基礎材料，隨著電子資訊技術的發展，市場對其性能的要求越來越高，尤其是耐熱性能、耐老化性能、阻燃性能和黏接性能。較常見的膠膜、覆蓋膜和三層法撓性覆銅板所用膠黏劑以環氧樹脂/丁腈橡膠為主要成分並且搭配固化劑、阻燃劑及其他助劑組分，其剝離強度一般較低，耐熱性和耐老化性能較差。為改善耐熱性，中國專利CN101323773B和中國專利申請公開號CN102199413A以雙馬來醯亞胺預聚物改性環氧樹脂/丁腈橡膠體系；中國專利申請公開號CN104531030A不使用丁腈橡膠，而是以酚醛樹脂改性柔性環氧體系；中國專利CN103834343B以柔性固化劑固化多官能環氧樹脂。上述方法均能夠提高覆銅板製品的耐熱性，但製品的柔韌性能會有較大損失。Adhesive film, cover film and copper-clad board are the basic materials for making flexible printed circuit boards. With the development of electronic information technology, the market has increasingly demanded performance, especially heat resistance, aging resistance, and flame retardancy. And adhesive properties. More common adhesive films, cover films and three-layer flexible copper-clad laminates use epoxy / nitrile rubber as the main component and are combined with curing agents, flame retardants and other auxiliary components. Lower, poor heat resistance and aging resistance. In order to improve heat resistance, Chinese patent CN101323773B and Chinese patent application publication number CN102199413A use bismaleimide imide prepolymer to modify epoxy resin / nitrile rubber system; Chinese patent application publication number CN104531030A does not use nitrile rubber, but instead Flexible epoxy system is modified with phenolic resin; Chinese patent CN103834343B is used to cure multifunctional epoxy resin with flexible curing agent. The above methods can improve the heat resistance of copper clad laminate products, but the flexibility of the products will be greatly lost.
日本專利JP2009-96940A、中國專利申請公開號CN105482442A等採用聚胺酯樹脂為主體樹脂，搭配環氧樹脂、酚醛樹脂等其他樹脂及阻燃劑，製備了覆蓋膜及覆銅板，產品的柔韌性和剝離強度均較佳。中國專利CN102822304B以聚胺酯為主體樹脂，搭配聚酯樹脂、環氧樹脂，製得的膠黏劑耐濕熱性能、低溫彎折性能和流動性較好。但聚胺酯受胺基甲酸酯結構的影響，耐熱性能和耐老化性能較差，浸錫後的剝離強度較低。Japanese patent JP2009-96940A, Chinese Patent Application Publication No. CN105482442A, etc. use polyurethane resin as the main resin, with epoxy resin, phenolic resin and other resins and flame retardants to prepare cover films and copper clad laminates. The product's flexibility and peel strength Both are better. Chinese patent CN102822304B uses polyurethane as the main resin, with polyester resin and epoxy resin. The adhesive produced has good moisture resistance, low temperature bending performance and fluidity. However, polyurethane is affected by the urethane structure, and has poor heat resistance and aging resistance. The peel strength after immersion in tin is low.
因此，目前迫切期望開發出一種新的樹脂組合物，通過採用該樹脂組合物所製備的膠膜、覆蓋膜和覆銅板具有優異的柔韌性、耐熱性、耐老化性和剝離強度。Therefore, it is currently urgent to develop a new resin composition, and the adhesive film, cover film, and copper clad laminate prepared by using the resin composition have excellent flexibility, heat resistance, aging resistance, and peeling strength.
從以上闡述的技術問題出發，本發明的一個目的是提供一種以含羧基聚酯樹脂、多官能環氧樹脂、含氮環氧化合物為主要成分的無鹵樹脂組合物，並且通過其製備膠膜、覆蓋膜和覆銅板。本發明人經過深入細緻的研究，完成了本發明。Starting from the technical problems explained above, an object of the present invention is to provide a halogen-free resin composition containing a carboxyl-containing polyester resin, a polyfunctional epoxy resin, and a nitrogen-containing epoxy compound as main components, and to prepare a film therefrom. , Cover film and copper clad board. The present inventors have completed the present invention after intensive and careful research.
根據本發明的一個方面，提供了一種無鹵樹脂組合物，所述無鹵樹脂組合物包含： 60至100重量份的含羧基聚酯樹脂； 5至30重量份的多官能環氧樹脂； 0.5至10重量份的含氮環氧化合物； 10至40重量份的阻燃劑；和 40至100重量份的溶劑。According to an aspect of the present invention, there is provided a halogen-free resin composition comprising: 60 to 100 parts by weight of a carboxyl-containing polyester resin; 5 to 30 parts by weight of a polyfunctional epoxy resin; 0.5 To 10 parts by weight of a nitrogen-containing epoxy compound; 10 to 40 parts by weight of a flame retardant; and 40 to 100 parts by weight of a solvent.
根據本發明的某些優選實施方案，所述含羧基聚酯樹脂的數均分子量在5000至50000的範圍內，玻璃化轉變溫度在-10℃至70℃的範圍內，並且酸值在5 mgKOH/g至50 mgKOH/g的範圍內。According to some preferred embodiments of the present invention, the number average molecular weight of the carboxyl-containing polyester resin is in the range of 5,000 to 50,000, the glass transition temperature is in the range of -10 ° C to 70 ° C, and the acid value is 5 mgKOH / g to 50 mgKOH / g.
根據本發明的某些優選實施方案，所述多官能環氧樹脂的環氧當量在100克/當量至500克/當量的範圍內並且數均分子量小於或等於8000。According to some preferred embodiments of the present invention, the epoxy equivalent of the multifunctional epoxy resin is in the range of 100 g / equivalent to 500 g / equivalent and the number average molecular weight is less than or equal to 8000.
根據本發明的某些優選實施方案，所述多官能環氧樹脂選自下列各項中的一種或多種：苯酚型酚醛環氧樹脂、鄰甲酚型酚醛環氧樹脂、雙酚A型酚醛環氧樹脂、雙環戊二烯型環氧樹脂、聯苯型環氧樹脂、萘型環氧樹脂和四官能環氧樹脂。According to some preferred embodiments of the present invention, the multifunctional epoxy resin is selected from one or more of the following: phenol-type phenolic epoxy resin, o-cresol-type phenolic epoxy resin, bisphenol A-type phenolic ring Oxygen resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin and tetrafunctional epoxy resin.
根據本發明的某些優選實施方案，所述多官能環氧樹脂的含量在10至30重量份的範圍內。According to some preferred embodiments of the present invention, the content of the multifunctional epoxy resin is in a range of 10 to 30 parts by weight.
根據本發明的某些優選實施方案，所述含氮環氧化合物具有縮水甘油胺結構。According to certain preferred embodiments of the present invention, the nitrogen-containing epoxy compound has a glycidylamine structure.
根據本發明的某些優選實施方案，所述含氮環氧化合物的環氧當量在50克/當量至500克/當量的範圍內並且數均分子量小於或等於4000。According to some preferred embodiments of the present invention, the nitrogen-containing epoxy compound has an epoxy equivalent in a range of 50 g / equivalent to 500 g / equivalent and a number average molecular weight of less than or equal to 4000.
根據本發明的某些優選實施方案，所述含氮環氧化合物選自下列各項中的一種或多種：四縮水甘油基二胺基二苯基甲烷、三縮水甘油基對胺基苯酚、四縮水甘油基雙胺基甲基環己酮和N,N,N’,N’-四縮水甘油基間二甲苯二胺。According to certain preferred embodiments of the present invention, the nitrogen-containing epoxy compound is selected from one or more of the following: tetraglycidyl diamino diphenylmethane, triglycidyl p-aminophenol, tetra Glycidylbisaminomethylcyclohexanone and N, N, N ', N'-tetraglycidyl-m-xylylenediamine.
根據本發明的某些優選實施方案，所述含氮環氧化合物的含量在1至5重量份的範圍內。According to some preferred embodiments of the present invention, the content of the nitrogen-containing epoxy compound is in a range of 1 to 5 parts by weight.
根據本發明的某些優選實施方案，所述阻燃劑為含磷阻燃劑或含氮阻燃劑。According to certain preferred embodiments of the present invention, the flame retardant is a phosphorus-containing flame retardant or a nitrogen-containing flame retardant.
根據本發明的某些優選實施方案，所述無鹵樹脂組合物還包含0至2重量份的固化促進劑。According to some preferred embodiments of the present invention, the halogen-free resin composition further includes 0 to 2 parts by weight of a curing accelerator.
根據本發明的某些優選實施方案，所述固化促進劑選自下列各項中的一種或多種：2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、十一烷基咪唑和氰基咪唑。According to certain preferred embodiments of the present invention, the curing accelerator is selected from one or more of the following: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, ten Monoalkylimidazole and cyanoimidazole.
根據本發明的某些優選實施方案，所述無鹵樹脂組合物還包含0至2重量份的胺類固化劑。According to some preferred embodiments of the present invention, the halogen-free resin composition further includes 0 to 2 parts by weight of an amine-based curing agent.
