CN108864924A - A kind of halogen-free resin composition and the flexible printed-circuit board cover film prepared with it - Google Patents
A kind of halogen-free resin composition and the flexible printed-circuit board cover film prepared with it Download PDFInfo
- Publication number
- CN108864924A CN108864924A CN201810725392.6A CN201810725392A CN108864924A CN 108864924 A CN108864924 A CN 108864924A CN 201810725392 A CN201810725392 A CN 201810725392A CN 108864924 A CN108864924 A CN 108864924A
- Authority
- CN
- China
- Prior art keywords
- halogen
- resin composition
- parts
- polyurethane
- 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.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 114
- 239000013039 cover film Substances 0.000 title claims abstract description 82
- 229920002635 polyurethane Polymers 0.000 claims abstract description 96
- 239000004814 polyurethane Substances 0.000 claims abstract description 96
- 239000003822 epoxy resin Substances 0.000 claims abstract description 42
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 39
- 229920006147 copolyamide elastomer Polymers 0.000 claims abstract description 37
- 239000010408 film Substances 0.000 claims abstract description 31
- 150000001412 amines Chemical class 0.000 claims abstract description 25
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003063 flame retardant Substances 0.000 claims abstract description 18
- 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 16
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000004952 Polyamide Substances 0.000 claims description 54
- 229920002647 polyamide Polymers 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 43
- 239000007787 solid Substances 0.000 claims description 31
- 239000004642 Polyimide Substances 0.000 claims description 29
- 229920001721 polyimide Polymers 0.000 claims description 29
- 230000009477 glass transition Effects 0.000 claims description 25
- 229920001577 copolymer Polymers 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 9
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 8
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 8
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 8
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 claims description 8
- 229920001400 block copolymer Polymers 0.000 claims description 7
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 7
- RPHYLOMQFAGWCD-UHFFFAOYSA-N ethane;phenol Chemical compound CC.OC1=CC=CC=C1 RPHYLOMQFAGWCD-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000004843 novolac epoxy resin Substances 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims description 5
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- -1 and it is dry Substances 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229910004674 SiO0.5 Inorganic materials 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 125000005375 organosiloxane group Chemical group 0.000 claims description 2
- 150000002924 oxiranes Chemical class 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 8
- 238000012360 testing method Methods 0.000 abstract description 8
- 238000012546 transfer Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 23
- 239000010410 layer Substances 0.000 description 18
- 150000004767 nitrides Chemical class 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical group C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000037427 ion transport Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000012745 toughening agent Substances 0.000 description 3
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification 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
- 238000007719 peel strength test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- JOHZPMXAZQZXHR-UHFFFAOYSA-N pipemidic acid Chemical compound N1=C2N(CC)C=C(C(O)=O)C(=O)C2=CN=C1N1CCNCC1 JOHZPMXAZQZXHR-UHFFFAOYSA-N 0.000 description 1
- 229960001732 pipemidic acid Drugs 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/08—Polyurethanes from polyethers
-
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a kind of halogen-free resin compositions, including each component for the following parts by weight being scattered in organic solvent：35-50 parts of 10-20 parts of phosphorous epoxy resin, 10-15 parts of polyfunctional epoxy resin, polyurethane and polyamide block copolymer, 10-20 parts of MQ resin, 5-10 parts of amine curing agent, 5-15 parts of phosphonium flame retardant；The invention also discloses a kind of cover films prepared using the halogen-free resin composition；The cover film has excellent flexibility, ion concentration is low, is not in dendrite, good insulating in the test of resistance to Ion transfer, there is excellent peel strength, heat resistance, dimensional stability, chemical resistance, storage characteristics and processing performance simultaneously, anti-flammability is up to VTM-0 grades of UL94.
Description
Technical field
The present invention relates to polymer composite manufacturing field more particularly to a kind of halogen-free resin composition and its preparations
Flexible printed circuit cover film.
Background technique
Flexible printed circuit is the film made of Kapton or polyester film surface single spreading with cover film
Shape insulating materials is the most common protective layer of flexible printed-circuit board.Similar to the solder mask of rigid printed circuit boards, but function
Can be more powerful, welding resistance effect is not only acted as, and protection circuit is not damaged by forms such as dust, moisture, chemicals pollutions
Effect, while there is certain flexibility and humidification, reduce the influence of conductor stress during bending, improve flexible
The resistance to deflection of printed circuit board.
In current industry, the maximum cover film of usage amount is Kapton cover film, it is thin in polyimides
Film surface single side coats one layer of adhesive and forms, and common adhesive is by using nbr carboxyl terminal toughening modifying epoxy
And be aided with fire retardant, filler and other auxiliary agents and be prepared, such as United States Patent (USP) US20030091842 and Chinese patent
Method described in CN102093667A, CN101486883B.However, the usual flexibility of the cover film prepared in this way
It is bad, anti-flammability is poor, and the problems such as that there are rubber components is easy to aging, resistance to ion transport is poor.
With the development of flexible printed-circuit board technology, flexibility, heat resistance and reliability requirement of the market to cover film
It is higher and higher.Increasingly strict technology has obviously been unable to satisfy with cover film prepared by nbr carboxyl terminal toughening modifying epoxy
It is required that.Therefore, it is badly in need of the new resin combination of one kind in industry at present to solve the problems of prior art.
Summary of the invention
It is an object of the invention to overcome the defect of the prior art, provides a kind of halogen-free resin composition and prepared with it
Flexible printed-circuit board cover film, the composition have excellent flexibility, anti-flammability and heat resistance；The cover film has
Excellent flexibility, ion concentration is low, is not in dendrite in the test of resistance to Ion transfer, good insulating has simultaneously
Excellent peel strength, heat resistance, dimensional stability, chemical resistance, storage characteristics and processing performance, anti-flammability is up to UL94VTM-
0 grade.
