CN108864924B - Halogen-free resin composition and cover film for flexible printed circuit board prepared from same - Google Patents
Halogen-free resin composition and cover film for flexible printed circuit board prepared from same Download PDFInfo
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- CN108864924B CN108864924B CN201810725392.6A CN201810725392A CN108864924B CN 108864924 B CN108864924 B CN 108864924B CN 201810725392 A CN201810725392 A CN 201810725392A CN 108864924 B CN108864924 B CN 108864924B
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- Prior art keywords
- halogen
- resin composition
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- polyurethane
- free resin
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- 239000011342 resin composition Substances 0.000 title claims abstract description 115
- 239000013039 cover film Substances 0.000 title description 29
- 229920002635 polyurethane Polymers 0.000 claims abstract description 95
- 239000004814 polyurethane Substances 0.000 claims abstract description 95
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 39
- 239000011574 phosphorus Substances 0.000 claims abstract description 39
- 239000003822 epoxy resin Substances 0.000 claims abstract description 37
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 37
- 229920006147 copolyamide elastomer Polymers 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 150000001412 amines Chemical class 0.000 claims abstract description 24
- 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 20
- 239000003063 flame retardant Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000010408 film Substances 0.000 claims description 76
- 239000004952 Polyamide Substances 0.000 claims description 61
- 229920002647 polyamide Polymers 0.000 claims description 61
- 229920001721 polyimide Polymers 0.000 claims description 39
- 239000004642 Polyimide Substances 0.000 claims description 30
- 230000009477 glass transition Effects 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 26
- 229920001577 copolymer Polymers 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 239000004843 novolac epoxy resin Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 13
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 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 8
- 229920001400 block copolymer Polymers 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 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
- 239000004593 Epoxy Substances 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012787 coverlay film Substances 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- 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
- 150000004985 diamines Chemical class 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- -1 phosphate ester 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
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 1
- 238000010030 laminating Methods 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 12
- 230000005012 migration Effects 0.000 abstract description 10
- 238000013508 migration Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 23
- 239000010410 layer Substances 0.000 description 18
- 238000005096 rolling process Methods 0.000 description 14
- 239000008247 solid mixture Substances 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 11
- 238000003860 storage Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 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 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000012745 toughening agent Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000005406 washing 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 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)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
The invention discloses a halogen-free resin composition which comprises the following components in parts by weight dispersed in an organic solvent: 10-20 parts of phosphorus-containing epoxy resin, 10-15 parts of multifunctional epoxy resin, 35-50 parts of polyurethane and polyamide block copolymer, 10-20 parts of MQ resin, 5-10 parts of amine curing agent and 5-15 parts of phosphorus-containing flame retardant; the invention also discloses a covering film prepared by using the halogen-free resin composition; the covering film has excellent flexibility, low ion content, good insulativity, excellent peel strength, heat resistance, dimensional stability, chemical resistance, storability and processability, and the flame retardance can reach UL94VTM-0 level, and dendritic crystals can not appear in an ion migration resistance test.
Description
Technical Field
The invention relates to the field of polymer composite material manufacturing, in particular to a halogen-free resin composition and a cover film for a flexible printed circuit prepared from the same.
Background
The cover film for flexible printed circuit is a film-like insulating material prepared by coating one side of polyimide film or polyester film with glue, and is the most commonly used protective layer for flexible printed circuit board. The flexible printed circuit board has the advantages of being similar to a solder mask of a rigid printed circuit board, having stronger functions, not only having a solder mask function, but also protecting a circuit from being damaged by dust, moisture, chemical pollution and the like, having certain flexibility and strengthening function, reducing the influence of stress of a conductor in the bending process, and improving the flexibility resistance of the flexible printed circuit board.
In the current industry, the cover film with the largest use amount is a polyimide film cover film, which is formed by coating a layer of adhesive on one surface of a polyimide film, and the commonly used adhesive is prepared by toughening and modifying epoxy by adopting carboxyl-terminated butadiene-acrylonitrile rubber and assisting with a flame retardant, a filler and other auxiliary agents, such as the methods described in U.S. patent No. 20030091842, Chinese patents CN102093667A and CN 101486883B. However, the cover film prepared in this way is generally poor in flexibility, poor in flame retardancy, and has problems that the rubber component is apt to be aged, poor in ion migration resistance, and the like.
With the development of flexible printed circuit board technology, the market has higher and higher requirements on the flexibility, heat resistance and reliability of the cover film. The cover film prepared by toughening and modifying epoxy by carboxyl-terminated nitrile rubber obviously cannot meet increasingly strict technical requirements. Therefore, there is a need in the industry for a new resin composition to solve the problems of the prior art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a halogen-free resin composition and a cover film for a flexible printed circuit board prepared by using the same, wherein the composition has excellent flexibility, flame retardance and heat resistance; the covering film has excellent flexibility, low ion content, good insulativity, excellent peel strength, heat resistance, dimensional stability, chemical resistance, storability and processability, and the flame retardance can reach UL94VTM-0 level, and dendritic crystals can not appear in an ion migration resistance test.