根據本發明的某些優選實施方案，所述胺類固化劑選自下列各項中的一種或多種：雙氰胺、4,4’-二胺基二苯碸和4,4’-二胺基二苯醚。According to some preferred embodiments of the present invention, the amine curing agent is selected from one or more of the following: dicyandiamide, 4,4'-diaminodiphenylhydrazone, and 4,4'-diamine Diphenyl ether.
根據本發明的某些優選實施方案，所述無鹵樹脂組合物還包含0至2重量份的封閉型異氰酸酯。According to some preferred embodiments of the present invention, the halogen-free resin composition further includes 0 to 2 parts by weight of a blocked isocyanate.
根據本發明的某些優選實施方案，所述封閉型異氰酸酯選自下列各項中的一種或多種：封閉型甲苯二異氰酸酯、封閉型六亞甲基二異氰酸酯和封閉型異佛爾酮二異氰酸酯。According to certain preferred embodiments of the present invention, the blocked isocyanate is selected from one or more of the following: blocked toluene diisocyanate, blocked hexamethylene diisocyanate, and blocked isophorone diisocyanate.
根據本發明的某些優選實施方案，所述溶劑選自丙酮、丁酮、環己酮、甲苯、乙二醇甲醚、丙二醇甲醚、丙二醇甲醚醋酸酯和二甲基甲醯胺中的一種或多種。According to certain preferred embodiments of the present invention, the solvent is selected from the group consisting of acetone, methyl ethyl ketone, cyclohexanone, toluene, ethylene glycol methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate and dimethylformamide. One or more.
根據本發明的另一個方面，提供了一種膠膜，所述膠膜包括： 離型膜； 所述離型膜上的膠黏層，所述膠黏層由如上所述的無鹵樹脂組合物形成；和 離型紙。According to another aspect of the present invention, there is provided an adhesive film including: a release film; an adhesive layer on the release film, the adhesive layer being composed of the halogen-free resin composition as described above Form; and release paper.
根據本發明的某些優選實施方案，所述離型膜的厚度在50至150 µm的範圍內，所述膠黏層的厚度在5至45 µm的範圍內，並且所述離型紙的厚度在50至150 µm的範圍內。According to some preferred embodiments of the present invention, the thickness of the release film is in a range of 50 to 150 µm, the thickness of the adhesive layer is in a range of 5 to 45 µm, and the thickness of the release paper is between In the range of 50 to 150 µm.
根據本發明的又一個方面，提供了一種覆蓋膜，所述覆蓋膜包括： 聚醯亞胺層； 所述聚醯亞胺層上的膠黏層，所述膠黏層由如上所述的無鹵樹脂組合物形成；和 所述膠黏層上的離型紙。According to another aspect of the present invention, a cover film is provided, the cover film includes: a polyimide layer; an adhesive layer on the polyimide layer, the adhesive layer is A halogen resin composition is formed; and a release paper on the adhesive layer.
根據本發明的某些優選實施方案，所述聚醯亞胺層的厚度在10至100 µm的範圍內，所述膠黏層的厚度在5至45 µm的範圍內，並且所述離型紙的厚度在50至150 µm的範圍內。According to some preferred embodiments of the present invention, the thickness of the polyimide layer is 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 The thickness is in the range of 50 to 150 µm.
根據本發明的再一個方面，提供了一種覆銅板，所述覆銅板包括： 聚醯亞胺層； 所述聚醯亞胺層上的膠黏層，所述膠黏層由如上所述的無鹵樹脂組合物形成；和 所述膠黏層上的銅箔。According to still another aspect of the present invention, there is provided a copper-clad laminate, the copper-clad laminate comprising: a polyimide layer; an adhesive layer on the polyimide layer, the adhesive layer comprising A halogen resin composition is formed; and a copper foil on the adhesive layer.
根據本發明的某些優選實施方案，所述聚醯亞胺層的厚度在10至100 µm的範圍內，所述膠黏層的厚度在5至45 µm的範圍內，並且所述銅箔的厚度在6至70 µm的範圍內。According to some preferred embodiments of the present invention, the thickness of the polyimide layer is in a range of 10 to 100 µm, the thickness of the adhesive layer is in a range of 5 to 45 µm, and The thickness is in the range of 6 to 70 µm.
與本領域中的現有技術相比，本發明的優點在於：根據本發明的無鹵樹脂組合物中的含羧基聚酯樹脂可與多官能環氧樹脂及含氮環氧化合物反應，所述含氮環氧化合物可以促進多官能環氧樹脂的自聚及其與含羧基聚酯樹脂的反應，使得膠黏劑能夠形成互穿網絡結構，固化產物具有優異的耐熱性能、黏結性能和耐離子遷移性能。採用該無鹵樹脂組合物製作的膠膜、覆蓋膜及覆銅板具有優異的耐熱性能、耐老化性能、柔韌性能和較高的剝離強度。覆銅板製品以及貼合銅箔後的膠膜和覆蓋膜可通過在360℃下歷時20秒的高溫浸錫測試，在288℃下浸錫60秒後剝離強度保持率高、高溫老化處理後剝離強度保持率高、阻燃等級達到UL94-V0等優點。Compared with the prior art in the art, the present invention has the advantage that the carboxyl group-containing polyester resin in the halogen-free resin composition according to the present invention can react with a polyfunctional epoxy resin and a nitrogen-containing epoxy compound, which contains Nitrogen epoxy compounds can promote the self-polymerization of polyfunctional epoxy resins and their reaction with carboxyl-containing polyester resins, allowing the adhesive to form an interpenetrating network structure, and the cured product has excellent heat resistance, adhesion properties and resistance to ion migration performance. Adhesive films, cover films and copper clad laminates made from the halogen-free resin composition have excellent heat resistance, aging resistance, flexibility and high peel strength. The copper-clad laminate products and the adhesive film and cover film after copper foil bonding can pass the high-temperature tin dipping test at 360 ° C for 20 seconds. After peeling tin at 288 ° C for 60 seconds, the peel strength retention rate is high. The strength retention rate is high, and the flame retardant grade reaches UL94-V0.
應當理解，在不脫離本公開的範圍或精神的情況下，本領域技術人員能夠根據本說明書的教導設想其他各種實施方案並能夠對其進行修改。因此，以下的具體實施方式不具有限制性意義。It should be understood that those skilled in the art can envision and modify other various embodiments based on the teachings of this specification without departing from the scope or spirit of the present disclosure. Therefore, the following specific embodiments are not restrictive.
除非另外指明，否則本說明書和申請專利範圍中使用的表示特徵尺寸、數量和物化特性的所有數字均應該理解為在所有情況下均是由術語「約」來修飾的。因此，除非有相反的說明，否則上述說明書和所附申請專利範圍中列出的數值參數均是近似值，本領域的技術人員能夠利用本文所公開的教導內容尋求獲得的所需特性，適當改變這些近似值。用端點表示的數值範圍的使用包括該範圍內的所有數字以及該範圍內的任何範圍，例如，1至5包括1、1.1、1.3、1.5、2、2.75、3、3.80、4和5等等。Unless otherwise indicated, all numbers expressing feature sizes, quantities, and physicochemical properties used in this specification and the scope of the patent application should be understood to be modified in all cases by the term "about." Therefore, unless stated to the contrary, the numerical parameters listed in the above description and the scope of the appended patent applications are approximate values. Those skilled in the art can use the teachings disclosed herein to seek for the required characteristics and appropriately change these. approximation. The use of numerical ranges represented by endpoints includes all numbers within the range and any range within the range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4 and 5, etc. Wait.
根據本發明的一個方面，提供了一種無鹵樹脂組合物，所述無鹵樹脂組合物包含： 60至100重量份的含羧基聚酯樹脂； 5至30重量份的多官能環氧樹脂； 0.5至10重量份的含氮環氧化合物； 10至40重量份的阻燃劑；和 40至100重量份的溶劑。According to an aspect of the present invention, there is provided a halogen-free resin composition comprising: 60 to 100 parts by weight of a carboxyl-containing polyester resin; 5 to 30 parts by weight of a polyfunctional epoxy resin; 0.5 To 10 parts by weight of a nitrogen-containing epoxy compound; 10 to 40 parts by weight of a flame retardant; and 40 to 100 parts by weight of a solvent.