The invention is realized in this way：
It is an object of the present invention to provide a kind of halogen-free resin composition, which includes to be scattered in have
The each component of following parts by weight in solvent：10-20 parts of phosphorous epoxy resin, 10-15 parts of polyfunctional epoxy resin, polyurethane
With 35-50 parts of polyamide block copolymer, 10-20 parts of MQ resin, 5-10 parts of amine curing agent, 5-15 parts of phosphonium flame retardant.
Preferably, the solid content of the halogen-free resin composition is 40wt%~70wt%.
Preferably, the phosphorous epoxy resin be DOPO type phosphorous epoxy resin, DOPO-HQ type phosphorous epoxy resin,
One or more of phosphate modified epoxy resin mixture.
Preferably, the epoxide equivalent of the polyfunctional epoxy resin is between 160-380g/eq, preferably phenol type phenolic aldehyde
Epoxy resin, bisphenol A-type novolac epoxy resin, Study On O-cresol Epoxy Resin, one in four phenol ethane, four glycidol ether
Kind or a variety of mixtures.The polyfunctional epoxy resin can not only increase the cohesive strength of composition, improve peel strength, together
When the heat resistance and chemical resistance of composition also can be improved.
Preferably, the polyurethane and polyamide block copolymer by diisocyanate, polyether Glycols, binary acid and
Binary amine copolymer is made, and wherein polyurethane segment is soft segment, the number-average molecular weight 1500-2200 of polyurethane segment, vitrifying turn
Temperature Tg is -40~-20 DEG C；Polyamide segment is hard section, and the number-average molecular weight of polyamide-block is 3000-4500, glass
Changing transition temperature is 10~20 DEG C.
Preferably, the amine value of the polyurethane and polyamide block copolymer be 12-18mgKOH/g, amine value too it is low then
Heat resistance is insufficient；Amine value is too high, then easily leads to halogen-free resin composition storage stability variation, and processability is deteriorated.
Polyamide segment content is more, then heat resistance is better, but flexibility is deteriorated, toughening increasing is soft not sufficiently effective, and inhales
Water rate is got higher, and electrical property is deteriorated；Polyurethane segment content is more, and it is better that toughening increases soft effect, but heat resistance is insufficient.Therefore,
Preferably, polyamide segment molal quantity accounts in block copolymer and is no less than 60% in polyurethane and polyamide total mole number；Poly- ammonia
Ester segment molal quantity accounts in block copolymer and is no less than 20% in polyurethane and polyamide total mole number.
Preferably, the MQ resin has core-shell structure, preferably by M group organic silicon monomer and Q group organosilicon list
Body is through made of hydrolytic condensation, M/Q value is 1.0~1.5.Its M/Q value is too low, then polarity is too high, in resin combination
Other components compatibility poor；M/Q value is too high, then is not easy to wash, and remains excessive inorganic ions, influences resistance to Ion transfer performance.
Preferably, the M group organic silicon monomer is that simple function organosiloxane closes chain link R3SiO0.5；In R base
Amino can be reacted with epoxy group, make to form chemical bonds between MQ resin and epoxy resin, improve MQ resin and epoxy group
The compatibility divided.
Specifically, the M group organic silicon monomer has the following structure：
Wherein n, m take the integer between 8 to 20.
The Q group organic silicon monomer is tetra functional silicon monomer, be can be selected from methyl orthosilicate or ethyl orthosilicate
One kind.
The MQ resin is prepared as follows：
(1) deionized water, dehydrated alcohol, toluene, salt are added in the reaction kettle for having agitating paddle, thermometer, condenser pipe
Acid and M group organic silicon monomer, are warming up to 60-80 DEG C, are stirred to react 0.5-2h；
(2) the tetra functional silicon monomer of Q group is added dropwise, continues to be stirred to react 0.5-2h at 75-80 DEG C；
(3) it extracts, wash, revolving, obtaining MQ resin.
Preferably, the amine curing agent is selected from 4,4'-diaminodiphenyl sulfone, 3,3'- diaminodiphenylsulfone, double cyanogen
One of amine, m-phenylene diamine (MPD), diethylenetriamine and diaminodiphenylmethane are a variety of.
Preferably, SPB-100, the German section Lay of the preferred Ben Otsuka Chemical Co., Ltd manufacture of the phosphonium flame retardant
The OP-935 and OP-930 etc. of benefactor department manufacture.
Preferably, the organic solvent is acetone, butanone, cyclohexanone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, acetic acid second
One or more of ester, propylene glycol methyl ether acetate, dimethylformamide mixture.
The preparation method of halogen-free resin composition of the present invention is：Using solvent by the phosphorous asphalt mixtures modified by epoxy resin of said ratio
Rouge, polyfunctional epoxy resin, polyurethane and polyamide block copolymer, MQ resin and amine curing agent dissolution, are then added and contain
Phosphorus fire retardant, and use the equipment such as ball mill, three-roller, planetary mixer by the solid and liquid component in the present composition
Mixing is dispersed with, and obtained liquid dispersion is the halogen-free resin composition.
The second object of the present invention is to provide a kind of flexible printing electricity prepared using the halogen-free resin composition
Road plate cover film, formed including Kapton, by above-mentioned composition Kapton surface composition layer and
Release paper on composition layer.
Preferably, the Kapton is with a thickness of 5-50 μm；
Preferably, the halogen-free resin composition layer is with a thickness of 5-35 μm.
