CN116410684A - Resin composition and coating film prepared from same - Google Patents
Resin composition and coating film prepared from same Download PDFInfo
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- CN116410684A CN116410684A CN202111666940.0A CN202111666940A CN116410684A CN 116410684 A CN116410684 A CN 116410684A CN 202111666940 A CN202111666940 A CN 202111666940A CN 116410684 A CN116410684 A CN 116410684A
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- Prior art keywords
- resin
- resin composition
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- epoxy resin
- film
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- 239000011342 resin composition Substances 0.000 title claims abstract description 67
- 239000011248 coating agent Substances 0.000 title description 11
- 238000000576 coating method Methods 0.000 title description 11
- 239000013039 cover film Substances 0.000 claims abstract description 29
- 239000010408 film Substances 0.000 claims abstract description 28
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 26
- 239000003822 epoxy resin Substances 0.000 claims abstract description 24
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 24
- 229920001225 polyester resin Polymers 0.000 claims abstract description 21
- 239000004645 polyester resin Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005011 phenolic resin Substances 0.000 claims abstract description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 239000010410 layer Substances 0.000 claims description 10
- 239000012790 adhesive layer Substances 0.000 claims description 8
- 229920001721 polyimide Polymers 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- 239000004843 novolac epoxy resin Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 239000012766 organic filler Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011256 inorganic filler Substances 0.000 claims description 4
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 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
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 239000000839 emulsion Substances 0.000 claims 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 22
- 238000003878 thermal aging Methods 0.000 abstract description 9
- 238000003825 pressing Methods 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 6
- 230000032683 aging Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 230000037303 wrinkles Effects 0.000 description 5
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 229920006332 epoxy adhesive Polymers 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000012787 coverlay film Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000013034 phenoxy resin Substances 0.000 description 3
- 229920006287 phenoxy resin Polymers 0.000 description 3
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BIIBYWQGRFWQKM-JVVROLKMSA-N (2S)-N-[4-(cyclopropylamino)-3,4-dioxo-1-[(3S)-2-oxopyrrolidin-3-yl]butan-2-yl]-2-[[(E)-3-(2,4-dichlorophenyl)prop-2-enoyl]amino]-4,4-dimethylpentanamide Chemical compound CC(C)(C)C[C@@H](C(NC(C[C@H](CCN1)C1=O)C(C(NC1CC1)=O)=O)=O)NC(/C=C/C(C=CC(Cl)=C1)=C1Cl)=O BIIBYWQGRFWQKM-JVVROLKMSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- FONQHTXMAWNKQM-UHFFFAOYSA-N 2-ethyl-4-isocyano-5-methyl-1H-imidazole Chemical compound CCC1=NC(=C(N1)C)[N+]#[C-] FONQHTXMAWNKQM-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- CYJRNFFLTBEQSQ-UHFFFAOYSA-N 8-(3-methyl-1-benzothiophen-5-yl)-N-(4-methylsulfonylpyridin-3-yl)quinoxalin-6-amine Chemical compound CS(=O)(=O)C1=C(C=NC=C1)NC=1C=C2N=CC=NC2=C(C=1)C=1C=CC2=C(C(=CS2)C)C=1 CYJRNFFLTBEQSQ-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- INKDAKMSOSCDGL-UHFFFAOYSA-N [O].OC1=CC=CC=C1 Chemical compound [O].OC1=CC=CC=C1 INKDAKMSOSCDGL-UHFFFAOYSA-N 0.000 description 1
- REBHQKBZDKXDMN-UHFFFAOYSA-M [PH2]([O-])=O.C(C)[Al+]CC Chemical compound [PH2]([O-])=O.C(C)[Al+]CC REBHQKBZDKXDMN-UHFFFAOYSA-M 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a resin composition and a cover film prepared from the same, wherein the resin composition comprises the following components in parts by weight: 45-55 parts of carboxyl-containing polyester resin, 18-25 parts of phenolic resin, 10-15 parts of multifunctional epoxy resin and 0.2-0.6 part of curing agent, wherein the curing agent is 2, 4-diamino-6- [2- (2-methyl-1-imidazole) ethyl ] -s-triazine. The covering film prepared by the resin composition has higher peel strength, excellent thermal aging resistance and chemical resistance after long-time treatment at high temperature, is very suitable for a multi-layer flexible printed circuit board, and can meet the processing requirements of repeated pressing and repeated SMT of the rigid-flex circuit board and the occasion of long-time use at high temperature.