根據本發明的如上技術方案，本發明的所述無鹵樹脂組合物採用含羧基聚酯樹脂作為主體樹脂，其可與多官能環氧樹脂共同溶解於有機溶劑中，並能相互反應，與多官能環氧樹脂形成互穿交聯網絡結構；含氮環氧化合物可以促進多官能環氧樹脂的自聚及其與含羧基聚酯樹脂的交聯，形成更多數量和更多種類的交聯點，提高固化產物的性能（例如，通過採用根據本發明的無鹵樹脂組合物製備的膠膜、覆蓋膜和覆銅板具有無鹵、耐高溫、耐老化、柔韌性優並且剝離強度高的優點）。According to the above technical solution of the present invention, the halogen-free resin composition of the present invention uses a carboxyl-containing polyester resin as a main resin, which can be dissolved in an organic solvent together with a polyfunctional epoxy resin, and can react with each other, and Functional epoxy resins form an interpenetrating cross-linking network structure; nitrogen-containing epoxy compounds can promote the self-polymerization of polyfunctional epoxy resins and their cross-linking with carboxyl-containing polyester resins, forming a greater number and variety of cross-linkings Point to improve the properties of the cured product (for example, adhesive films, cover films, and copper clad laminates prepared by using the halogen-free resin composition according to the present invention have the advantages of being halogen-free, high temperature resistance, aging resistance, excellent flexibility, and high peel strength ).
具體地，所述含羧基聚酯樹脂的數均分子量在5000至50000的範圍內，玻璃化轉變溫度在-10℃至70℃的範圍內，並且酸值在5 mgKOH/g至50 mgKOH/g的範圍內。當所述含羧基聚酯樹脂的酸值低於5 mgKOH/g時，無鹵樹脂組合物固化後的交聯密度低，力學性能差；當所述含羧基聚酯樹脂的酸值高於50 mgKOH/g時，無鹵樹脂組合物完全固化後柔韌性低，對線路的填充性差。所述含羧基聚酯樹脂的含量為60至100重量份、優選70至100重量份。用量太多，將導致所述樹脂組合物的交聯密度較低，耐熱性下降；用量太少，將導致所述樹脂組合物的柔韌性下降，且以其製作的覆蓋膜溢膠量增大，使用性不佳。可以在本發明中使用的所述含羧基聚酯樹脂的具體實例包括由日本東洋紡公司提供的BX-39SS，其數均分子量為16000，玻璃化轉變溫度為15℃，酸值為17 mgKOH/g，並且固體含量為40重量%。Specifically, the number average molecular weight of the carboxyl-containing polyester resin is in the range of 5000 to 50,000, the glass transition temperature is in the range of -10 ° C to 70 ° C, and the acid value is 5 mgKOH / g to 50 mgKOH / g In the range. When the acid value of the carboxyl-containing polyester resin is less than 5 mgKOH / g, the crosslinking density of the halogen-free resin composition after curing is low and the mechanical properties are poor; when the acid value of the carboxyl-containing polyester resin is higher than 50 At mgKOH / g, the halogen-free resin composition has low flexibility after being completely cured, and has poor filling properties for circuits. The content of the carboxyl-containing polyester resin is 60 to 100 parts by weight, preferably 70 to 100 parts by weight. Too much amount will result in lower crosslink density of the resin composition and decrease in heat resistance; too little amount will cause the flexibility of the resin composition to decrease, and the amount of overflow of the cover film made with it will increase , Poor usability. Specific examples of the carboxyl-containing polyester resin that can be used in the present invention include BX-39SS provided by Japan Toyobo Co., Ltd., having a number average molecular weight of 16000, a glass transition temperature of 15 ° C, and an acid value of 17 mgKOH / g And has a solids content of 40% by weight.
具體地，在本發明中採用的所述多官能環氧樹脂的環氧當量在100克/當量至500克/當量的範圍內並且數均分子量小於或等於8000。優選地，所述多官能環氧樹脂的數均分子量小於或等於6000。優選地，所述多官能環氧樹脂的數均分子量大於或等於400。優選地，所述多官能環氧樹脂選自下列各項中的一種或多種：苯酚型酚醛環氧樹脂、鄰甲酚型酚醛環氧樹脂、雙酚A型酚醛環氧樹脂、雙環戊二烯型環氧樹脂、聯苯型環氧樹脂、萘型環氧樹脂和四官能環氧樹脂。所述多官能環氧樹脂可以提高樹脂組合物的固化交聯密度，進而提高由所述樹脂組合物形成的膠膜、覆蓋膜和覆銅板的耐熱性和耐老化性。優選地，所述多官能環氧樹脂為分子量小於或等於6000的鄰甲酚型酚醛環氧樹脂。優選地，所述多官能環氧樹脂的含量在10至30重量份的範圍內。當所述多官能環氧樹脂的用量太少時，導致由所述樹脂組合物形成的膠膜、覆蓋膜和覆銅板的交聯密度較低；當所述多官能環氧樹脂的用量太多時，導致由所述樹脂組合物形成的膠膜、覆蓋膜和覆銅板的柔韌性較差。優選地，所述多官能環氧樹脂的含量在10至20重量份的範圍內。可以在本發明中使用的多官能環氧樹脂的具體實例包括由韓國科隆公司提供的鄰甲酚型酚醛環氧樹脂KEC-2185A75，其環氧當量為214g/eq，數均分子量為1100，並且固體含量為75重量%。Specifically, the epoxy equivalent of the multifunctional epoxy resin used in the present invention is in the range of 100 g / equivalent to 500 g / equivalent and the number average molecular weight is less than or equal to 8000. Preferably, the number average molecular weight of the multifunctional epoxy resin 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 multifunctional epoxy resin is selected from one or more of the following: phenol-type phenolic epoxy resin, o-cresol-type phenolic epoxy resin, bisphenol A-type phenolic epoxy resin, dicyclopentadiene Epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, and tetrafunctional epoxy resin. The multifunctional epoxy resin can increase the curing cross-linking density of the resin composition, and further improve the heat resistance and aging resistance of the adhesive film, the cover film, and the copper-clad board formed from the resin composition. Preferably, the polyfunctional epoxy resin is an o-cresol-type phenolic epoxy resin having a molecular weight of less than or equal to 6000. Preferably, the content of the polyfunctional epoxy resin is in a range of 10 to 30 parts by weight. When the amount of the polyfunctional epoxy resin is too small, the crosslinking density of the adhesive film, the cover film, and the copper-clad board formed by the resin composition is low; when the amount of the polyfunctional epoxy resin is too much, As a result, the flexibility of the adhesive film, the cover film, and the copper clad laminate formed from the resin composition is poor. Preferably, the content of the polyfunctional epoxy resin is in a range of 10 to 20 parts by weight. Specific examples of the polyfunctional epoxy resin that can be used in the present invention include an o-cresol-type phenolic epoxy resin KEC-2185A75 provided by Korea Cologne Company, which has an epoxy equivalent of 214 g / eq and a number average molecular weight of 1100, and The solids content was 75% by weight.
根據本發明的技術方案，在所述無鹵樹脂組合物中加入含氮環氧化合物，所述含氮環氧化合物可以促進多官能環氧樹脂與含羧基聚酯樹脂的反應及多官能環氧樹脂的自聚反應，可以在較低的溫度下，通過短時間加熱，使本發明的樹脂組合物達到半固化狀態。優選地，所述含氮環氧化合物具有縮水甘油胺結構。優選地，所述含氮環氧化合物的環氧當量在80克/當量至300克/當量的範圍內並且數均分子量在小於或等於2000的範圍內。所述含氮環氧化合物選自下列各項中的一種或多種：四縮水甘油基二胺基二苯基甲烷、三縮水甘油基對胺基苯酚、四縮水甘油基雙胺基甲基環己酮和N,N,N’,N’-四縮水甘油基間二甲苯二胺。最優選地，所述含氮環氧化合物為三縮水甘油基對胺基苯酚。所述含氮環氧化合物的含量為0.5至10重量份。當用所述含氮環氧化合物的量少於0.5重量份時，其促進效果較差，需要較長時間達到半固化態；當用所述含氮環氧化合物的量大於10重量份時，剛性過高，黏結性降低，並且保存中容易促進交聯反應，膠液儲存性變差。較佳地，所述含氮環氧化合物的含量為1至5重量份。所述含氮環氧化合物的具體實例包括由上海華誼公司提供的三縮水甘油基對胺基苯酚AFG-90，其環氧當量為105克/當量並且數均分子量為277。優選地，所述含氮環氧化合物的含量在1至5重量份的範圍內。According to the technical solution of the present invention, a nitrogen-containing epoxy compound is added to the halogen-free resin composition, and the nitrogen-containing epoxy compound can promote the reaction between the polyfunctional epoxy resin and the carboxyl-containing polyester resin and the polyfunctional epoxy resin. The self-polymerization reaction of the resin can achieve a semi-cured state of the resin composition of the present invention by heating at a low temperature for a short time. Preferably, the nitrogen-containing epoxy compound has a glycidylamine structure. Preferably, the epoxy equivalent of the nitrogen-containing epoxy compound is in the range of 80 g / equivalent to 300 g / equivalent and the number average molecular weight is in the range of less than or equal to 2000. The nitrogen-containing epoxy compound is selected from one or more of the following: tetraglycidyl diamine diphenylmethane, triglycidyl p-aminophenol, tetraglycidyl diaminomethylcyclohexyl Ketones and N, N, N ', N'-tetraglycidyl-m-xylylenediamine. Most preferably, the nitrogen-containing epoxy compound is triglycidyl-p-aminophenol. The content of the nitrogen-containing epoxy compound is 0.5 to 10 parts by weight. When the amount of the nitrogen-containing epoxy compound is less than 0.5 parts by weight, its promoting effect is poor, and it takes a long time to reach a semi-cured state; when the amount of the nitrogen-containing epoxy compound is more than 10 parts by weight, rigidity If it is too high, the adhesiveness is reduced, and the cross-linking reaction is easily promoted during storage, and the glue storage is deteriorated. Preferably, the content of the nitrogen-containing epoxy compound is 1 to 5 parts by weight. Specific examples of the nitrogen-containing epoxy compound include triglycidyl p-aminophenol AFG-90 provided by Shanghai Huayi Company, which has an epoxy equivalent of 105 g / equivalent and a number average molecular weight of 277. Preferably, the content of the nitrogen-containing epoxy compound is in a range of 1 to 5 parts by weight.