Preferably, the release paper is with a thickness of 50-150 μm；
Wherein, the flexible printed circuit cover film, preparation method are as follows：By the halogen-free resin composition
Side coated on Kapton, then by online dry baking oven, 70-160 DEG C baking 2-4 minutes, have with removing
Solvent, and the composition layer of semi-solid preparation is formed, then compound with release paper at 50-70 DEG C, winding obtains described scratching
Property printed circuit cover film.
Compared with prior art, the invention has the advantages that and effect：
1, a kind of halogen-free resin composition provided by the invention, the glass transition of polyurethane and polyamide block copolymer
Temperature is low, and flexibility is good.MQ resin is a kind of organic/inorganic silicone resin with core-shell structure, and internal is cage modle SiO2Core,
Outside is amino-containing long alkyl chain and amino-containing aromatic series segment, and amino-containing long alkyl chain and amino-containing aromatic series
The molar ratio of segment is 1：1, while there is good flexibility, heat resistance and suitable reactivity, and place can be effectively controlled
In the gummosis behavior of the resin combination of B scalariform state.The present invention using polyurethane and polyamide block copolymer as main toughener,
MQ resin increases soft modified epoxy as auxiliary toughener, common toughening；Both contain amino, can all occur with epoxy resin
Cross-linking and curing reaction, the compatibility being effectively improved between three, overcoming silicone surface can be low, compatible with other organic resins
Property difference problem, and the heat resistance of resin combination can be effectively improved.Appropriate mutually separation can be formed in solidification objects system, and is formed
Island structure, when by external force, toughening particle can induce and terminate crazing generation, energy be absorbed, to obtain excellent
Different toughening effect.
2, a kind of cover film prepared using the halogen-free resin composition provided by the invention, with the resin combination
Prepared cover film has excellent flexibility, and ion concentration is low, is not in dendrite in the test of resistance to Ion transfer,
Good insulating, at the same have excellent peel strength, heat resistance, resistance to ag(e)ing, dimensional stability, chemical resistance, storage characteristics and
Processing performance, anti-flammability is up to UL94VTM-0 grades.
Specific embodiment
Embodiment 1
One, halogen-free resin composition
1, the halogen-free resin composition includes 10 parts of DOPO type phosphorous epoxy resin, phenol type novolac epoxy resin 10
Part, polyurethane and 35 parts of polyamide block copolymer, 10 parts of MQ resin, 2 parts of dicyandiamide, 3 parts of m-phenylene diamine (MPD), phosphonium flame retardant
(SPB-100) 5 parts.
2, the amine value 12mgKOH/g of the polyurethane and polyamide block copolymer, wherein the number of polyurethane segment is equal
Molecular weight is 1500, and glass transition temperature Tg is -40 DEG C；The number-average molecular weight of polyamide segment is 3000, glass transition
Temperature Tg is 10 DEG C；Polyamide segment accounts for 60% of polyurethane and polyamide segment total mole number in copolymer, polyurethane segment
Account for polyurethane and the 40% of polyamide segment total mole number in copolymer.
3, above-mentioned each component dissolved with acetone, mix and is separated into halogen-free resin composition, solid content 40wt%.
Two, flexible printed circuit cover film
Included the following steps with cover film prepared by the halogen-free resin composition：By the halogen-free resin composition
Applied to flexible printed circuit cover film.Using coating equipment by the resin composition in 10 μm of polyimide insulative films
Surface, 5 μm of rubberization thickness；Toast semi-solid preparation with polyimide insulative film surface formed solid-state composition nitride layer, be finally bonded from
Type paper winds to obtain the cover film.
Embodiment 2
One, halogen-free resin composition
1, the halogen-free resin composition includes 15 parts of DOPO-HQ type phosphorous epoxy resin, bisphenol A-type novolac epoxy resin
40 parts of 10 parts, polyurethane and polyamide block copolymer, 15 parts of MQ resin, 5 parts of 4,4 '-diaminodiphenylsulfone, diethylenetriamine 2
Part, 8 parts of phosphonium flame retardant (OP-935).
2, the amine value 15mgKOH/g of the polyurethane and polyamide block copolymer, wherein the number of polyurethane segment is equal
Molecular weight is 1800, and glass transition temperature Tg is -35 DEG C；The number-average molecular weight of polyamide segment is 3500, glass transition
Temperature Tg is 15 DEG C；Polyamide segment accounts for 70% of polyurethane and polyamide segment total mole number in copolymer, polyurethane segment
Account for polyurethane and the 30% of polyamide segment total mole number in copolymer.
3, above-mentioned each component dissolved with cyclohexanone, mix and is separated into halogen-free resin composition, solid content 40wt%.
Two, flexible printed circuit cover film
Included the following steps with cover film prepared by the halogen-free resin composition：By the halogen-free resin composition
Applied to flexible printed circuit cover film, using coating equipment by the resin composition in 25 μm of polyimide insulative films
Surface, 15 μm of rubberization thickness；Toast semi-solid preparation with polyimide insulative film surface formed solid-state composition nitride layer, be finally bonded from
Type paper winds to obtain the cover film.
Embodiment 3
One, halogen-free resin composition
1, the halogen-free resin composition includes 20 parts of phosphate modified epoxy resin, Study On O-cresol Epoxy Resin 15
Part, polyurethane and 45 parts of polyamide block copolymer, 20 parts of MQ resin, 10 parts of 3,3 '-diaminodiphenylsulfone, phosphonium flame retardant
(OP-930) 15 parts.