Description
Technical Field
The invention belongs to the field of electronic circuit base materials, relates to a resin composition and a coating film prepared from the resin composition, and particularly relates to a high heat aging resistance resin composition and a coating film prepared from the resin composition.
Background
The covering film is used as a surface protection layer of a Flexible Printed Circuit Board (FPCB), protects a circuit from being polluted by dust, moisture and chemicals and other forms of damages, has insulating and solder resisting functions, has certain flexibility and reinforcing functions, can reduce the influence of stress of a conductor in a bending process, and improves the bending resistance of the flexible printed circuit board. The cover film with the largest FPCB usage amount is a polyimide film type cover film, and is formed by coating an adhesive (resin composition) on one side of a polyimide film (PI film), and then drying and partially crosslinking. For twenty years, the covering film for the FPCB mainly adopts an epoxy adhesive, the epoxy adhesive adopts epoxy resin as main resin and carboxyl nitrile rubber as a toughening agent, but because the carboxyl nitrile rubber contains a large amount of unsaturated double bonds, oxidation chain breakage easily occurs at high temperature, and the thermal aging resistance is poor, so that the peeling strength of the epoxy adhesive covering film is greatly reduced after long-time baking, heat treatment or multiple pressing, the bonding reliability is reduced, and the processing requirements of multiple high-temperature pressing and multiple SMT of a multilayer flexible circuit board and a rigid-flex combined circuit board are not met, and the requirement of the circuit board for long-time use in a high-temperature environment is met.
CN102010569a discloses a halogen-free flame retardant epoxy resin composition and a high-flexibility cover film prepared by using the same, CN102010567a discloses a halogen-free phosphorus-free epoxy resin composition and a cover film prepared by using the same, which are all epoxy resin compositions with different characteristics, and all adopt carboxyl nitrile rubber, but when the actual application test and evaluation are carried out, the thermal aging resistance of the cover film prepared by using the epoxy resin compositions is poor due to the poor thermal aging resistance of the carboxyl nitrile rubber.
Accordingly, in the art, it is desired to develop a material capable of solving the problem of thermal aging resistance of an epoxy adhesive cover film, and also capable of having high peel strength, chemical resistance, and good workability.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a resin composition and a coating film prepared from the same, and particularly provides a high heat aging resistance resin composition and a coating film prepared from the same. The resin composition has good thermal aging resistance, and the coating film prepared by the resin composition still has higher peel strength after being treated at high temperature for a long time, has excellent thermal aging resistance and chemical resistance, is very suitable for multi-layer flexible printed circuit boards, and can meet the processing requirements of repeated pressing and repeated SMT of rigid-flex combined circuit boards and occasions of long-term use at high temperature.
To achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a resin composition comprising the following components in parts by weight:
45-55 parts of carboxyl-containing polyester resin, 18-25 parts of phenolic resin, 10-15 parts of multifunctional epoxy resin, 0.2-0.6 part of curing agent, 15-25 parts of filler and 0.05-0.15 part of antioxidant, wherein the curing agent is 2, 4-diamino-6- [2- (2-methyl-1-imidazole) ethyl ] -s-triazine.
The resin composition of the invention takes carboxyl-containing polyester resin as main resin, and is matched with phenol oxygen resin and multifunctional epoxy resin to improve the flexibility resistance and heat resistance of the resin composition, so that the resin composition is endowed with high heat aging resistance, adhesiveness and flexibility, and 2, 4-diamino-6- [2- (2-methyl-1-imidazole) ethyl ] -s-triazine is taken as curing agent to improve the crosslinking density and chemical resistance of the resin composition.
In the resin composition of the present invention, the content of the carboxyl group-containing polyester resin may be 45 parts, 48 parts, 50 parts, 52 parts or 55 parts, the content of the phenoxy resin may be 18 parts, 20 parts, 23 parts or 25 parts, the content of the multifunctional epoxy resin may be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts, and the content of the curing agent may be 0.2 parts, 0.4 parts, 0.5 parts or 0.6 parts.