根據本發明中的技術方案，在所述無鹵樹脂組合物中加入阻燃劑，用作使固化後的樹脂組合物達到無鹵阻燃；其用於製備覆蓋膜時，阻燃劑的添加量除了影響阻燃效率外，還對溢膠量、剝離強度、儲存期有影響。對可以在本發明中採用的阻燃劑的具體種類沒有特別限制，只要其可以提供阻燃效果並且不影響所述無鹵樹脂組合物中各個組分之間的作用並且影響由所述無鹵樹脂組合物形成的覆蓋膜的機械性質即可。優選地，所述阻燃劑為含磷阻燃劑或含氮阻燃劑。含磷阻燃劑的具體實例包括由德國科萊恩公司製造的OP-930和OP-935以及由日本大塚化學株式會社製造的SPB-100。在所述含磷阻燃劑，優選使用阻燃效率較高、粒徑較小的OP-935。此外，含氮阻燃劑的具體實例包括由日本三菱瓦斯製造的MC-5S以及由泰星化工公司製造的HT-209。在所述含氮阻燃劑中，優選使用分散性較好的MC-5S。根據本發明的技術方案，所述無鹵樹脂組合物包含10至40重量份的阻燃劑。According to the technical solution of the present invention, a flame retardant is added to the halogen-free resin composition, which is used to make the cured resin composition achieve halogen-free flame retardant; when used for preparing a cover film, the addition of a flame retardant In addition to the amount of flame retardant effect, it also affects the amount of glue overflow, peel strength, storage period. There is no particular limitation on the specific kind of the flame retardant that can be used in the present invention, as long as it can provide a flame retardant effect and does not affect the effects between the various components in the halogen-free resin composition and affect the halogen-free resin composition. The mechanical properties of the cover film formed from the resin composition may be sufficient. Preferably, the flame retardant is a phosphorus-containing flame retardant or a nitrogen-containing flame retardant. Specific examples of the phosphorus-containing flame retardant include OP-930 and OP-935 manufactured by Clariant, Germany, and SPB-100 manufactured by Otsuka Chemical Co., Ltd., Japan. Among the phosphorus-containing flame retardants, OP-935, which has a high flame retardance and a small particle diameter, is preferably used. In addition, specific examples of the nitrogen-containing flame retardant include MC-5S manufactured by Mitsubishi Gas Japan and HT-209 manufactured by Taixing Chemical Company. Among the nitrogen-containing flame retardants, MC-5S having good dispersibility is preferably used. According to the technical solution of the present invention, the halogen-free resin composition includes 10 to 40 parts by weight of a flame retardant.
為進一步提高要得到的膠黏劑的交聯密度，所述無鹵樹脂組合物可以任選地包含固化促進劑、胺類固化劑和封閉型異氰酸酯中的一種或多種。優選地，所述固化促進劑選自下列各項中的一種或多種：2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、十一烷基咪唑和氰基咪唑。無鹵樹脂組合物還包含0至2重量份的固化促進劑。優選地，所述胺類固化劑選自下列各項中的一種或多種：雙氰胺、4,4’-二胺基二苯碸和4,4’-二胺基二苯醚。所述無鹵樹脂組合物還包含0至2重量份的胺類固化劑。優選地，所述封閉型異氰酸酯選自下列各項中的一種或多種：封閉型甲苯二異氰酸酯、封閉型六亞甲基二異氰酸酯和封閉型異佛爾酮二異氰酸酯。所述無鹵樹脂組合物還包含0至2重量份的封閉型異氰酸酯。To further increase the crosslinking density of the adhesive to be obtained, the halogen-free resin composition may optionally include one or more of a curing accelerator, an amine-based curing agent, and a blocked isocyanate. Preferably, the curing accelerator is selected from one or more of the following: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, undecylimidazole, and cyano Imidazole. The halogen-free resin composition further contains 0 to 2 parts by weight of a curing accelerator. Preferably, the amine curing agent is selected from one or more of the following: dicyandiamide, 4,4'-diaminodiphenylphosphonium, and 4,4'-diaminodiphenyl ether. The halogen-free resin composition further contains 0 to 2 parts by weight of an amine-based curing agent. Preferably, the blocked isocyanate is selected from one or more of the following: blocked toluene diisocyanate, blocked hexamethylene diisocyanate, and blocked isophorone diisocyanate. The halogen-free resin composition further contains 0 to 2 parts by weight of a blocked isocyanate.
在根據本發明的無鹵樹脂組合物中加入溶劑，以溶解各個組分，並且調節樹脂組合物的固含量，以調節所製備的樹脂膠液的黏度。對可以在本發明中採用的溶劑的具體類型沒有特別限制，只要其可以溶解或分散各個組分並且不影響本發明的效果即可。優選地，所述溶劑選自丙酮、丁酮、環己酮、甲苯、乙二醇甲醚、丙二醇甲醚、丙二醇甲醚醋酸酯和二甲基甲醯胺中的一種或多種。A solvent is added to the halogen-free resin composition according to the present invention to dissolve the respective components, and the solid content of the resin composition is adjusted to adjust the viscosity of the prepared resin glue solution. The specific type of the solvent that can be used in the present invention is not particularly limited as long as it can dissolve or disperse the various components without affecting the effects of the present invention. Preferably, the solvent is selected from one or more of acetone, methyl ethyl ketone, cyclohexanone, toluene, ethylene glycol methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate and dimethylformamide.
根據本發明的另一個方面，提供了一種膠膜，所述膠膜包括： 離型膜； 所述離型膜上的膠黏層，所述膠黏層由如上所述的無鹵樹脂組合物形成；和 離型紙。According to another aspect of the present invention, there is provided an adhesive film including: a release film; an adhesive layer on the release film, the adhesive layer being composed of the halogen-free resin composition as described above Form; and release paper.
優選地，所述離型膜的厚度在50至150 µm的範圍內，所述膠黏層的厚度在5至45 µm的範圍內，並且所述離型紙的厚度在50至150 µm的範圍內。Preferably, the thickness of the release film is in a range of 50 to 150 µm, the thickness of the adhesive layer is in a range of 5 to 45 µm, and the thickness of the release paper is in a range of 50 to 150 µm. .
該膠膜的製作方法包括如下步驟：將所述無鹵樹脂組合物塗覆於所述離型膜的離型面上，然後將該塗覆有所述無鹵樹脂組合物的離型膜置於120～160℃高溫試驗箱烘烤2～6分鐘進行半固化，再將離型紙覆合於半固化的膠黏層上。The method for manufacturing the adhesive film includes the steps of coating the halogen-free resin composition on a release surface of the release film, and then placing the release film coated with the halogen-free resin composition. Bake in a high temperature test box at 120-160 ° C for 2-6 minutes for semi-curing, and then release paper is overlaid on the semi-cured adhesive layer.
根據本發明的又一個方面，提供了一種覆蓋膜，所述覆蓋膜包括： 聚醯亞胺層； 所述聚醯亞胺層上的膠黏層，所述膠黏層由如上所述的無鹵樹脂組合物形成；和 所述膠黏層上的離型紙。According to another aspect of the present invention, a cover film is provided, the cover film includes: a polyimide layer; an adhesive layer on the polyimide layer, the adhesive layer is A halogen resin composition is formed; and a release paper on the adhesive layer.
優選地，所述聚醯亞胺層的厚度在10至100 µm的範圍內，所述膠黏層的厚度在5至45 µm的範圍內，並且所述離型紙的厚度在50至150 µm的範圍內。Preferably, the thickness of the polyimide layer is in a range of 10 to 100 µm, the thickness of the adhesive layer is in a range of 5 to 45 µm, and the thickness of the release paper is in a range of 50 to 150 µm. Within range.
該覆蓋膜的製作方法包括如下步驟：將所述無鹵樹脂組合物塗覆於所述聚醯亞胺薄膜的表面上，然後將該塗覆有樹脂組合物的聚醯亞胺層置於120～160℃高溫試驗箱烘烤2～6分鐘進行半固化，再將離型紙覆合於半固化的膠黏層上。The manufacturing method of the cover film includes the steps of coating the halogen-free resin composition on the surface of the polyimide film, and then placing the polyimide layer coated with the resin composition at 120 Bake at ～ 160 ℃ in a high-temperature test box for 2 to 6 minutes for semi-curing, and then lay the release paper on the semi-curing adhesive layer.