2, the amine value 18mgKOH/g of the polyurethane and polyamide block copolymer, wherein the number of polyurethane segment is equal
Molecular weight is 2200, and glass transition temperature Tg is -20 DEG C；The number-average molecular weight of polyamide segment is 4500, glass transition
Temperature Tg is 20 DEG C；Polyamide segment accounts for 80% of polyurethane and polyamide segment total mole number in copolymer, polyurethane segment
Account for polyurethane and the 20% of polyamide segment total mole number in copolymer.
3, above-mentioned each component dissolved with dimethylformamide, mix and is separated into halogen-free resin composition, solid content
50wt%.
Two, flexible printed circuit cover film
Included the following steps with cover film prepared by the halogen-free resin composition：By the halogen-free resin composition
Applied to flexible printed circuit cover film, using coating equipment by the resin composition in 35 μm of polyimide insulative films
Surface, 25 μm of rubberization thickness；Toast semi-solid preparation with polyimide insulative film surface formed solid-state composition nitride layer, be finally bonded from
Type paper winds to obtain the cover film.
Embodiment 4
One, halogen-free resin composition
1, the halogen-free resin composition includes 18 parts of DOPO type phosphorous epoxy resin, four phenol ethane, four glycidol ether
50 parts of 13 parts, polyurethane and polyamide block copolymer, 20 parts of MQ resin, 9 parts of diaminodiphenylmethane, phosphonium flame retardant (OP-
935) 14 parts.
2, the amine value 16mgKOH/g of the polyurethane and polyamide block copolymer, wherein the number of polyurethane segment is equal
Molecular weight is 2000, and glass transition temperature Tg is -25 DEG C；The number-average molecular weight of polyamide segment is 4200, glass transition
Temperature Tg is 20 DEG C；Polyamide segment accounts for 75% of polyurethane and polyamide segment total mole number in copolymer, polyurethane segment
Account for polyurethane and the 25% of polyamide segment total mole number in copolymer.
3, above-mentioned each component dissolved with butanone, mix and is separated into halogen-free resin composition, solid content 50wt%.
Two, flexible printed circuit cover film
Included the following steps with cover film prepared by the halogen-free resin composition：By the halogen-free resin composition
Applied to flexible printed circuit cover film, using coating equipment by the resin composition in 50 μm of polyimide insulative films
Surface, 35 μm of rubberization thickness；Toast semi-solid preparation with polyimide insulative film surface formed solid-state composition nitride layer, be finally bonded from
Type paper winds to obtain the cover film.
Comparative example 1
One, halogen-free resin composition
1, for the halogen-free resin composition of the comparative example in addition to without MQ resin, other are consistent with embodiment 1.Specifically, institute
Halogen-free resin composition is stated to include 10 parts of DOPO type phosphorous epoxy resin, 10 parts of phenol type novolac epoxy resin, polyurethane and gather
35 parts of amide block copolymers, 2 parts of dicyandiamide, 3 parts of m-phenylene diamine (MPD), 5 parts of phosphonium flame retardant (SPB-100).
2, the amine value 12mgKOH/g of the polyurethane and polyamide block copolymer, wherein the number of polyurethane segment is equal
Molecular weight is 1500, and glass transition temperature Tg is -40 DEG C；The number-average molecular weight of polyamide segment is 3000, glass transition
Temperature Tg is 10 DEG C；Polyamide segment accounts for 60% of polyurethane and polyamide segment total mole number in copolymer, polyurethane segment
Account for polyurethane and the 40% of polyamide segment total mole number in copolymer.
3, above-mentioned each component dissolved with acetone, mix and is separated into halogen-free resin composition, solid content 40wt%.
Two, flexible printed circuit cover film
Included the following steps with cover film prepared by the halogen-free resin composition：By the halogen-free resin composition
Applied to flexible printed circuit cover film, using coating equipment by the resin composition in 10 μm of polyimide insulative films
Surface, 5 μm of rubberization thickness；Toast semi-solid preparation with polyimide insulative film surface formed solid-state composition nitride layer, be finally bonded from
Type paper winds to obtain the cover film.
Comparative example 2
One, halogen-free resin composition
1, the halogen-free resin composition of the comparative example is in addition to without polyurethane and polyamide block copolymer, other and implementation
Example 2 is consistent.Specifically, the halogen-free resin composition, including 15 parts of DOPO-HQ type phosphorous epoxy resin, bisphenol A-type phenolic aldehyde ring
10 parts of oxygen resin, 15 parts of MQ resin, 5 parts of 4,4 '-diaminodiphenylsulfone, 2 parts of diethylenetriamine, phosphonium flame retardant (OP-935) 8
Part.
2, above-mentioned each component dissolved with cyclohexanone, mix and is separated into halogen-free resin composition, solid content 40wt%.
Two, flexible printed circuit cover film
Included the following steps with cover film prepared by the halogen-free resin composition：By the halogen-free resin composition
Applied to flexible printed circuit cover film.Using coating equipment by the resin composition in 25 μm of polyimide insulative films
Surface, 15 μm of rubberization thickness；Toast semi-solid preparation with polyimide insulative film surface formed solid-state composition nitride layer, be finally bonded from
Type paper winds to obtain the cover film.
Comparative example 3
One, halogen-free resin composition
1, polyurethane and polyamide block copolymer replace with outside polyurethane in the halogen-free resin composition of the comparative example,
He and embodiment 3 are consistent.Specifically, the halogen-free resin composition, including 20 parts of phosphate modified epoxy resin, o-Hydroxytoluene
15 parts of formaldehyde epoxy resin, 45 parts of polyurethane, 20 parts of MQ resin, 10 parts of 3,3 '-diaminodiphenylsulfone, phosphonium flame retardant (OP-930)
15 parts.
2, the number-average molecular weight of the polyurethane is 2200, and glass transition temperature Tg is -20 DEG C.