The carboxyl group-containing polyester resin has excellent heat aging resistance and heat resistance, and has high reactivity due to high carboxyl groups and acid values, and can react with epoxy resin. The carboxyl group-containing polyester resin may use commercial products, and exemplary include, but are not limited to: BX-39SS from Toyo-yo or H204 from hyperbranched resin technology.
In the present invention, if the amount of the carboxyl group-containing polyester resin is too much, the glass transition temperature of the resin composition is low, the coating film prepared therefrom has a large touch adhesiveness, and the FPCB laminated with the coating film is folded to generate wrinkles; if the carboxyl group-containing polyester resin is too small, the flexibility and adhesion of the resin composition may be lowered.
In the present invention, the high glass transition temperature of the phenoxy resin can improve the flexibility, modulus, glass transition temperature of the resin composition and improve the touch adhesiveness of the cover film. In the present invention, if the amount of the phenoxy resin is too large, the adhesiveness of the resin composition is lowered; if the amount of the phenol resin is too small, the modulus and glass transition temperature of the resin composition are low, and the cover film is folded after the FPCB is pressed, and wrinkles are generated in the cover film. The phenol-oxygen Resin may be used commercially, and exemplary products include, but are not limited to 1276 from Mitsubishi chemical corporation, EPONL Resin53-BH-35 from Momentiye, or PKHH from Inchem.
Preferably, the carboxyl group containing polyester resin has an acid value of 25 to 65mgKOH/g, for example 25mgKOH/g, 28mgKOH/g, 30mgKOH/g, 32mgKOH/g, 35mgKOH/g, 38mgKOH/g, 40mgKOH/g, 42mgKOH/g, 45mgKOH/g, 48mgKOH/g, 50mgKOH/g, 52mgKOH/g, 55mgKOH/g, 58mgKOH/g, 60mgKOH/g, 62mgKOH/g or 65mgKOH/g. The carboxyl group-containing polyester resin in the present invention may be in the form of a solid or a resin solution, and the acid value of the carboxyl group-containing polyester resin is the acid value corresponding to the solid state.
Preferably, the carboxyl group-containing saturated polyester resin has a number average molecular weight of 5000 to 20000, for example 5000, 8000, 10000, 12000, 15000, 18000 or 20000.
Preferably, the glass transition temperature of the carboxyl group-containing saturated polyester resin is-10 to 50 ℃, for example-10 ℃, -8 ℃, -5 ℃, -3 ℃, 0 ℃, 3 ℃, 5 ℃, 8 ℃, 10 ℃, 13 ℃, 15 ℃, 18 ℃, 20 ℃, 25 ℃, 28 ℃, 30 ℃, 35 ℃, 38 ℃, 40 ℃, 43 ℃, 45 ℃, 48 ℃, or 50 ℃.
In the present invention, the multifunctional epoxy resin can improve the curing crosslinking density of the resin composition, and further can improve the heat resistance and chemical resistance of the resin cured product. Preferably, the multifunctional epoxy resin is selected from one or a combination of at least two of biphenyl type epoxy resin, phenol type novolac epoxy resin, o-cresol type novolac epoxy resin, bisphenol a type novolac epoxy resin, dicyclopentadiene phenol type epoxy resin.
In the present invention, the curing agent is 2, 4-diamino-6- [2- (2-methyl-1-imidazole) ethyl ] -s-triazine, CAS No. 38668-46-1.
In the present invention, 2, 4-diamino-6- [2- (2-methyl-1-imidazole) ethyl ] -s-triazine acts as a latent curing agent in the resin composition, allowing the resin composition solution and the coverlay to have a longer pot life, which reacts with the epoxy resin, increasing the crosslinking density, heat resistance and chemical resistance of the resin composition. If 2, 4-diamino-6- [2- (2-methyl-1-imidazole) ethyl ] -s-triazine is used in too little amount, the chemical resistance of the resin composition is poor; if 2, 4-diamino-6- [2- (2-methyl-1-imidazole) ethyl ] -s-triazine is too much, the gelation time of the resin composition is shortened, which is disadvantageous for the storage of the resin composition solution. Experiments have found that imidazole compounds such as 2-methylimidazole, 2-undecylimidazole and isocyano-2-ethyl-4-methylimidazole (2E 4 MZ-CN) which are commonly used and amine curing agents such as dicyandiamide are not suitable as curing agents for the resin composition of the present invention, and that the imidazole compounds which are commonly used reduce the chemical resistance and pot life of the cover film, while dicyandiamide reduces the heat resistance and moist heat resistance of the cover film.