根據本發明的再一個方面，提供了一種覆銅板，所述覆銅板包括： 聚醯亞胺層； 所述聚醯亞胺層上的膠黏層，所述膠黏層由如上所述的無鹵樹脂組合物形成；和 所述膠黏層上的銅箔。According to still another aspect of the present invention, there is provided a copper-clad laminate, the copper-clad laminate comprising: a polyimide layer; an adhesive layer on the polyimide layer, the adhesive layer comprising A halogen resin composition is formed; and a copper foil on the adhesive layer.
優選地，所述聚醯亞胺層的厚度在10至100 µm的範圍內，所述膠黏層的厚度在5至45 µm的範圍內，並且所述銅箔的厚度在6至70 µm的範圍內。Preferably, the thickness of the polyimide layer is in a range of 10 to 100 µm, the thickness of the adhesive layer is in a range of 5 to 45 µm, and the thickness of the copper foil is in a range of 6 to 70 µm. Within range.
優選地，所述覆銅板為三層法單面板或雙面板。以單面板為例，三層法單面覆銅板包括：聚醯亞胺層；所述聚醯亞胺層的一側上的膠黏層，所述膠黏層由如上所述的無鹵樹脂組合物形成；和所述膠黏層上的銅箔。優選地，所述聚醯亞胺層的厚度在10至100 µm的範圍內，所述膠黏層的厚度在5至45 µm的範圍內，並且所述銅箔的厚度在6至70 µm的範圍內。該三層法單面覆銅板的製作方法如下：將所述無鹵樹脂組合物塗覆於所述聚醯亞胺膜的其中一個側面上，將該塗覆有樹脂組合物的聚醯亞胺膜置於120～160℃高溫試驗箱烘烤2～6分鐘進行半固化，再將銅箔覆合於半固化的膠黏層上，按設計程序將此半固化態組合物進行後固化。Preferably, the copper-clad board is a three-layer single-panel or double-panel method. Taking a single panel as an example, a three-layer single-sided copper-clad board includes: a polyimide layer; an adhesive layer on one side of the polyimide layer, and the adhesive layer is made of the halogen-free resin as described above A composition is formed; and a copper foil on the adhesive layer. Preferably, the thickness of the polyimide layer is in a range of 10 to 100 µm, the thickness of the adhesive layer is in a range of 5 to 45 µm, and the thickness of the copper foil is in a range of 6 to 70 µm. Within range. The three-layer method single-sided copper-clad board is manufactured as follows: the halogen-free resin composition is coated on one side of the polyimide film, and the polyimide coated with the resin composition is applied The film was placed in a high temperature test box at 120-160 ° C for 2 to 6 minutes for semi-curing, and then the copper foil was laminated on the semi-cured adhesive layer, and the semi-cured composition was post-cured according to the design procedure.
下面結合實施例對本發明進行更詳細的描述。需要指出，這些描述和實施例都是為了使本發明便於理解，而非對本發明的限制。本發明的保護範圍以所附的申請專利範圍為準。The present invention will be described in more detail with reference to the following embodiments. It should be noted that these descriptions and examples are intended to facilitate understanding of the present invention, but not to limit the present invention. The protection scope of the present invention is subject to the scope of the attached patent application.
實施例Examples
在本發明中，除非另外指出，所採用的試劑均為商購產品，直接使用而沒有進一步純化處理。此外，所提及的「份」為「重量份」。In the present invention, unless otherwise indicated, the reagents used are all commercially available products and used directly without further purification. In addition, the "part" mentioned is "part by weight".
測試方法Test Methods
在本公開內容中，對在以下實施例1～8和比較例1～8中得到的覆蓋膜或覆銅板的各項性能（覆型性、極限耐浸焊溫度、剝離強度、阻燃性和耐浸焊性）進行了測試。具體測試方法描述如下。In the present disclosure, various properties (coverability, extreme solder resistance temperature, peel strength, flame retardancy, and impregnation resistance) of the cover films or copper-clad sheets obtained in the following Examples 1 to 8 and Comparative Examples 1 to 8 are described. Solderability) was tested. The specific test method is described below.
覆型性Overlay
覆型性可以定性地反映出以下實施例1～4和比較例1～4中得到的覆蓋膜對印刷電路板上的線路的填充能力。覆型性具體地通過下列方法進行測量。The formability can qualitatively reflect the ability of the cover films obtained in the following Examples 1 to 4 and Comparative Examples 1 to 4 to fill circuits on a printed circuit board. Coverability was specifically measured by the following method.
將以下實施例和比較例中得到的覆蓋膜分別貼合於測試線路，用EWEDO-KY04C快壓機在180℃，100Kgf快壓80s，利用50倍以上的放大鏡觀察，檢查線路間是否存在缺膠、氣泡、填充不良、壓不實或影響使用的其他缺陷。The covering films obtained in the following examples and comparative examples were attached to test circuits, respectively, using an EWEDO-KY04C fast press at 180 ° C and 100Kgf for 80s. Observe with a magnifying glass more than 50 times to check whether there is a lack of glue between the circuits. , Bubbles, poor filling, compaction or other defects that affect use.
測試線路包含100 mm±10 mm長直線、半圓和直角的圖形，線路銅厚為25 μm，線寬及線距為100 μm。The test line includes 100 mm ± 10 mm long straight, semi-circular and right-angled patterns. The copper thickness of the line is 25 μm, and the line width and line spacing are 100 μm.
從測量結果可知，當不存在缺膠、氣泡、填充不良、壓不實或影響使用的其他缺陷時，即為合格，否則，即為不合格。It can be known from the measurement results that when there is no lack of glue, air bubbles, poor filling, compaction or other defects affecting the use, it is qualified, otherwise it is unqualified.
極限耐浸焊溫度Extreme dip soldering temperature
極限耐浸焊溫度用於定性地反映出實施例1～8和比較例1～8中得到的覆蓋膜或覆銅板的耐熱性能。極限耐浸焊溫度具體地通過下列方法進行測量。The limiting dip soldering temperature is used to qualitatively reflect the heat resistance of the cover films or copper-clad boards obtained in Examples 1 to 8 and Comparative Examples 1 to 8. The ultimate resistance to dip soldering is specifically measured by the following method.
覆蓋膜：將以下實施例和比較例中得到的覆蓋膜的離型紙剝離，並且將所述覆蓋層的膠黏層與尺寸為5 cm× 5 cm的銅箔的光面覆合，用EWEDO-KY04C快壓機在180℃、100Kgf快壓1分鐘以後，置於普通恆溫試驗箱170℃固化1小時，得到貼附有覆蓋膜的銅箔。製備多個樣品，分別浸漬到280+10n℃（n=1、2、3、4、5、6、7和8）的錫液中20s，取出，觀察是否有分層、熔融或起泡現象，合格通過的最高溫度為極限耐浸焊溫度。Cover film: The release paper of the cover films obtained in the following examples and comparative examples was peeled off, and the adhesive layer of the cover layer and the smooth surface of a copper foil with a size of 5 cm × 5 cm were laminated, and EWEDO- The KY04C fast press was pressed at 180 ° C and 100Kgf for 1 minute, and then placed in an ordinary constant temperature test box at 170 ° C for 1 hour to obtain a copper foil with a cover film attached. Prepare multiple samples and immerse them in 280 + 10n ℃ (n = 1, 2, 3, 4, 5, 6, 7, and 8) tin baths for 20s, and take them out to observe whether there is delamination, melting or blistering. , The highest temperature that passes is the ultimate resistance to dip soldering.
覆銅板：將以下實施例和比較例中得到的覆銅板在170℃固化2h後裁取5 cm× 5 cm的樣品，按照覆蓋膜浸錫方法測試。Copper-clad sheet: The copper-clad sheets obtained in the following examples and comparative examples were cured at 170 ° C. for 2 hours, and then a 5 cm × 5 cm sample was cut and tested according to the method of dipping tin with a cover film.
剝離強度Peel strength
將以下實施例1～4和比較例1～4得到的覆蓋膜的每一個的離型紙剝離，並且分別將所述覆蓋膜的膠黏層與尺寸為20 cm（長）×20 cm（寬）×18 µm（厚度）的銅箔的光面覆合，用EWEDO-KY04C快壓機在180℃、100Kgf快壓1分鐘以後，置於普通恆溫試驗箱170℃固化1小時，得到分別貼附有對應於實施例1～4和比較例1～4的覆蓋膜的銅箔。The release paper of each of the cover films obtained in the following Examples 1 to 4 and Comparative Examples 1 to 4 was peeled off, and the adhesive layer and the size of the cover film were 20 cm (length) × 20 cm (width), respectively. × 18 µm (thickness) copper foil, laminated with EWEDO-KY04C fast press at 180 ° C and 100Kgf for 1 minute, and then placed in an ordinary constant temperature test box at 170 ° C for 1 hour. Copper foils corresponding to the cover films of Examples 1 to 4 and Comparative Examples 1 to 4.