The invention is realized by the following steps:
one of the objectives of the present invention is to provide a halogen-free resin composition, which comprises the following components dispersed in an organic solvent in parts by weight: 10-20 parts of phosphorus-containing epoxy resin, 10-15 parts of multifunctional epoxy resin, 35-50 parts of polyurethane and polyamide block copolymer, 10-20 parts of MQ resin, 5-10 parts of amine curing agent and 5-15 parts of phosphorus-containing flame retardant.
Preferably, the halogen-free resin composition has a solid content of 40 wt% to 70 wt%.
Preferably, the phosphorus-containing epoxy resin is one or a mixture of more of DOPO type phosphorus-containing epoxy resin, DOPO-HQ type phosphorus-containing epoxy resin and phosphate modified epoxy resin.
Preferably, the epoxy equivalent of the multifunctional epoxy resin is between 160-380g/eq, and one or more of phenol novolac epoxy resin, bisphenol A novolac epoxy resin, o-cresol novolac epoxy resin and tetraphenol ethane tetraglycidyl ether are preferably selected as the mixture. The multifunctional epoxy resin can not only increase the cohesive strength and the peeling strength of the composition, but also improve the heat resistance and the chemical resistance of the composition.
Preferably, the polyurethane and polyamide block copolymer is prepared by copolymerizing diisocyanate, polyether diol, dibasic acid and diamine, wherein the polyurethane chain segment is a soft segment, the number average molecular weight of the polyurethane chain segment is 1500-2200, and the glass transition temperature Tg is-40 to-20 ℃; the polyamide chain segment is a hard segment, the number average molecular weight of the polyamide block is 3000-4500, and the glass transition temperature is 10-20 ℃.
Preferably, the amine value of the polyurethane and polyamide block copolymer is 12-18mgKOH/g, and if the amine value is too low, the heat resistance is insufficient; if the amine value is too high, the halogen-free resin composition tends to have poor storage stability and poor processability.
The more the content of the polyamide segment is, the better the heat resistance is, but the flexibility becomes worse, the toughening and flexibility increasing effect is insufficient, the water absorption rate becomes higher, and the electrical property becomes worse; the higher the content of the polyurethane segment, the better the toughening and flexibilizing effect, but the insufficient heat resistance. Therefore, it is preferable that the number of moles of the polyamide segment is not less than 60% of the total number of moles of the polyurethane and the polyamide in the block copolymer; the mole number of the polyurethane chain segment accounts for not less than 20 percent of the total mole number of the polyurethane and the polyamide in the block copolymer.
Preferably, the MQ resin has a core-shell structure, is preferably prepared by hydrolyzing and condensing an M group organic silicon monomer and a Q group organic silicon monomer, and has an M/Q value of 1.0-1.5. If the M/Q value is too low, the polarity becomes too high, and the compatibility with other components in the resin composition becomes poor; if the M/Q value is too high, the washing is not easy, too many inorganic ions remain, and the ion migration resistance is influenced.
Preferably, the organosilicon monomer of M group is a monofunctional organosiloxane closed chain R3SiO0.5(ii) a The amino group in the R group can react with the epoxy group to form chemical bond combination between the MQ resin and the epoxy resin, thereby improving the compatibility of the MQ resin and the epoxy component.
Specifically, the M group organosilicon monomer has the following structure:
The Q group organosilicon monomer is a tetrafunctional silicon monomer and can be selected from one of methyl orthosilicate and ethyl orthosilicate.
The MQ resin is prepared by the following steps:
(1) adding deionized water, absolute ethyl alcohol, toluene, hydrochloric acid and an M-group organic silicon monomer into a reaction kettle with a stirring paddle, a thermometer and a condenser, heating to 60-80 ℃, and stirring for reaction for 0.5-2 h;
(2) dripping a tetrafunctional silicon monomer of a Q group, and continuously stirring and reacting for 0.5-2h at 75-80 ℃;
(3) extracting, washing and rotary steaming to obtain the MQ resin.
Preferably, the amine curing agent is selected from one or more of 4,4 '-diaminodiphenyl sulfone, 3' -diaminodiphenyl sulfone, dicyandiamide, m-phenylenediamine, diethylenetriamine and diaminodiphenylmethane.
Preferably, the phosphorus-containing flame retardant is preferably SPB-100 manufactured by Otsuka chemical Co., Ltd., OP-935 and OP-930 manufactured by Clariant Germany, or the like.
Preferably, the organic solvent is one or a mixture of acetone, butanone, cyclohexanone, propylene glycol methyl ether, ethylene glycol methyl ether, ethyl acetate, propylene glycol methyl ether acetate and dimethylformamide.