Preferably, the resin composition further contains 15 to 25 parts of filler, and the content of the filler may be 15 parts, 18 parts, 20 parts, 22 parts, or 25 parts.
The filler is inorganic filler or organic filler, wherein the inorganic filler is at least one of aluminum hydroxide, magnesium hydroxide, boehmite, talcum powder, silicon dioxide, kaolin and aluminum oxide, and the organic filler is at least one of organic filler such as diethyl aluminum phosphinate, melamine cyanuric acid and the like.
Preferably, the resin composition further contains 0.05 to 0.15 part of an antioxidant, and the content of the antioxidant may be 0.05 part, 0.08 part, 0.1 part, 0.12 part, or 0.15 part.
The antioxidants are hindered phenol antioxidants or hindered amine antioxidants, the antioxidants can delay oxidation of the epoxy resin composition in the high-temperature curing and subsequent processing application processes, and the antioxidants can be hindered phenol antioxidants CHINOX 1010, CHINOX 1076, CHINOX 1098, CHIN0Z 1325 (all are double bond chemical industry Co., ltd.) and the like, and the antioxidants can be hindered amine antioxidants DNP (Kaiyuan fine chemical industry) and the like.
In another aspect, the present invention provides a resin dope obtained by dissolving or dispersing the resin composition described above in an organic solvent.
Preferably, the organic solvent is selected from one or a combination of at least two of acetone, butanone, cyclohexanone, ethylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl acetate, butyl acetate and dimethyl sulfoxide.
In the present invention, the organic solvent is used to dissolve the curing agent and the resin, disperse the filler, and adjust the solution viscosity of the resin composition. The prepared resin composition solution has 35-45% of solid content and proper solution viscosity, and can provide good processability.
In another aspect, the present invention provides a cover film comprising a polymer-based film, an adhesive layer on the polymer-based film, and a release paper layer on the adhesive layer, the adhesive layer being formed of the resin composition as described above.
Preferably, the polymer-based film is a polyimide film.
Preferably, the thickness of the polymer-based film is 7.5-50 μm, for example 7.5 μm, 9 μm, 15 μm, 18 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm.
Preferably, the thickness of the adhesive layer is 5-50 μm, for example 5 μm, 10 μm, 15 μm, 18 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm.
Preferably, the thickness of the release paper layer is 110-130 μm, for example 110 μm, 112 μm, 115 μm, 118 μm, 120 μm, 122 μm, 125 μm, 128 μm or 130 μm.
After the components of the resin composition are mixed, a bead mill is used and matched with high-shear stirring dispersing equipment to mix the components of the composition together so as to prepare the resin composition. The resin composition was then coated on one surface of the polyimide film using a coater, and oven-dried, heated at 140 ℃ for 5 minutes to remove the organic solvent and partially crosslink and cure the resin composition, thereby forming a semi-cured resin composition layer on the polyimide film. And then, pressing and compounding the film with a release paper roll at the pressing temperature of 80 ℃ and rolling the film to obtain the cover film.