根據IPC-TM-650 2.4.9方法，測試根據以上方法得到的分別貼附有對應於實施例1～4和比較例1～4的覆蓋膜的銅箔和以下實施例5～8和比較例5～8得到的覆銅板的剝離強度。測試結果顯示在以下表1～4中。其中，「剝離強度（A態）」表示所製備的貼附有覆蓋膜的銅箔或覆銅板在未經任何處理時測得的剝離強度；「剝離強度（288℃浸錫20s）」是指將所製備的覆蓋膜或覆銅板在288℃的錫液中浸漬20秒後測得的剝離強度；「剝離強度（288℃浸錫60s）」是指將所製備的覆蓋膜或覆銅板在288℃的錫液中浸漬60秒後測得的剝離強度；「剝離強度（170℃老化10h）」是指將所製備的覆蓋膜或覆銅板在170℃老化10小時後測得的剝離強度。According to the method of IPC-TM-650 2.4.9, the copper foils attached with the cover films corresponding to Examples 1 to 4 and Comparative Examples 1 to 4 obtained according to the above method, and the following Examples 5 to 8 and Comparative Examples were tested. Peel strength of the obtained copper-clad plates of 5-8. The test results are shown in Tables 1 to 4 below. Among them, "peeling strength (state A)" means the peeling strength of the prepared copper foil or copper-clad plate with a cover film measured without any treatment; "peeling strength (288 ° C immersion tin for 20s)" means Peel strength measured after immersing the prepared cover film or copper-clad board in a 288 ° C tin for 20 seconds; "Peel strength (immersion tin at 288 ° C for 60s)" refers to the prepared cover film or copper-clad board at 288 Peel strength measured after immersion in a tin solution at 60 ° C for 60 seconds; "peel strength (aged at 170 ° C for 10 hours)" refers to the peel strength measured after the prepared cover film or copper-clad plate was aged at 170 ° C for 10 hours.
阻燃性Flame retardancy
根據UL94垂直燃燒法測試在以下實施例1～8和比較例1～8中得到的覆蓋膜或覆銅板的阻燃性。其中實施例1～4和比較例1～4得到的覆蓋膜，要貼合固爾德18 µm壓延銅箔並固化後進行測試。The flame retardancy of the cover films or copper-clad boards obtained in the following Examples 1 to 8 and Comparative Examples 1 to 8 was tested according to the UL94 vertical combustion method. Wherein, the cover films obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were bonded to a 18 µm rolled copper foil and cured, and then tested.
實施例1Example 1
將90重量份的含羧基聚酯樹脂（由日本東洋紡公司提供的BX-39SS）、8重量份的鄰甲酚型環氧樹脂（由韓國科隆公司提供的KEC-2185A75）、2重量份的三縮水甘油基對胺基苯酚（由上海華誼公司提供的AFG-90）、25重量份的含氮阻燃劑（由日本三菱瓦斯公司提供的MC-5S）以及50重量份的丁酮（MEK）溶劑混合並攪拌，以得到無鹵樹脂組合物（樹脂膠液）。90 parts by weight of a carboxyl-containing polyester resin (BX-39SS provided by Japan Toyobo Co., Ltd.), 8 parts by weight of an o-cresol type epoxy resin (KEC-2185A75 provided by Korea Cologne), 2 parts by weight of three Glycidyl p-aminophenol (AFG-90 provided by Shanghai Huayi Company), 25 parts by weight of nitrogen-containing flame retardant (MC-5S provided by Mitsubishi Gas Corporation of Japan), and 50 parts by weight of methyl ethyl ketone (MEK ) The solvents are mixed and stirred to obtain a halogen-free resin composition (resin glue solution).
採用塗覆機將該樹脂膠液塗覆在厚度為12.5 µm的聚醯亞胺薄膜（Taimide TL-012，臺灣達邁）上，控制塗膠（乾膠）厚度為15 µm，隨後在140℃的高溫試驗箱中烘烤2分鐘，以在聚醯亞胺薄膜上形成部分交聯固化的膠黏層，然後將離型紙（厚度50 µm，日本住友化學公司）與該膠黏層覆合，製得撓性印刷電路板用覆蓋膜。The resin glue solution was coated on a polyimide film (Taimide TL-012, Taimai, Taiwan) with a thickness of 12.5 µm by a coater, and the thickness of the glue (dry glue) was controlled to 15 µm, followed by 140 ° C. Baking in a high-temperature test box for 2 minutes to form a partially cross-linked cured adhesive layer on the polyimide film, and then laminating a release paper (50 μm thick, Japan Sumitomo Chemical Co., Ltd.) with the adhesive layer, A cover film for a flexible printed circuit board was obtained.
實施例2Example 2
將70重量份的含羧基聚酯樹脂（由日本東洋紡公司提供的BX-39SS）、25重量份的鄰甲酚型環氧樹脂（由韓國科隆公司提供的KEC-2185A75）、5重量份的三縮水甘油基對胺基苯酚（由上海華誼公司提供的AFG-90）、25重量份的含氮阻燃劑（由日本三菱瓦斯公司提供的MC-5S）以及75重量份的丁酮（MEK）溶劑混合並攪拌，以得到無鹵樹脂組合物（樹脂膠液）。70 parts by weight of a carboxyl-containing polyester resin (BX-39SS provided by Japan Toyobo Co., Ltd.), 25 parts by weight of an o-cresol type epoxy resin (KEC-2185A75 provided by South Korea Cologne), and 5 parts by weight of three Glycidyl p-aminophenol (AFG-90 provided by Shanghai Huayi Company), 25 parts by weight of nitrogen-containing flame retardant (MC-5S provided by Mitsubishi Gas Corporation of Japan), and 75 parts by weight of methyl ethyl ketone (MEK ) The solvents are mixed and stirred to obtain a halogen-free resin composition (resin glue solution).
以與實施例1類似的方式製備撓性印刷電路板用覆蓋膜。A cover film for a flexible printed circuit board was prepared in a similar manner to Example 1.
實施例3Example 3
將80重量份的含羧基聚酯樹脂（由日本東洋紡公司提供的BX-39SS）、17重量份的鄰甲酚型環氧樹脂（由韓國科隆公司提供的KEC-2185A75）、3重量份的三縮水甘油基對胺基苯酚（由上海華誼公司提供的AFG-90）、15重量份的含氮阻燃劑（由日本三菱瓦斯公司提供的MC-5S）以及45重量份的丁酮（MEK）溶劑混合並攪拌，以得到無鹵樹脂組合物（樹脂膠液）。80 parts by weight of carboxyl-containing polyester resin (BX-39SS provided by Japan Toyobo Co., Ltd.), 17 parts by weight of o-cresol type epoxy resin (KEC-2185A75 provided by South Korea Cologne Company), and 3 parts by weight of three Glycidyl p-aminophenol (AFG-90 provided by Shanghai Huayi Company), 15 parts by weight of nitrogen-containing flame retardant (MC-5S provided by Mitsubishi Gas Corporation of Japan), and 45 parts by weight of methyl ethyl ketone (MEK ) The solvents are mixed and stirred to obtain a halogen-free resin composition (resin glue solution).
以與實施例1類似的方式製備撓性印刷電路板用覆蓋膜。A cover film for a flexible printed circuit board was prepared in a similar manner to Example 1.
實施例4Example 4
將80重量份的含羧基聚酯樹脂（由日本東洋紡公司提供的BX-39SS）、17重量份的鄰甲酚型環氧樹脂（由韓國科隆公司提供的KEC-2185A75）、3重量份的三縮水甘油基對胺基苯酚（由上海華誼公司提供的AFG-90）、15重量份的含氮阻燃劑（由德國科萊恩公司提供的OP-935）以及45重量份的丁酮（MEK）溶劑混合並攪拌，以得到無鹵樹脂組合物（樹脂膠液）。80 parts by weight of carboxyl-containing polyester resin (BX-39SS provided by Japan Toyobo Co., Ltd.), 17 parts by weight of o-cresol type epoxy resin (KEC-2185A75 provided by South Korea Cologne Company), and 3 parts by weight Glycidyl p-aminophenol (AFG-90 provided by Shanghai Huayi Company), 15 parts by weight of nitrogen-containing flame retardant (OP-935 provided by Clariant, Germany), and 45 parts by weight of methyl ethyl ketone (MEK ) The solvents are mixed and stirred to obtain a halogen-free resin composition (resin glue solution).
以與實施例1類似的方式製備撓性印刷電路板用覆蓋膜。A cover film for a flexible printed circuit board was prepared in a similar manner to Example 1.