3, above-mentioned each component dissolved with dimethylformamide, mix and is separated into halogen-free resin composition, solid content
50wt%.
Two, flexible printed circuit cover film
Included the following steps with cover film prepared by the halogen-free resin composition：
The halogen-free resin composition is applied to flexible printed circuit cover film, using coating equipment by the resin
Composition be coated on 35 μm of polyimide insulative film surfaces, 25 μm of rubberization thickness；Semi-solid preparation is toasted in polyimide insulative film
Surface forms solid-state composition nitride layer, is finally bonded release paper and winds to obtain the cover film.
Comparative example 4
One, halogen-free resin composition
1, polyurethane and polyamide block copolymer replace with outside polyamide in the halogen-free resin composition of the comparative example,
He and embodiment 3 are consistent.Specifically, the halogen-free resin composition, including 20 parts of phosphate modified epoxy resin, o-Hydroxytoluene
15 parts of formaldehyde epoxy resin, 45 parts of polyamide, 20 parts of MQ resin, 10 parts of 3,3 '-diaminodiphenylsulfone, phosphonium flame retardant (OP-930)
15 parts.
2, the amine value 18mgKOH/g of the polyamide, number-average molecular weight 4500, glass transition temperature Tg 20
℃。
3, above-mentioned each component dissolved with dimethylformamide, mix and is separated into halogen-free resin composition, solid content
50wt%.
Two, flexible printed circuit cover film
Included the following steps with cover film prepared by the halogen-free resin composition：Using coating equipment by the resin group
Close object be coated on 35 μm of polyimide insulative film surfaces, 25 μm of rubberization thickness；Semi-solid preparation is toasted in polyimide insulative film table
Face forms solid-state composition nitride layer, is finally bonded release paper and winds to obtain the cover film.
Comparative example 5
One, halogen-free resin composition
1, polyurethane and polyamide block copolymer replace with the poly- of not block in the halogen-free resin composition of the comparative example
Outside amide and polyurethane, other are consistent with embodiment 3.Specifically, the halogen-free resin composition, including phosphate modified epoxy
20 parts of resin, 15 parts of Study On O-cresol Epoxy Resin, 15 parts of polyurethane, 0 part of kymene, 20 parts of MQ resin, 3,3 '-diamino
10 parts of diphenyl sulphone (DPS), 15 parts of phosphonium flame retardant (OP-930).
2, the number-average molecular weight of the middle polyurethane segment is 2200, and glass transition temperature Tg is -20 DEG C；Polyamide
Amine value 18mgKOH/g, number-average molecular weight 4500, glass transition temperature Tg be 20 DEG C.
3, above-mentioned each component dissolved with dimethylformamide, mix and is separated into halogen-free resin composition, solid content
50wt%.
Two, flexible printed circuit cover film
Included the following steps with cover film prepared by the halogen-free resin composition：Using coating equipment by the resin group
Close object be coated on 35 μm of polyimide insulative film surfaces, 25 μm of rubberization thickness；Semi-solid preparation is toasted in polyimide insulative film table
Face forms solid-state composition nitride layer, is finally bonded release paper and winds to obtain the cover film.
Comparative example 6
One, halogen-free resin composition
1, the amine value of polyurethane and polyamide block copolymer is lower than in the halogen-free resin composition of the comparative example
Outside 12mgKOH/g, other are consistent with embodiment 4.Specifically, the halogen-free resin composition, including the phosphorous asphalt mixtures modified by epoxy resin of DOPO type
18 parts of rouge, 13 parts of four phenol ethane, four glycidol ether, polyurethane and 50 parts of polyamide block copolymer, 20 parts of MQ resin, two
9 parts of diaminodiphenylmethane, 14 parts of phosphonium flame retardant (OP-935).
2, the amine value 11mgKOH/g of the polyurethane and polyamide block copolymer, wherein the number of polyurethane segment is equal
Molecular weight is 2000, and glass transition temperature Tg is -25 DEG C；The number-average molecular weight of polyamide segment is 4200, glass transition
Temperature Tg is 20 DEG C；Polyamide segment accounts for 75% of polyurethane and polyamide segment total mole number in copolymer, polyurethane segment
Account for polyurethane and the 25% of polyamide segment total mole number in copolymer.
3, above-mentioned each component dissolved with butanone, mix and is separated into halogen-free resin composition, solid content 50wt%.
Two, flexible printed circuit cover film
Included the following steps with cover film prepared by the halogen-free resin composition：Using coating equipment by the resin group
Close object be coated on 50 μm of polyimide insulative film surfaces, 35 μm of rubberization thickness；Semi-solid preparation is toasted in polyimide insulative film table
Face forms solid-state composition nitride layer, is finally bonded release paper and winds to obtain the cover film.
Comparative example 7
One, halogen-free resin composition
1, the amine value of polyurethane and polyamide block copolymer is higher than in the halogen-free resin composition of the comparative example
Outside 18mgKOH/g, other are consistent with embodiment 4.Specifically, the halogen-free resin composition, including the phosphorous asphalt mixtures modified by epoxy resin of DOPO type
18 parts of rouge, 13 parts of four phenol ethane, four glycidol ether, polyurethane and 50 parts of polyamide block copolymer, 20 parts of MQ resin, two
9 parts of diaminodiphenylmethane, 14 parts of phosphonium flame retardant (OP-935).
2, the amine value 19mgKOH/g of the polyurethane and polyamide block copolymer, wherein the number of polyurethane segment is equal
Molecular weight is 2000, and glass transition temperature Tg is -25 DEG C；The number-average molecular weight of polyamide segment is 4200, glass transition
Temperature Tg is 20 DEG C；Polyamide segment accounts for 75% of polyurethane and polyamide segment total mole number in copolymer, polyurethane segment
Account for polyurethane and the 25% of polyamide segment total mole number in copolymer.