The preparation method of the halogen-free resin composition comprises the following steps: the phosphorus-containing epoxy resin, the multifunctional epoxy resin, the polyurethane and polyamide block copolymer, the MQ resin and the amine curing agent which are proportioned in the above-mentioned proportion are dissolved by using a solvent, then the phosphorus-containing flame retardant is added, and the solid and liquid components in the composition of the present invention are mixed and dispersed together by using the equipment of ball mill, three-roll machine, planetary stirrer, etc. so as to obtain the liquid dispersoid, namely the halogen-free resin composition.
The second purpose of the invention is to provide a covering film for a flexible printed circuit board prepared by using the halogen-free resin composition, which comprises a polyimide film, a composition layer formed on the surface of the polyimide film by using the composition, and release paper on the composition layer.
Preferably, the thickness of the polyimide film is 5-50 μm;
preferably, the thickness of the layer of the halogen-free resin composition is 5-35 μm.
Preferably, the thickness of the release paper is 50-150 μm;
the preparation method of the cover film for the flexible printed circuit comprises the following steps: coating the halogen-free resin composition on one side of a polyimide film, then baking for 2-4 minutes at 70-160 ℃ through an online drying oven to remove the organic solvent and form a semi-cured composition layer, then compounding with release paper at 50-70 ℃, and rolling to obtain the cover film for the flexible printed circuit.
Compared with the prior art, the invention has the following advantages and effects:
1. the halogen-free resin composition provided by the invention has the advantages of low glass transition temperature and good flexibility of polyurethane and polyamide segmented copolymer. MQ resin is organic/inorganic silicon resin with a core-shell structure, and the interior of the MQ resin is cage-shaped SiO2A core, wherein the outside is an amino-containing alkyl long chain and an amino-containing aromatic chain segment, and the molar ratio of the amino-containing alkyl long chain to the amino-containing aromatic chain segment is 1: 1, has good flexibility, heat resistance and proper reactivity, and can effectively control the gummosis behavior of the resin composition in a B-stage state. The invention takes polyurethane and polyamide block copolymer as a main toughening agent, and MQ resin as an auxiliary toughening agent to jointly toughen, soften and modify the epoxy resin; both of the two contain amino groups, can generate crosslinking curing reaction with the epoxy resin, effectively improve the compatibility of the three, overcome the problems of low surface energy of the silicon resin and poor compatibility with other organic resins, and effectively improve the heat resistance of the resin composition. Proper phase separation can be formed in the curing system, and sea-island structure is formed, when external force is acted, the toughening particles can induce and reactThe generation of silver lines is stopped, and energy is absorbed, so that excellent toughening effect is obtained.
2. The covering film prepared from the halogen-free resin composition has excellent flexibility, low ion content, good insulativity, excellent peel strength, heat resistance, aging resistance, dimensional stability, chemical resistance, storage property and processability, and the flame retardance can reach UL94VTM-0 level.
Detailed Description
Example 1
Halogen-free resin composition
1. The halogen-free resin composition comprises 10 parts of DOPO type phosphorus-containing epoxy resin, 10 parts of phenol type novolac epoxy resin, 35 parts of polyurethane and polyamide block copolymer, 10 parts of MQ resin, 2 parts of dicyandiamide, 3 parts of m-phenylenediamine and 5 parts of phosphorus-containing flame retardant (SPB-100).
2. The amine value of the polyurethane and polyamide block copolymer is 12mgKOH/g, wherein the number average molecular weight of a polyurethane chain segment is 1500, and the glass transition temperature Tg is-40 ℃; the number average molecular weight of the polyamide chain segment is 3000, and the glass transition temperature Tg is 10 ℃; the polyamide chain segment accounts for 60 percent of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer, and the polyurethane chain segment accounts for 40 percent of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer.
3. The components are dissolved, mixed and dispersed by acetone to obtain the halogen-free resin composition with the solid content of 40 wt%.
Covering film for flexible printed circuit
The covering film prepared by the halogen-free resin composition comprises the following steps: the halogen-free resin composition is applied to a covering film for a flexible printed circuit. Coating the resin composition on the surface of a polyimide insulating film with the thickness of 5 mu m by using coating equipment; and baking and semi-curing to form a solid composition layer on the surface of the polyimide insulating film, and finally attaching release paper and rolling to obtain the cover film.
Example 2
Halogen-free resin composition
1. The halogen-free resin composition comprises 15 parts of DOPO-HQ type phosphorus-containing epoxy resin, 10 parts of bisphenol A type novolac epoxy resin, 40 parts of polyurethane and polyamide block copolymer, 15 parts of MQ resin, 5 parts of 4, 4' -diamino diphenyl sulfone, 2 parts of diethylenetriamine and 8 parts of phosphorus-containing flame retardant (OP-935).
2. The amine value of the polyurethane and polyamide block copolymer is 15mgKOH/g, wherein the number average molecular weight of a polyurethane chain segment is 1800, and the glass transition temperature Tg is-35 ℃; the number average molecular weight of the polyamide chain segment is 3500, and the glass transition temperature Tg is 15 ℃; the polyamide chain segment accounts for 70% of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer, and the polyurethane chain segment accounts for 30% of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer.