Compared with the prior art, the invention has the following beneficial effects:
the resin composition disclosed by the invention takes carboxyl-containing polyester resin as main resin, and is matched with phenol-oxygen resin and multifunctional epoxy resin to improve the flexibility and heat resistance of the resin composition, so that the resin composition is endowed with high heat aging resistance, adhesiveness and flexibility, and 2, 4-diamino-6- [2- (2-methyl-1-imidazole) ethyl ] -s-triazine is taken as a curing agent to improve the crosslinking density and chemical resistance of the resin composition, so that a coating film prepared from the resin composition still has high peel strength after being treated at high temperature for a long time, is excellent in heat aging resistance and chemical resistance, is very suitable for multi-layer flexible printed circuit boards, and can meet the processing requirements of repeated lamination and repeated SMT of rigid-flexible combined circuit boards and occasions of long-term use at high temperature.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
A resin composition comprising: 50 parts by weight of carboxyl group-containing polyester resin (BX-39 SS, toyo Kagaku Co., ltd.), 21 parts by weight of phenol resin (1276, mitsubishi chemical Co., ltd.), 12 parts by weight of biphenyl type epoxy resin (NC-3000H, japanese chemical Co., ltd.), 0.4 part by weight of 2, 4-diamino-6- [2- (2-methyl-1-imidazole) ethyl ] -s-triazine (2 MZ-A, sizhou chemical Co., ltd.), 20 parts by weight of aluminum diethylphosphinate (OP-935, clariant Co., ltd.), and 0.1 part by weight of antioxidant 1010 (CHINOX 1010, double bond chemical Co., ltd.).
The solid components are dissolved and dispersed in the organic solvent according to the proportion, and the butanone is used for adjusting to obtain the resin composition glue solution with the solid content of 40 percent.
Examples 2 to 3 and comparative examples 1 to 12
A resin composition, the components and the contents of which are shown in table 1 and table 2; the amount of each component in tables 1-2 is in parts by weight (i.e., parts by weight of solids without solvent).
The resin composition glue solutions of examples 1 to 3 and comparative examples 1 to 12 were applied onto polyimide films (TL-012, michael science and technology Co., ltd.) having a thickness of 12.5 μm, respectively, with a coater, the thickness of the resin composition layer was controlled to 15 μm, and the resultant was baked in an oven at 160℃for 5 minutes to form a partially crosslinked cured resin composition layer on the polyimide film, which was then roll-compounded with a 120 μm release paper at a press temperature of 75℃to obtain a coverlay film.
The performance of the cover films of examples 1 to 3 and comparative examples 1 to 12 was measured, and the results are shown in tables 1 and 2.
TABLE 1
TABLE 2
The test method of the performance of the covering film is as follows:
(1) Peel strength: the test was carried out according to the IPC-TM-650.2.4.9 method, and the peel strength was measured by first pressing the cover film against a polished surface of an 18 μm rolled copper foil (BHYX-92F-T, nitsche Metal Co., ltd.) and baking at 160℃for 1 hour.
(2) Thermal aging resistance: the cover film was first laminated on a smooth surface of 18 μm rolled copper foil (BHYX-92F-T, nitsche Metal Co., ltd.), and then baked in an oven at 200℃for 6 hours, followed by taking out and testing the peel strength.
(3) Chemical resistance: the test was performed according to the IPC-TM-650.2.3.2 method. The chemical resistance of the cover film is characterized by peel strength retention, i.e., peel strength of the test sample after chemical treatment/peel strength before treatment x 100%. The higher the peel strength retention, the better the chemical resistance and vice versa, the worse the FPCB processing over-wet flow, with line-out.
(4) Bending and folding: the cover film was laminated on both sides of a flexible copper clad laminate SF305 10H20DE (a commercially available product of the life science and technology Co., ltd.) and baked at 160℃for 1 hour. The cured material was cut into test bars having a width of 10mm and a length of not less than 50 mm. Selecting a 1.0mm thick plug gauge, and manually bending for 5 times. The folded sample was subjected to a slice analysis and the fold height was measured, and the fold condition of the film was observed at the folded position, and the folded position was classified into no fold (folded surface smooth, fold height 0 μm), slight fold (0 μm < fold height 15 μm) and severe fold (fold height > 15 μm) according to the fold degree (fold height).
As can be seen from Table 1, the resin composition of the present invention provides a cover film peel strength of 1.12N/mm or more, a thermal aging resistance of 0.73N/mm or more, a chemical resistance of 95% or more, and no bending wrinkles.