3, above-mentioned each component dissolved with butanone, mix and is separated into halogen-free resin composition, solid content 50wt%.
Two, flexible printed circuit cover film
Included the following steps with cover film prepared by the halogen-free resin composition：By the halogen-free resin composition
Applied to flexible printed circuit cover film, using coating equipment by the resin composition in 50 μm of polyimide insulative films
Surface, 35 μm of rubberization thickness；Toast semi-solid preparation with polyimide insulative film surface formed solid-state composition nitride layer, be finally bonded from
Type paper winds to obtain the cover film.
Comparative example 8
One, halogen-free resin composition
1, the polyamide of polyurethane and polyamide block copolymer is few (described in the halogen-free resin composition of the comparative example
Polyamide segment molal quantity account for polyurethane and polyamide total mole number in block copolymer less than 60%) outside, other and implementation
Example 4 is consistent.Specifically, the halogen-free resin composition, including 18 parts of DOPO type phosphorous epoxy resin, four phenol ethane four shrink
50 parts of 13 parts of glycerin ether, polyurethane and polyamide block copolymer, 20 parts of MQ resin, 9 parts of diaminodiphenylmethane, phosphor-containing flame-proof
14 parts of agent (OP-935).
2, the amine value 16mgKOH/g of the polyurethane and polyamide block copolymer, wherein the number of polyurethane segment is equal
Molecular weight is 2000, and glass transition temperature Tg is -25 DEG C；The number-average molecular weight of polyamide segment is 4200, glass transition
Temperature Tg is 20 DEG C；Polyamide segment accounts for 50% of polyurethane and polyamide segment total mole number in copolymer, polyurethane segment
Account for polyurethane and the 50% of polyamide segment total mole number in copolymer.
3, above-mentioned each component dissolved with butanone, mix and is separated into halogen-free resin composition, solid content 50wt%.
Two, flexible printed circuit cover film
Included the following steps with cover film prepared by the halogen-free resin composition：By the halogen-free resin composition
Applied to flexible printed circuit cover film, using coating equipment by the resin composition in 50 μm of polyimide insulative films
Surface, 35 μm of rubberization thickness；Toast semi-solid preparation with polyimide insulative film surface formed solid-state composition nitride layer, be finally bonded from
Type paper winds to obtain the cover film.
Comparative example 9
One, halogen-free resin composition
1, the polyurethane of polyurethane and polyamide block copolymer is few (described in the halogen-free resin composition of the comparative example
Polyurethane segment molal quantity account for polyurethane and polyamide total mole number in block copolymer less than 20%) outside, other and implementation
Example 4 is consistent.Specifically, the halogen-free resin composition, including 18 parts of DOPO type phosphorous epoxy resin, four phenol ethane four shrink
50 parts of 13 parts of glycerin ether, polyurethane and polyamide block copolymer, 20 parts of MQ resin, 9 parts of diaminodiphenylmethane, phosphor-containing flame-proof
14 parts of agent (OP-935).
2, the amine value 16mgKOH/g of the polyurethane and polyamide block copolymer, wherein the number of polyurethane segment is equal
Molecular weight is 2000, and glass transition temperature Tg is -25 DEG C；The number-average molecular weight of polyamide segment is 4200, glass transition
Temperature Tg is 20 DEG C；Polyamide segment accounts for 90% of polyurethane and polyamide segment total mole number in copolymer, polyurethane segment
Account for polyurethane and the 10% of polyamide segment total mole number in copolymer.
3, above-mentioned each component dissolved with butanone, mix and is separated into halogen-free resin composition, solid content 50wt%.
Two, flexible printed circuit cover film
Included the following steps with cover film prepared by the halogen-free resin composition：By the halogen-free resin composition
Applied to flexible printed circuit cover film, using coating equipment by the resin composition in 50 μm of polyimide insulative films
Surface, 35 μm of rubberization thickness；Toast semi-solid preparation with polyimide insulative film surface formed solid-state composition nitride layer, be finally bonded from
Type paper winds to obtain the cover film.
The measurement of experimental example correlated performance
1, cover film made from above-described embodiment and comparative example is tested for the property, performance is as shown in table 1, table 2.Its
Middle commercial product is that CTBN modified epoxy prepares cover film.
2, test method is as follows：
(1) peel strength：It is tested according to IPC-TM-650 method, using fast press in 180 DEG C, 100kgf/cm2Condition
It is lower to press cover film and copper foil shiny surface 60 seconds, 180 ° of peel strengths of etching test after solidification.
(2) glue overflow amount：It is tested according to IPC-TM-650 method.
(3) type is covered：Covering filling capacity of the cover film to route in quantitative reaction embodiment and comparative example.By embodiment
Measurement circuit is fitted in gained cover film in comparative example, in 180 DEG C, 100kgf/cm2Under the conditions of press 60 seconds fastly after, observation line
It whether there is starved, bubble between road, fill bad, the not firm or other defect of pressure.
(4) the resistance to soldering dip temperature of the limit：By cover film copper foil smooth surface in 180 DEG C, 100kgf/cm2Under the conditions of press 60 seconds fastly after
Solidify 3 hours in 170 DEG C.Sample after solidification is cut into having a size of 50mm × 50mm sample, then immerses 288 DEG C, 320 respectively
DEG C and 360 DEG C of tin liquors in 60 seconds, seen whether layering foaming phenomena, by maximum temperature be the resistance to soldering dip temperature of the limit.