3. The components are dissolved, mixed and dispersed by cyclohexanone to obtain the halogen-free resin composition with the solid content of 40 wt%.
Covering film for flexible printed circuit
The covering film prepared by the halogen-free resin composition comprises the following steps: the halogen-free resin composition is applied to a covering film for a flexible printed circuit, and is coated on the surface of a polyimide insulating film with the thickness of 15 microns by using coating equipment; and baking and semi-curing to form a solid composition layer on the surface of the polyimide insulating film, and finally attaching release paper and rolling to obtain the cover film.
Example 3
Halogen-free resin composition
1. The halogen-free resin composition comprises 20 parts of phosphate modified epoxy resin, 15 parts of o-cresol novolac epoxy resin, 45 parts of polyurethane and polyamide block copolymer, 20 parts of MQ resin, 10 parts of 3,3' -diaminodiphenyl sulfone and 15 parts of phosphorus-containing flame retardant (OP-930).
2. The amine value of the polyurethane and polyamide block copolymer is 18mgKOH/g, wherein the number average molecular weight of a polyurethane chain segment is 2200, and the glass transition temperature Tg is-20 ℃; the number average molecular weight of the polyamide chain segment is 4500, and the glass transition temperature Tg is 20 ℃; the polyamide chain segment accounts for 80% of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer, and the polyurethane chain segment accounts for 20% of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer.
3. The components are dissolved, mixed and dispersed by dimethylformamide to obtain the halogen-free resin composition, and the solid content is 50 wt%.
Covering film for flexible printed circuit
The covering film prepared by the halogen-free resin composition comprises the following steps: the halogen-free resin composition is applied to a covering film for a flexible printed circuit, and is coated on the surface of a polyimide insulating film with the thickness of 25 mu m by using coating equipment; and baking and semi-curing to form a solid composition layer on the surface of the polyimide insulating film, and finally attaching release paper and rolling to obtain the cover film.
Example 4
Halogen-free resin composition
1. The halogen-free resin composition comprises 18 parts of DOPO type phosphorus-containing epoxy resin, 13 parts of tetraphenol ethane tetraglycidyl ether, 50 parts of polyurethane and polyamide block copolymer, 20 parts of MQ resin, 9 parts of diaminodiphenylmethane and 14 parts of phosphorus-containing flame retardant (OP-935).
2. The amine value of the polyurethane and polyamide block copolymer is 16mgKOH/g, wherein the number average molecular weight of a polyurethane chain segment is 2000, and the glass transition temperature Tg is-25 ℃; the number average molecular weight of the polyamide segment is 4200, and the glass transition temperature Tg is 20 ℃; the polyamide chain segment accounts for 75 percent of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer, and the polyurethane chain segment accounts for 25 percent of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer.
3. The components are dissolved, mixed and dispersed by butanone to obtain the halogen-free resin composition with the solid content of 50 wt%.
Covering film for flexible printed circuit
The covering film prepared by the halogen-free resin composition comprises the following steps: the halogen-free resin composition is applied to a covering film for a flexible printed circuit, and is coated on the surface of a polyimide insulating film with the thickness of 35 mu m by coating equipment; and baking and semi-curing to form a solid composition layer on the surface of the polyimide insulating film, and finally attaching release paper and rolling to obtain the cover film.
Comparative example 1
Halogen-free resin composition
1. The halogen-free resin composition of this comparative example was identical to example 1 except that no MQ resin was included. Specifically, the halogen-free resin composition comprises 10 parts of DOPO type phosphorus-containing epoxy resin, 10 parts of phenol type novolac epoxy resin, 35 parts of polyurethane and polyamide block copolymer, 2 parts of dicyandiamide, 3 parts of m-phenylenediamine and 5 parts of phosphorus-containing flame retardant (SPB-100).
2. The amine value of the polyurethane and polyamide block copolymer is 12mgKOH/g, wherein the number average molecular weight of a polyurethane chain segment is 1500, and the glass transition temperature Tg is-40 ℃; the number average molecular weight of the polyamide chain segment is 3000, and the glass transition temperature Tg is 10 ℃; the polyamide chain segment accounts for 60 percent of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer, and the polyurethane chain segment accounts for 40 percent of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer.
3. The components are dissolved, mixed and dispersed by acetone to obtain the halogen-free resin composition with the solid content of 40 wt%.
Covering film for flexible printed circuit
The covering film prepared by the halogen-free resin composition comprises the following steps: the halogen-free resin composition is applied to a covering film for a flexible printed circuit, and is coated on the surface of a polyimide insulating film with the thickness of 5 mu m by coating equipment; and baking and semi-curing to form a solid composition layer on the surface of the polyimide insulating film, and finally attaching release paper and rolling to obtain the cover film.