實施例5Example 5
將以上實施例1中得到的無鹵樹脂組合物塗覆於12.5 µm的聚醯亞胺薄膜（Taimide TL-012，臺灣達邁）上，控制塗膠（乾膠）厚度為15 µm。將該塗覆有無鹵樹脂組合物的聚醯亞胺薄膜置於140℃高溫試驗箱烘烤2分鐘進行半固化，再將尺寸為40 cm（長）×25 cm（寬）×18 µm（厚度）的壓延銅箔（由日本日礦公司提供的BHY-22B-T）覆合於半固化的膠黏層上，100℃過塑，180℃/100kg壓力快壓60s，170℃固化2小時，以製備撓性印刷電路板用單面覆銅板。The halogen-free resin composition obtained in the above Example 1 was coated on a 12.5 µm polyimide film (Taimide TL-012, Taiwan Damai), and the thickness of the coating (dry adhesive) was controlled to 15 µm. The polyimide film coated with the halogen-free resin composition was baked in a 140 ° C high-temperature test box for 2 minutes for semi-curing, and then the size was 40 cm (length) × 25 cm (width) × 18 µm (thickness). ) Rolled copper foil (BHY-22B-T provided by Japan Nippon Mining Corporation) is laminated on the semi-cured adhesive layer, overmolded at 100 ° C, fast pressed at 180 ° C / 100kg for 60s, and cured at 170 ° C for 2 hours. To prepare a single-sided copper-clad board for a flexible printed circuit board.
實施例6Example 6
以與實施例5相同的方法製備撓性印刷電路板用單面覆銅板，不同之處在於採用實施例2中得到的無鹵樹脂組合物。A single-sided copper-clad board for a flexible printed circuit board was prepared in the same manner as in Example 5, except that the halogen-free resin composition obtained in Example 2 was used.
實施例7Example 7
以與實施例5相同的方法製備撓性印刷電路板用單面覆銅板，不同之處在於採用實施例3中得到的無鹵樹脂組合物。A single-sided copper-clad board for a flexible printed circuit board was prepared in the same manner as in Example 5, except that the halogen-free resin composition obtained in Example 3 was used.
實施例8Example 8
以與實施例5相同的方法製備撓性印刷電路板用單面覆銅板，不同之處在於採用實施例4中得到的無鹵樹脂組合物。A single-sided copper-clad board for a flexible printed circuit board was prepared in the same manner as in Example 5, except that the halogen-free resin composition obtained in Example 4 was used.
比較例1Comparative Example 1
將75重量份的聚酯型聚胺酯樹脂（由日本東洋紡公司提供的UR-3500，其酸值為35mgKOH/g）、20重量份的鄰甲酚型環氧樹脂（由韓國科隆公司提供的KEC-2185A75）、5重量份的三縮水甘油基對胺基苯酚（由上海華誼公司提供的AFG-90）、25重量份的含氮阻燃劑（由日本三菱瓦斯公司提供的MC-5S）以及70重量份的丁酮（MEK）溶劑混合並攪拌，以得到無鹵樹脂組合物（樹脂膠液）。75 parts by weight of a polyester polyurethane resin (UR-3500 provided by Japan Toyobo Co., Ltd. with an acid value of 35 mgKOH / g), and 20 parts by weight of an o-cresol type epoxy resin (KEC- 2185A75), 5 parts by weight of triglycidyl p-aminophenol (AFG-90 provided by Shanghai Huayi Company), 25 parts by weight of nitrogen-containing flame retardant (MC-5S provided by Mitsubishi Gas Corporation of Japan), and 70 parts by weight of methyl ethyl ketone (MEK) solvent was mixed and stirred to obtain a halogen-free resin composition (resin glue solution).
以與實施例1類似的方式製備撓性印刷電路板用覆蓋膜。A cover film for a flexible printed circuit board was prepared in a similar manner to Example 1.
比較例2Comparative Example 2
將75重量份的含羧基聚酯樹脂（由日本東洋紡公司提供的BX-39SS）、20重量份的鄰甲酚型環氧樹脂（由韓國科隆公司提供的KEC-2185A75）、5重量份的封閉型異氰酸酯（由德國德固薩公司提供的B-1358A）、25重量份的含氮阻燃劑（由日本三菱瓦斯公司提供的MC-5S）以及70重量份的丁酮（MEK）溶劑混合並攪拌，以得到無鹵樹脂組合物（樹脂膠液）。75 parts by weight of carboxyl-containing polyester resin (BX-39SS provided by Japan Toyobo Co., Ltd.), 20 parts by weight of o-cresol type epoxy resin (KEC-2185A75 provided by Korea Cologne), and 5 parts by weight of seal Type isocyanate (B-1358A provided by Degussa, Germany), 25 parts by weight of nitrogen-containing flame retardant (MC-5S provided by Mitsubishi Gas Corporation, Japan), and 70 parts by weight of methyl ethyl ketone (MEK) solvent are mixed and mixed. Stir to obtain a halogen-free resin composition (resin glue).
以與實施例1類似的方式製備撓性印刷電路板用覆蓋膜。A cover film for a flexible printed circuit board was prepared in a similar manner to Example 1.
比較例3Comparative Example 3
將75重量份的含羧基聚酯樹脂（由日本東洋紡公司提供的BX-39SS）、25重量份的鄰甲酚型環氧樹脂（由韓國科隆公司提供的KEC-2185A75）、25重量份的含氮阻燃劑（由日本三菱瓦斯公司提供的MC-5S）以及65重量份的丁酮（MEK）溶劑混合並攪拌，以得到無鹵樹脂組合物（樹脂膠液）。75 parts by weight of a carboxyl-containing polyester resin (BX-39SS provided by Japan Toyobo Co., Ltd.), 25 parts by weight of an o-cresol type epoxy resin (KEC-2185A75 provided by Korea Cologne), and 25 parts by weight of A nitrogen flame retardant (MC-5S provided by Mitsubishi Gas Corporation of Japan) and 65 parts by weight of methyl ethyl ketone (MEK) solvent were mixed and stirred to obtain a halogen-free resin composition (resin glue solution).
以與實施例1類似的方式製備撓性印刷電路板用覆蓋膜。A cover film for a flexible printed circuit board was prepared in a similar manner to Example 1.
比較例4Comparative Example 4
將50重量份的含羧基聚酯樹脂（由日本東洋紡公司提供的BX-39SS）、35重量份的鄰甲酚型環氧樹脂（由韓國科隆公司提供的KEC-2185A75）、15重量份的三縮水甘油基對胺基苯酚（由上海華誼公司提供的AFG-90）、25重量份的含氮阻燃劑（由日本三菱瓦斯公司提供的MC-5S）以及100重量份的丁酮（MEK）溶劑混合並攪拌，以得到無鹵樹脂組合物（樹脂膠液）。50 parts by weight of a carboxyl-containing polyester resin (BX-39SS provided by Japan Toyobo Co., Ltd.), 35 parts by weight of an o-cresol type epoxy resin (KEC-2185A75 provided by South Korea Cologne), and 15 parts by weight of three Glycidyl p-aminophenol (AFG-90 provided by Shanghai Huayi Company), 25 parts by weight of nitrogen-containing flame retardant (MC-5S provided by Mitsubishi Gas Corporation of Japan), and 100 parts by weight of methyl ethyl ketone (MEK ) The solvents are mixed and stirred to obtain a halogen-free resin composition (resin glue solution).
以與實施例1類似的方式製備撓性印刷電路板用覆蓋膜。A cover film for a flexible printed circuit board was prepared in a similar manner to Example 1.
比較例5Comparative Example 5
以與實施例5相同的方法製備撓性印刷電路板用單面覆銅板，不同之處在於採用比較例1中得到的無鹵樹脂組合物。A single-sided copper-clad board for a flexible printed circuit board was prepared in the same manner as in Example 5 except that the halogen-free resin composition obtained in Comparative Example 1 was used.
比較例6Comparative Example 6
以與實施例5相同的方法製備撓性印刷電路板用單面覆銅板，不同之處在於採用比較例2中得到的無鹵樹脂組合物。A single-sided copper-clad board for a flexible printed circuit board was prepared in the same manner as in Example 5 except that the halogen-free resin composition obtained in Comparative Example 2 was used.
比較例7Comparative Example 7
以與實施例5相同的方法製備撓性印刷電路板用單面覆銅板，不同之處在於採用比較例3中得到的無鹵樹脂組合物。A single-sided copper-clad board for a flexible printed circuit board was prepared in the same manner as in Example 5 except that the halogen-free resin composition obtained in Comparative Example 3 was used.
比較例8Comparative Example 8
以與實施例5相同的方法製備撓性印刷電路板用單面覆銅板，不同之處在於採用比較例4中得到的無鹵樹脂組合物。A single-sided copper-clad board for a flexible printed circuit board was prepared in the same manner as in Example 5 except that the halogen-free resin composition obtained in Comparative Example 4 was used.