(5) flammability：After tearing release paper, tested according to UL94 vertical combustion.
(6) resistance to ion transport：Cover film is pressed with the route for having formed special pattern up to test sample.Double 85
Under the conditions of, apply 100V DC voltage in sample electrode, continues 1000 hours.It is obstructed if occurring short circuit in 1000 hours
It crosses；Conversely, then passing through test.
(7) dendrite：Whether observe between the route for the sample of resistance to Ion transfer has " dendritic growth object ".
(8) resistance to ag(e)ing：Cover film and copper foil smooth surface are pressed, after 170 DEG C solidify 3 hours, 177 DEG C are toasted 240 hours,
Then 180 ° of peel strengths are tested according to above-mentioned peel strength test method, and records peel strength conservation rate.
(9) storage characteristics：Cover film is stored 30 days in 25 DEG C, 50%RH environment, if glue overflow amount is less than 0.1mm, no
Pass through；Conversely, then passing through test.
Table 1
Table 2
By table 1, table 2 it is found that the cover film prepared in embodiment using halogen-free resin composition of the invention is with excellent
Heat resistance, ageing-resistant performance, storage characteristics and resistance to Ion transfer performance, and resistance to Ion transfer test after be not in dendritic knot
It is brilliant.The proportion and structure of resin combination in comparative example be not in optimized scope, although also having excellent resistance to ion transport
Can, but comprehensive performance is poor, is covering type, glue overflow amount, peel strength, the resistance to aspect of performance such as dip solderability not as good as embodiment, nothing
Method meets the performance requirement of flexible printed wiring board.Especially comparative example 7, used polyurethane and polyamide-block are copolymerized
Object amine value is excessively high, leads to signified cover film storage characteristics decline.Therefore, resin combination of the invention requires suitable construction
The cover film haveing excellent performance could be obtained with the polyurethane and polyamide block copolymer of proportion, MQ tree collocation other components.
In conclusion halogen-free resin composition of the invention, using polyurethane and polyamide block copolymer as main increasing
Tough dose, MQ resin cooperates phosphorous epoxy resin, polyfunctional epoxy resin, curing agent and phosphonium flame retardant as auxiliary toughener, can
To be cross-linked with each other, reaction forms the polymer network with island structure, not only has excellent flexibility, storage characteristics and heat-resisting
Property, and resistance to Ion transfer performance is excellent, and prepared cover film can be used for the field of high reliability request.
Described is only presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on should all include within protection scope of the present invention.
Claims (10)
1. a kind of halogen-free resin composition, which is characterized in that according to parts by weight, the halogen-free resin composition includes being scattered in
Following component in organic solvent：10-20 parts of phosphorous epoxy resin, 10-15 parts of polyfunctional epoxy resin, polyurethane and polyamide
35-50 parts of block copolymer, 10-20 parts of MQ resin, 5-10 parts of amine curing agent, 5-15 parts of phosphonium flame retardant.
2. halogen-free resin composition as described in claim 1, which is characterized in that the solid content of the halogen-free resin composition is
40-70wt%.
3. halogen-free resin composition as described in claim 1, which is characterized in that the organic solvent is acetone, butanone, ring
One of hexanone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethyl acetate, propylene glycol methyl ether acetate, dimethylformamide are several
Kind mixture.
4. halogen-free resin composition as described in claim 1, which is characterized in that the phosphorous epoxy resin is that DOPO type is phosphorous
One or more of epoxy resin, DOPO-HQ type phosphorous epoxy resin, phosphate modified epoxy resin mixture.
5. halogen-free resin composition as described in claim 1, which is characterized in that the epoxide equivalent of the polyfunctional epoxy resin
For 160-380g/eq, including phenol type novolac epoxy resin, bisphenol A-type novolac epoxy resin, Study On O-cresol Epoxy Resin,
One of four phenol ethane, four glycidol ether or a variety of mixtures.
6. halogen-free resin composition as described in claim 1, which is characterized in that the polyurethane and polyamide block copolymer
Amine value be 12~18mgKOH/g；It is total to account for block for polyurethane segment molal quantity in the polyurethane and polyamide block copolymer
20% is no less than in polyurethane segment and polyamide segment total mole number in polymers；Polyamide segment molal quantity accounts for block copolymer
No less than 60% in middle polyurethane segment and polyamide segment total mole number；The polyurethane and polyamide block copolymer by
Diisocyanate, polyether Glycols, binary acid and binary amine copolymer are made, and wherein polyurethane segment is soft segment, the polyurethane
The number-average molecular weight 1500-2200 of segment, glass transition temperature Tg are -40~-20 DEG C；Polyamide segment is hard section, described
The number-average molecular weight of polyamide-block is 3000-4500, and glass transition temperature is 10~20 DEG C.
7. halogen-free resin composition as described in claim 1, which is characterized in that the MQ resin is by M group organosilicon list
Body is formed with Q group organic silicon monomer through hydrolytic condensation, and M/Q value is 1.0~1.5；The organic silicon monomer of the M group is single
Function organosiloxane closes chain link R3SiO0.5；The organic silicon monomer of the M group has the following structure：
Wherein n, m take the integer between 8 to 20；
The Q group is tetra functional silicon monomer, including any one in methyl orthosilicate or ethyl orthosilicate.
8. halogen-free resin composition as described in claim 1, which is characterized in that the amine curing agent is 4,4 '-diamino
One of diphenyl sulphone (DPS), 3,3'- diaminodiphenylsulfone, dicyandiamide, m-phenylene diamine (MPD), diethylenetriamine and diaminodiphenylmethane or
It is a variety of.