Comparative example 2
Halogen-free resin composition
1. The halogen-free resin composition of this comparative example was identical to example 2 except that it did not contain the polyurethane and polyamide block copolymers. Specifically, the halogen-free resin composition comprises 15 parts of DOPO-HQ type phosphorus-containing epoxy resin, 10 parts of bisphenol A type novolac epoxy resin, 15 parts of MQ resin, 5 parts of 4, 4' -diamino diphenyl sulfone, 2 parts of diethylenetriamine and 8 parts of phosphorus-containing flame retardant (OP-935).
2. The components are dissolved, mixed and dispersed by cyclohexanone to obtain the halogen-free resin composition with the solid content of 40 wt%.
Covering film for flexible printed circuit
The covering film prepared by the halogen-free resin composition comprises the following steps: the halogen-free resin composition is applied to a covering film for a flexible printed circuit. Coating the resin composition on the surface of a polyimide insulating film with the thickness of 15 mu m by using a coating device; and baking and semi-curing to form a solid composition layer on the surface of the polyimide insulating film, and finally attaching release paper and rolling to obtain the cover film.
Comparative example 3
Halogen-free resin composition
1. The halogen-free resin composition of this comparative example was identical to example 3 except that the polyurethane-polyamide block copolymer was replaced with polyurethane. Specifically, the halogen-free resin composition comprises 20 parts of phosphate modified epoxy resin, 15 parts of o-cresol novolac epoxy resin, 45 parts of polyurethane, 20 parts of MQ resin, 10 parts of 3,3' -diaminodiphenyl sulfone and 15 parts of phosphorus-containing flame retardant (OP-930).
2. The number average molecular weight of the polyurethane is 2200, and the glass transition temperature Tg is-20 ℃.
3. The components are dissolved, mixed and dispersed by dimethylformamide to obtain the halogen-free resin composition, and the solid content is 50 wt%.
Covering film for flexible printed circuit
The covering film prepared by the halogen-free resin composition comprises the following steps:
the halogen-free resin composition is applied to a covering film for a flexible printed circuit, and is coated on the surface of a polyimide insulating film with the thickness of 25 mu m by using coating equipment; and baking and semi-curing to form a solid composition layer on the surface of the polyimide insulating film, and finally attaching release paper and rolling to obtain the cover film.
Comparative example 4
Halogen-free resin composition
1. The halogen-free resin composition of this comparative example was identical to example 3 except that the block copolymer of polyurethane and polyamide was replaced with polyamide. Specifically, the halogen-free resin composition comprises 20 parts of phosphate modified epoxy resin, 15 parts of o-cresol novolac epoxy resin, 45 parts of polyamide, 20 parts of MQ resin, 10 parts of 3,3' -diaminodiphenyl sulfone and 15 parts of phosphorus-containing flame retardant (OP-930).
2. The polyamide has an amine value of 18mgKOH/g, a number average molecular weight of 4500 and a glass transition temperature Tg of 20 ℃.
3. The components are dissolved, mixed and dispersed by dimethylformamide to obtain the halogen-free resin composition, and the solid content is 50 wt%.
Covering film for flexible printed circuit
The covering film prepared by the halogen-free resin composition comprises the following steps: coating the resin composition on the surface of a polyimide insulating film with the thickness of 25 mu m by using a coating device, wherein the thickness of the polyimide insulating film is 35 mu m; and baking and semi-curing to form a solid composition layer on the surface of the polyimide insulating film, and finally attaching release paper and rolling to obtain the cover film.
Comparative example 5
Halogen-free resin composition
1. The halogen-free resin composition of this comparative example was identical to example 3 except that the block copolymers of polyurethane and polyamide were replaced with non-blocked polyamide and polyurethane. Specifically, the halogen-free resin composition comprises 20 parts of phosphate modified epoxy resin, 15 parts of o-cresol novolac epoxy resin, 15 parts of polyurethane, 30 parts of polyamide, 20 parts of MQ resin, 10 parts of 3,3' -diaminodiphenyl sulfone and 15 parts of phosphorus-containing flame retardant (OP-930).
2. The number average molecular weight of the middle polyurethane chain segment is 2200, and the glass transition temperature Tg is-20 ℃; the polyamide had an amine value of 18mgKOH/g, a number average molecular weight of 4500 and a glass transition temperature Tg of 20 ℃.
3. The components are dissolved, mixed and dispersed by dimethylformamide to obtain the halogen-free resin composition, and the solid content is 50 wt%.
Covering film for flexible printed circuit
The covering film prepared by the halogen-free resin composition comprises the following steps: coating the resin composition on the surface of a polyimide insulating film with the thickness of 25 mu m by using a coating device, wherein the thickness of the polyimide insulating film is 35 mu m; and baking and semi-curing to form a solid composition layer on the surface of the polyimide insulating film, and finally attaching release paper and rolling to obtain the cover film.