根據在以上測試方法部分中描述的測量方法，對在以上實施例1～8和比較例1～8中得到的覆蓋膜或覆銅板的各項性能（覆型性、極限耐浸焊溫度、剝離強度、阻燃性和耐浸焊性）進行了測試。其中，關於撓性印刷電路板用覆蓋膜的測試結果顯示在以下表1～表2中；關於撓性印刷電路板用單面覆銅板的測試結果顯示在以下表3～表4中。According to the measurement methods described in the above test method section, the properties of the cover film or copper-clad board obtained in the above Examples 1 to 8 and Comparative Examples 1 to 8 (coverability, extreme dip soldering temperature, peel strength) , Flame retardancy and solder resistance) were tested. The test results of the cover film for flexible printed circuit boards are shown in Tables 1 to 2 below, and the test results of the single-sided copper-clad boards for flexible printed circuit boards are shown in Tables 3 to 4 below.
〔表1〕實施例1～4中得到的撓性印刷電路板用覆蓋膜的性能測試結果
〔表2〕比較例1～4中得到的撓性印刷電路板用覆蓋膜的性能測試結果
由表1中的實施例1～4的測量結果可以看出，採用本發明無鹵樹脂組合物製備的覆蓋膜具有優異的耐熱性能，極限耐浸焊溫度超過360℃，288℃浸錫20s剝離強度保持率大於85%；搭配含氮阻燃劑時，288℃浸錫60s剝離強度保持率仍然大於85%，部分製品的剝離強度甚至有所提高，170℃老化10h後的剝離強度保持率均大於80%。另外，覆蓋膜的溢膠量適中，覆型性合格，覆合銅箔後燃燒性達到V0級。From the measurement results of Examples 1 to 4 in Table 1, it can be seen that the cover film prepared by using the halogen-free resin composition of the present invention has excellent heat resistance performance, the ultimate resistance to dip soldering temperature exceeds 360 ° C, and the peel strength of 288 ° C immersion tin for 20 seconds The retention rate is greater than 85%; when the nitrogen-containing flame retardant is used, the peel strength retention rate of immersion tin at 288 ℃ for 60s is still greater than 85%, and the peel strength of some products is even improved. 80%. In addition, the overflow of the cover film is moderate, and the moldability is acceptable. The flammability after the copper foil is laminated reaches V0 level.
反觀表2中的比較例1～4的測試結果，可以看出，比較例1中以聚胺酯膠黏劑製備的覆蓋膜極限耐浸焊溫度明顯低於本發明樹脂組合物製備的覆蓋膜，且浸錫後剝離強度突降。比較例2中以異氰酸酯代替含氮環氧化合物，促進樹脂組合物固化，製得的覆蓋膜，雖然360℃浸錫20s無起泡現象，但288℃浸錫後的剝離強度會急劇下降，說明其綜合耐熱性能不佳。如關於比較例3的結果可知，若無含氮環氧化合物作為固化促進劑，膠黏劑達到半固化狀態的時間較長，288℃浸錫後剝離強度急劇下降。另外，比較例4採用的樹脂種類與本發明相同，但組分的比例不同，可以發現其耐熱性能不足，覆型性差。因此，本發明的樹脂組合物不僅要求含羧基聚酯樹脂、多官能環氧樹脂和含氮環氧化合物的搭配，還要求其各組分的配比，才能製得具有優異性能的覆蓋膜。Looking back at the test results of Comparative Examples 1 to 4 in Table 2, it can be seen that the limit dip soldering temperature of the cover film prepared by using the polyurethane adhesive in Comparative Example 1 is significantly lower than that of the cover film prepared by the resin composition of the present invention. After the tin peeling strength drops suddenly. In Comparative Example 2, the isocyanate was used instead of the nitrogen-containing epoxy compound to promote the curing of the resin composition. Although the coating film obtained had no foaming after being immersed in tin at 360 ° C for 20s, the peel strength after immersion in tin at 288 ° C would decrease sharply. Its comprehensive heat resistance is poor. As can be seen from the results of Comparative Example 3, if the nitrogen-containing epoxy compound is not used as a curing accelerator, it takes a long time for the adhesive to reach a semi-cured state, and the peel strength decreases sharply after dipping at 288 ° C. In addition, the resin used in Comparative Example 4 was the same as that of the present invention, but the proportions of the components were different, and it was found that the heat resistance was insufficient and the moldability was poor. Therefore, the resin composition of the present invention not only requires the combination of a carboxyl-containing polyester resin, a polyfunctional epoxy resin, and a nitrogen-containing epoxy compound, but also requires the proportion of each component thereof to obtain a cover film having excellent properties.
〔表3〕實施例5～8中得到的撓性印刷電路板用單面覆銅板的性能測試結果
〔表4〕比較例5～8中得到的撓性印刷電路板用單面覆銅板的性能測試結果
由表3和表4可以看出，撓性印刷電路板用單面覆銅板的剝離強度、耐浸焊性能、耐老化性能與無鹵樹脂組合物配方的關係和覆蓋膜與無鹵樹脂組合物配方的關係類似，按照本發明所述方法實施的實施例中得到覆銅板的性能優異。As can be seen from Tables 3 and 4, the relationship between the peel strength, dip solder resistance, and aging resistance of the single-sided copper-clad laminate for flexible printed circuit boards and the formulation of the halogen-free resin composition, and the formulation of the cover film and the halogen-free resin composition The relationship is similar, and the performance of the copper clad laminates obtained in the embodiments implemented according to the method of the present invention is excellent.
綜上所述，本發明的無鹵樹脂組合物包含含羧基的聚酯樹脂、多官能環氧樹脂、含氮環氧化合物、阻燃劑和有機溶劑，其中含羧基聚酯樹脂可與多官能環氧樹脂反應，多官能環氧樹脂可以發生自聚反應，並且含氮環氧化合物可以促進上述反應的進行，促進形成互穿聚合物網絡結構，使得固化產物具有優異的耐熱性能、耐老化性能和黏結性能。In summary, the halogen-free resin composition of the present invention comprises a carboxyl-containing polyester resin, a polyfunctional epoxy resin, a nitrogen-containing epoxy compound, a flame retardant, and an organic solvent. Epoxy resin reaction, polyfunctional epoxy resin can undergo self-polymerization reaction, and nitrogen-containing epoxy compounds can promote the above reaction and promote the formation of interpenetrating polymer network structure, so that the cured product has excellent heat resistance and aging resistance And adhesive properties.
本發明樹脂組合物製作的覆蓋膜和覆銅板具有優異的耐熱性能、耐老化性能，較高的剝離強度，覆合銅箔後阻燃等級達到UL94-V0級，綜合性能優異。The cover film and the copper-clad board made of the resin composition of the present invention have excellent heat resistance, aging resistance, high peel strength, and the flame-retardant grade after the copper foil is laminated reaches UL94-V0 level, and the comprehensive performance is excellent.
儘管本發明中已經示出和描述了具體的實施方式，但本領域技術人員將懂得，可以用各種替代的和/或等同的實施方式代替所示和所描述的具體實施方式，而不脫離本發明的範圍。本申請意欲包括對本發明中討論的具體實施方式的任何改進或更改。因此，本發明僅受限於申請專利範圍及其等同物。Although specific embodiments have been shown and described in the present invention, those skilled in the art will understand that the specific embodiments shown and described may be replaced with various alternative and / or equivalent embodiments without departing from the present invention. The scope of the invention. This application is intended to cover any adaptations or variations of the specific embodiments discussed in the present invention. Therefore, the present invention is limited only by the scope of patent applications and their equivalents.
本領域技術人員應當理解，在不背離本發明範圍的情況下，可以進行多種修改和改變。這樣的修改和改變意欲落入如後附申請專利範圍所限定的本發明的範圍之內。Those skilled in the art will understand that various modifications and changes can be made without departing from the scope of the present invention. Such modifications and changes are intended to fall within the scope of the invention as defined by the appended claims.
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| 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 |
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| 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 |
| 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 |
| 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 |
| CN116410684A (en) * | 2021-12-31 | 2023-07-11 | 广东生益科技股份有限公司 | A kind of resin composition and cover film prepared thereof |
| CN118725520A (en) * | 2023-03-28 | 2024-10-01 | 广东生益科技股份有限公司 | A resin composition and covering film |
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| CN105492534A (en) * | 2013-09-26 | 2016-04-13 | 东洋纺株式会社 | Polyurethane resin composition, adhesive composition using same, laminate, printed wiring board |
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| JP2007070481A (en) * | 2005-09-07 | 2007-03-22 | Toyobo Co Ltd | Adhesive composition and flexible printed wiring board using the same |
| KR101605221B1 (en) * | 2008-12-26 | 2016-03-21 | 도요보 가부시키가이샤 | Resin composition for adhesive, adhesive comprising same, adhesive sheet, and printed wiring board including same as adhesive layer |
| WO2010113945A1 (en) * | 2009-03-31 | 2010-10-07 | 日産化学工業株式会社 | Polyester composite for forming thermoset films |
| 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 |
| US9365717B2 (en) * | 2011-05-31 | 2016-06-14 | Toyobo Co., Ltd. | Carboxyl group-containing polyimide, thermosetting resin composition and flexible metal-clad laminate |
| 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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| CN105492534A (en) * | 2013-09-26 | 2016-04-13 | 东洋纺株式会社 | Polyurethane resin composition, adhesive composition using same, laminate, printed wiring board |
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