9. a kind of flexible printed-circuit board cover film prepared using halogen-free resin composition according to claims 1-8,
It is characterised in that it includes Kapton, the halogen-free resin composition layer coated in Kapton surface and pressure
Together in the release paper on the halogen-free resin composition layer.
10. flexible printed-circuit board cover film as claimed in claim 9, which is characterized in that preparation method is：By right
It is required that halogen-free resin composition described in any one of 1-8 is coated on polyimide insulative film, and it is dry, organic solvent is removed,
The halogen-free resin composition coating that semi-solid preparation is formed on polyimide insulative film, it is then pressed, obtain with release paper
To the flexible printed-circuit board cover film.
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| CN201810725392.6A CN108864924B (en) | 2018-07-04 | 2018-07-04 | Halogen-free resin composition and cover film for flexible printed circuit board prepared from same |
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| CN201810725392.6A CN108864924B (en) | 2018-07-04 | 2018-07-04 | Halogen-free resin composition and cover film for flexible printed circuit board prepared from same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705387A (en) * | 2018-12-27 | 2019-05-03 | 广东生益科技股份有限公司 | A kind of halogen-free resin composition, flexible printed-circuit board cover film and flexible printed-circuit board comprising it |
| CN110982385A (en) * | 2019-12-25 | 2020-04-10 | 上海中如智慧能源集团有限公司 | Special temperature-resistant coating for corrosion prevention in heat storage tank |
| CN114058249A (en) * | 2022-01-06 | 2022-02-18 | 天津凯华绝缘材料股份有限公司 | Polyurethane toughening modified epoxy powder encapsulating material, preparation method and application |
| CN114085492A (en) * | 2021-12-07 | 2022-02-25 | 苏州生益科技有限公司 | Resin composition, prepreg and laminated board thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101457012A (en) * | 2008-12-31 | 2009-06-17 | 广东生益科技股份有限公司 | Resin composition and copper clad laminate prepared by metal foil coated with resin composition |
| US20100155123A1 (en) * | 2008-12-22 | 2010-06-24 | Iteq Corporation | Halogen-free prepreg and resin for preparing the same |
| 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 |
| CN106084669A (en) * | 2016-06-21 | 2016-11-09 | 四川大学 | A kind of organic siliconresin modified epoxy resin composition |
| CN106700498A (en) * | 2016-12-29 | 2017-05-24 | 广东生益科技股份有限公司 | Thermoplastic resin composition and adhesive prepared from same, insulation adhesive film used for laminated bus bar and preparation method of insulation adhesive film |
-
2018
- 2018-07-04 CN CN201810725392.6A patent/CN108864924B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100155123A1 (en) * | 2008-12-22 | 2010-06-24 | Iteq Corporation | Halogen-free prepreg and resin for preparing the same |
| CN101457012A (en) * | 2008-12-31 | 2009-06-17 | 广东生益科技股份有限公司 | Resin composition and copper clad laminate prepared by metal foil coated with resin composition |
| 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 |
| CN106084669A (en) * | 2016-06-21 | 2016-11-09 | 四川大学 | A kind of organic siliconresin modified epoxy resin composition |
| CN106700498A (en) * | 2016-12-29 | 2017-05-24 | 广东生益科技股份有限公司 | Thermoplastic resin composition and adhesive prepared from same, insulation adhesive film used for laminated bus bar and preparation method of insulation adhesive film |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705387A (en) * | 2018-12-27 | 2019-05-03 | 广东生益科技股份有限公司 | A kind of halogen-free resin composition, flexible printed-circuit board cover film and flexible printed-circuit board comprising it |
| CN109705387B (en) * | 2018-12-27 | 2021-07-06 | 广东生益科技股份有限公司 | Halogen-free resin composition, cover film for flexible printed circuit board containing same and flexible printed circuit board |
| CN110982385A (en) * | 2019-12-25 | 2020-04-10 | 上海中如智慧能源集团有限公司 | Special temperature-resistant coating for corrosion prevention in heat storage tank |
| CN110982385B (en) * | 2019-12-25 | 2021-11-16 | 上海中如智慧能源集团有限公司 | Special temperature-resistant coating for corrosion prevention in heat storage tank |
| CN114085492A (en) * | 2021-12-07 | 2022-02-25 | 苏州生益科技有限公司 | Resin composition, prepreg and laminated board thereof |
| CN114085492B (en) * | 2021-12-07 | 2023-10-27 | 苏州生益科技有限公司 | Resin composition, prepreg and laminated board thereof |
| CN114058249A (en) * | 2022-01-06 | 2022-02-18 | 天津凯华绝缘材料股份有限公司 | Polyurethane toughening modified epoxy powder encapsulating material, preparation method and application |
| CN114058249B (en) * | 2022-01-06 | 2022-04-26 | 天津凯华绝缘材料股份有限公司 | Polyurethane toughening modified epoxy powder encapsulating material, preparation method and application |
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| CN108864924B (en) | 2020-10-27 |
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Denomination of invention: The invention relates to a halogen-free resin composition and a covering film for flexible printed circuit board prepared by the composition Effective date of registration: 20211216 Granted publication date: 20201027 Pledgee: Bank of China Limited Huangshi Branch Pledgor: HUBEI HENGCHI ELECTRONIC TECHNOLOGY Co.,Ltd. Registration number: Y2021420000146 |
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Denomination of invention: A halogen-free resin composition and a covering film for flexible printed circuit boards prepared from it Granted publication date: 20201027 Pledgee: Bank of China Limited Huangshi Branch Pledgor: HUBEI HENGCHI ELECTRONIC TECHNOLOGY Co.,Ltd. Registration number: Y2024980007119 |
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