Comparative example 6
Halogen-free resin composition
1. The halogen-free resin composition of this comparative example was identical to example 4 except that the amine value of the polyurethane and polyamide block copolymer was less than 12 mgKOH/g. Specifically, the halogen-free resin composition comprises 18 parts of DOPO type phosphorus-containing epoxy resin, 13 parts of tetraphenol ethane tetraglycidyl ether, 50 parts of polyurethane and polyamide block copolymer, 20 parts of MQ resin, 9 parts of diaminodiphenylmethane and 14 parts of phosphorus-containing flame retardant (OP-935).
2. The amine value of the polyurethane and polyamide block copolymer is 11mgKOH/g, wherein the number average molecular weight of a polyurethane chain segment is 2000, and the glass transition temperature Tg is-25 ℃; the number average molecular weight of the polyamide segment is 4200, and the glass transition temperature Tg is 20 ℃; the polyamide chain segment accounts for 75 percent of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer, and the polyurethane chain segment accounts for 25 percent of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer.
3. The components are dissolved, mixed and dispersed by butanone to obtain the halogen-free resin composition with the solid content of 50 wt%.
Covering film for flexible printed circuit
The covering film prepared by the halogen-free resin composition comprises the following steps: coating the resin composition on the surface of a polyimide insulating film with the thickness of 35 mu m by using a coating device; and baking and semi-curing to form a solid composition layer on the surface of the polyimide insulating film, and finally attaching release paper and rolling to obtain the cover film.
Comparative example 7
Halogen-free resin composition
1. The amine value of the polyurethane and polyamide block copolymer in the halogen-free resin composition of this comparative example was higher than 18mgKOH/g, and the others were the same as in example 4. Specifically, the halogen-free resin composition comprises 18 parts of DOPO type phosphorus-containing epoxy resin, 13 parts of tetraphenol ethane tetraglycidyl ether, 50 parts of polyurethane and polyamide block copolymer, 20 parts of MQ resin, 9 parts of diaminodiphenylmethane and 14 parts of phosphorus-containing flame retardant (OP-935).
2. The amine value of the polyurethane and polyamide block copolymer is 19mgKOH/g, wherein the number average molecular weight of a polyurethane chain segment is 2000, and the glass transition temperature Tg is-25 ℃; the number average molecular weight of the polyamide segment is 4200, and the glass transition temperature Tg is 20 ℃; the polyamide chain segment accounts for 75 percent of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer, and the polyurethane chain segment accounts for 25 percent of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer.
3. The components are dissolved, mixed and dispersed by butanone to obtain the halogen-free resin composition with the solid content of 50 wt%.
Covering film for flexible printed circuit
The covering film prepared by the halogen-free resin composition comprises the following steps: the halogen-free resin composition is applied to a covering film for a flexible printed circuit, and is coated on the surface of a polyimide insulating film with the thickness of 35 mu m by coating equipment; and baking and semi-curing to form a solid composition layer on the surface of the polyimide insulating film, and finally attaching release paper and rolling to obtain the cover film.
Comparative example 8
Halogen-free resin composition
1. The halogen-free resin composition of this comparative example was identical to example 4 except that the polyurethane and polyamide block copolymer had a low amount of polyamide (the number of moles of the polyamide segments was less than 60% of the total number of moles of polyurethane and polyamide in the block copolymer). Specifically, the halogen-free resin composition comprises 18 parts of DOPO type phosphorus-containing epoxy resin, 13 parts of tetraphenol ethane tetraglycidyl ether, 50 parts of polyurethane and polyamide block copolymer, 20 parts of MQ resin, 9 parts of diaminodiphenylmethane and 14 parts of phosphorus-containing flame retardant (OP-935).
2. The amine value of the polyurethane and polyamide block copolymer is 16mgKOH/g, wherein the number average molecular weight of a polyurethane chain segment is 2000, and the glass transition temperature Tg is-25 ℃; the number average molecular weight of the polyamide segment is 4200, and the glass transition temperature Tg is 20 ℃; the polyamide chain segment accounts for 50% of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer, and the polyurethane chain segment accounts for 50% of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer.
3. The components are dissolved, mixed and dispersed by butanone to obtain the halogen-free resin composition with the solid content of 50 wt%.
Covering film for flexible printed circuit
The covering film prepared by the halogen-free resin composition comprises the following steps: the halogen-free resin composition is applied to a covering film for a flexible printed circuit, and is coated on the surface of a polyimide insulating film with the thickness of 35 mu m by coating equipment; and baking and semi-curing to form a solid composition layer on the surface of the polyimide insulating film, and finally attaching release paper and rolling to obtain the cover film.
Comparative example 9
Halogen-free resin composition
1. The halogen-free resin composition of this comparative example was identical to example 4 except that the amount of polyurethane of the polyurethane-polyamide block copolymer was small (the number of moles of the polyurethane segment was less than 20% of the total number of moles of the polyurethane and the polyamide in the block copolymer). Specifically, the halogen-free resin composition comprises 18 parts of DOPO type phosphorus-containing epoxy resin, 13 parts of tetraphenol ethane tetraglycidyl ether, 50 parts of polyurethane and polyamide block copolymer, 20 parts of MQ resin, 9 parts of diaminodiphenylmethane and 14 parts of phosphorus-containing flame retardant (OP-935).