Comparative example 1 was not used with a phenol-oxygen resin, and the film was covered with severe wrinkles. In comparative examples 2 to 4, the chemical resistance of the corresponding cover film was significantly reduced by changing the curing agent to 2-undecylimidazole, 2E4MZ-A, and blocked isocyanate, respectively. In comparative example 5, the amount of the phenol resin used was too small, and the cover film was slightly wrinkled; in comparative example 6, the amount of the phenol resin used was too large, the peel strength of the cover film was lowered, and the heat aging resistance was deteriorated. In comparative example 7, the amount of the multifunctional epoxy resin used was too small, the heat aging resistance of the coverlay film was deteriorated, and the chemical resistance was deteriorated; in comparative example 8, the amount of the multifunctional epoxy resin used was excessive, the peel strength of the cover film was lowered, and the heat aging resistance was deteriorated. In comparative example 9, the curing agent 2, 4-diamino-6- [2- (2-methyl-1-imidazole) ethyl ] -S-triazine was used in too small an amount, and the heat aging resistance of the coverlay film was deteriorated and the chemical resistance was deteriorated; in comparative example 10, the amount of 2, 4-diamino-6- [2- (2-methyl-1-imidazole) ethyl ] -S-triazine as a curing agent was excessive, and the peel strength of the cover film was lowered, and the heat aging resistance was deteriorated. In comparative example 11, the carboxyl group-containing polyester resin was used in an excessive amount, and the chemical resistance of the cover film was lowered to generate slight wrinkles; in comparative example 12, the amount of the carboxyl group-containing polyester resin used was too small, the peel strength of the cover film was lowered, and the heat aging resistance was deteriorated.
The applicant states that the present invention is illustrated by the above examples for the highly heat aging resistant resin composition of the present invention and the cover film prepared therefrom, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention must be practiced depending on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A resin composition, characterized in that the resin composition comprises the following components in parts by weight:
45-55 parts of carboxyl-containing polyester resin, 18-25 parts of phenolic resin, 10-15 parts of multifunctional epoxy resin and 0.2-0.6 part of curing agent, wherein the curing agent is 2, 4-diamino-6- [2- (2-methyl-1-imidazole) ethyl ] -s-triazine.
2. The resin composition according to claim 1, wherein the carboxyl group-containing polyester resin has an acid value of 25 to 65mgKOH/g;
preferably, the carboxyl group-containing saturated polyester resin has a number average molecular weight of 5000 to 20000;
preferably, the glass transition temperature of the carboxyl group-containing saturated polyester resin is-10 to 50 ℃.
3. The resin composition according to claim 1 or 2, wherein the multifunctional epoxy resin is selected from one or a combination of at least two of biphenyl type epoxy resin, phenol type novolac epoxy resin, o-cresol type novolac epoxy resin, bisphenol a type novolac epoxy resin, dicyclopentadiene phenol type epoxy resin.
4. A resin composition according to any one of claims 1 to 3, wherein the resin composition further comprises 15 to 25 parts of a filler;
preferably, the filler is an inorganic filler or an organic filler;
preferably, the inorganic filler is at least one of aluminum hydroxide, magnesium hydroxide, boehmite, talc, silica, kaolin or alumina;
preferably, the organic filler is at least one of aluminum diethylphosphinate, melamine, or cyanuric acid.
5. The resin composition according to any one of claims 1 to 4, wherein the resin composition further contains 0.05 to 0.15 parts of an antioxidant;
preferably, the antioxidant is a hindered phenol antioxidant or a hindered amine antioxidant.
6. A resin emulsion obtained by dissolving or dispersing the resin composition according to any one of claims 1 to 5 in an organic solvent.
7. The resin glue solution according to claim 6, wherein the organic solvent is selected from one or a combination of at least two of acetone, butanone, cyclohexanone, ethylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl acetate, butyl acetate, and dimethyl sulfoxide.
8. A resin glue according to claim 6 or 7, wherein the solids content of the resin glue is 35-45%.
9. A cover film comprising a polymer-based film, an adhesive layer on the polymer-based film, and a release paper layer on the adhesive layer, the adhesive layer being formed from the resin composition of any one of claims 1-5.
10. The cover film of claim 9, wherein the polymer-based film is a polyimide film;
preferably, the thickness of the polymer-based film is 7.5-50 μm;
preferably, the thickness of the adhesive layer is 5-50 μm;
preferably, the thickness of the release paper layer is 110-130 μm.
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