2. The amine value of the polyurethane and polyamide block copolymer is 16mgKOH/g, wherein the number average molecular weight of a polyurethane chain segment is 2000, and the glass transition temperature Tg is-25 ℃; the number average molecular weight of the polyamide segment is 4200, and the glass transition temperature Tg is 20 ℃; the polyamide chain segment accounts for 90% of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer, and the polyurethane chain segment accounts for 10% of the total mole number of the polyurethane chain segments and the polyamide chain segments in the copolymer.
3. The components are dissolved, mixed and dispersed by butanone to obtain the halogen-free resin composition with the solid content of 50 wt%.
Covering film for flexible printed circuit
The covering film prepared by the halogen-free resin composition comprises the following steps: the halogen-free resin composition is applied to a covering film for a flexible printed circuit, and is coated on the surface of a polyimide insulating film with the thickness of 35 mu m by coating equipment; and baking and semi-curing to form a solid composition layer on the surface of the polyimide insulating film, and finally attaching release paper and rolling to obtain the cover film.
Determination of the Properties relevant to the examples
1. The coverlay films obtained in the above examples and comparative examples were subjected to performance tests, and the performances thereof are shown in tables 1 and 2. Wherein the commercial product is CTBN modified epoxy prepared cover film.
2. The test method is as follows:
(1) peel strength: measured according to the IPC-TM-650 method using a quick press at 180 ℃ and 100kgf/cm2And pressing the covering film and the smooth surface of the copper foil for 60 seconds under the condition, and etching and testing the 180-degree peel strength after curing.
(2) Glue overflow amount: the test was carried out according to IPC-TM-650 method.
(3) The formability is as follows: the coverlay filling capacity of the coverlay film for the lines in the reaction examples and comparative examples was quantified. The coverlay films obtained in examples and comparative examples were attached to the test line at 180 ℃ and 100kgf/cm2And (5) after fast pressing for 60 seconds under the condition, observing whether the lines have glue shortage, air bubbles, poor filling, compaction or other defects.
(4) Ultimate dip soldering temperature: coating the copper foil with a film having a smooth surface of 100kgf/cm at 180 deg.C2After rapid pressing under the conditions for 60 seconds, curing is carried out for 3 hours at 170 ℃. Cutting the solidified sample into a sample with the size of 50mm multiplied by 50mm, then respectively immersing the sample in tin liquor with the temperature of 288 ℃, 320 ℃ and 360 ℃ for 60 seconds, and observing whether the delamination and foaming phenomena exist or not, wherein the passing highest temperature is the limit dip-soldering resistant temperature.
(5) Combustibility: after the release paper was peeled off, the test was carried out according to the UL94 vertical burning method.
(6) Ion migration resistance: and pressing the covering film and the circuit with the formed specific pattern to obtain the test sample. Under the condition of double 85, 100V direct current voltage is applied to the sample electrode for 1000 hours. If the short circuit occurs within 1000 hours, the short circuit does not pass; otherwise, the test is passed.
(7) Dendritic crystal: and observing whether dendritic growth exists between the lines of the ion migration resistant sample.
(8) Aging resistance: and pressing the covering film and the smooth surface of the copper foil, curing at 170 ℃ for 3 hours, baking at 177 ℃ for 240 hours, testing the 180-degree peel strength according to the peel strength testing method, and recording the peel strength retention rate.
(9) Storage property: storing the cover film in an environment with the temperature of 25 ℃ and the RH of 50 percent for 30 days, and if the glue overflow amount is less than 0.1mm, the cover film does not pass; otherwise, the test is passed.
TABLE 1
TABLE 2
As can be seen from tables 1 and 2, the cover films prepared by using the halogen-free resin composition of the present invention in the examples have excellent heat resistance, aging resistance, storage property and ion migration resistance, and no dendrite occurs after the ion migration resistance test. The resin composition in the comparative example has a compounding ratio and a structure which are not in an optimal range, has excellent ion migration resistance, but has poor comprehensive performance, is not as good as the resin composition in the aspects of coating property, glue overflow amount, peeling strength, dip soldering resistance and the like, and cannot meet the performance requirements of the flexible printed circuit board. In particular, in comparative example 7, the amine number of the polyurethane and polyamide block copolymer used was too high, resulting in a decrease in the storage property of the covering film. Therefore, the resin composition of the present invention requires the polyurethane and polyamide block copolymer, MQ tree with proper structure and ratio and other components to obtain the covering film with excellent performance.
In conclusion, the halogen-free resin composition provided by the invention adopts the polyurethane and polyamide block copolymer as the main toughening agent, the MQ resin as the auxiliary toughening agent, and the phosphorus-containing epoxy resin, the multifunctional epoxy resin, the curing agent and the phosphorus-containing flame retardant are matched, so that the polymer network with the sea-island structure can be formed through mutual crosslinking reaction, the halogen-free resin composition not only has excellent flexibility, storage property and heat resistance, but also has excellent ion migration resistance, and the prepared cover film can be used in the field with high reliability requirements.
The invention is not to be considered as limited to the particular embodiments shown, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The halogen-free resin composition is characterized by comprising the following components dispersed in an organic solvent in parts by weight: 10-20 parts of phosphorus-containing epoxy resin, 10-15 parts of multifunctional epoxy resin, 35-50 parts of polyurethane and polyamide block copolymer, 10-20 parts of MQ resin, 5-10 parts of amine curing agent and 5-15 parts of phosphorus-containing flame retardant;
the amine value of the polyurethane and polyamide block copolymer is 12-18 mgKOH/g; the mole number of the polyurethane chain segment in the polyurethane and polyamide block copolymer accounts for not less than 20% of the total mole number of the polyurethane chain segment and the polyamide chain segment in the block copolymer; the mole number of the polyamide chain segment accounts for not less than 60% of the total mole number of the polyurethane chain segment and the polyamide chain segment in the block copolymer; the polyurethane and polyamide segmented copolymer is prepared by copolymerizing diisocyanate, polyether diol, dibasic acid and diamine, wherein a polyurethane chain segment is a soft segment, the number average molecular weight of the polyurethane chain segment is 1500-2200, and the glass transition temperature Tg is-40 to-20 ℃; the polyamide chain segment is a hard segment, the number average molecular weight of the polyamide block is 3000-4500, and the glass transition temperature is 10-20 ℃;
the MQ resin is prepared by hydrolyzing and condensing an M group organic silicon monomer and a Q group organic silicon monomer, and the M/Q value is 1.0-1.5; the organic silicon monomer of the M group is a monofunctional organic siloxane closed chain link R3SiO0.5(ii) a The organosilicon monomer of the M group has the following structure:
the Q group is a tetrafunctional silicon monomer and comprises any one of methyl orthosilicate and ethyl orthosilicate.
2. The halogen-free resin composition according to claim 1, wherein the halogen-free resin composition has a solid content of 40 to 70 wt%.
3. The halogen-free resin composition according to claim 1, wherein the organic solvent is one or a mixture of acetone, butanone, cyclohexanone, propylene glycol methyl ether, ethylene glycol methyl ether, ethyl acetate, propylene glycol methyl ether acetate, and dimethylformamide.
4. The halogen-free resin composition according to claim 1, wherein the phosphorus-containing epoxy resin is one or a mixture of DOPO type phosphorus-containing epoxy resin, DOPO-HQ type phosphorus-containing epoxy resin and phosphate ester modified epoxy resin.
5. The halogen-free resin composition according to claim 1, wherein the multifunctional epoxy resin has an epoxy equivalent of 160-380g/eq and comprises one or more of phenol novolac epoxy resin, bisphenol A novolac epoxy resin, o-cresol novolac epoxy resin, and tetraphenol ethane tetraglycidyl ether.
6. The halogen-free resin composition according to claim 1, wherein the amine curing agent is one or more of 4,4 '-diaminodiphenyl sulfone, 3' -diaminodiphenyl sulfone, dicyandiamide, m-phenylenediamine, diethylenetriamine and diaminodiphenylmethane.
7. The coverlay for flexible printed circuit boards prepared by using the halogen-free resin composition according to claims 1-6, which comprises a polyimide film, a halogen-free resin composition layer coated on the surface of the polyimide film, and a release paper laminated on the halogen-free resin composition layer.
8. The coverlay film for flexible printed circuit boards according to claim 7, which is prepared by the method comprising: coating the halogen-free resin composition of any one of claims 1 to 6 on a polyimide insulating film, drying, removing the organic solvent, forming a semi-cured halogen-free resin composition coating on the polyimide insulating film, and then laminating the semi-cured halogen-free resin composition coating with release paper to obtain the coverlay for the flexible printed circuit board.
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| 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 |
| 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 |
| 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 |
| 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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| 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 |
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| TWI432509B (en) * | 2008-12-22 | 2014-04-01 | Iteq Corp | Halogen-free bonding sheet and resin composition for preparing the same |
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| 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 |
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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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Date of cancellation: 20230106 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 coating film for flexible printed circuit board prepared therefrom Effective date of registration: 20230109 Granted publication date: 20201027 Pledgee: Bank of China Limited Huangshi Branch Pledgor: HUBEI HENGCHI ELECTRONIC TECHNOLOGY Co.,Ltd. Registration number: Y2023420000010 |
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Granted publication date: 20201027 Pledgee: Bank of China Limited Huangshi Branch Pledgor: HUBEI HENGCHI ELECTRONIC TECHNOLOGY Co.,Ltd. Registration number: Y2023420000010 |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
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 |