CN117604827A - Adhesive sheet and preparation method and application thereof - Google Patents
Adhesive sheet and preparation method and application thereof Download PDFInfo
- Publication number
- CN117604827A CN117604827A CN202311620824.4A CN202311620824A CN117604827A CN 117604827 A CN117604827 A CN 117604827A CN 202311620824 A CN202311620824 A CN 202311620824A CN 117604827 A CN117604827 A CN 117604827A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- parts
- resin
- resin composition
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000853 adhesive Substances 0.000 title claims description 28
- 230000001070 adhesive effect Effects 0.000 title claims description 28
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003063 flame retardant Substances 0.000 claims abstract description 131
- 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 130
- 239000011342 resin composition Substances 0.000 claims abstract description 71
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003822 epoxy resin Substances 0.000 claims abstract description 44
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 44
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 42
- 239000005011 phenolic resin Substances 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 27
- 239000011574 phosphorus Substances 0.000 claims abstract description 27
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 26
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 25
- 150000002367 halogens Chemical class 0.000 claims abstract description 25
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 23
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims abstract description 22
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005470 impregnation Methods 0.000 claims abstract description 18
- 239000012779 reinforcing material Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000003292 glue Substances 0.000 claims description 35
- 239000011188 CEM-1 Substances 0.000 claims description 25
- 101100257127 Caenorhabditis elegans sma-2 gene Proteins 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 229920000877 Melamine resin Polymers 0.000 claims description 15
- -1 antimony halide Chemical class 0.000 claims description 13
- 229920001131 Pulp (paper) Polymers 0.000 claims description 12
- 239000004640 Melamine resin Substances 0.000 claims description 9
- 239000011889 copper foil Substances 0.000 claims description 9
- 150000007974 melamines Chemical class 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- UADBQCGSEHKIBH-UHFFFAOYSA-N 3-phenoxy-2,4-dihydro-1h-1,3,5,2,4,6-triazatriphosphinine Chemical compound P1N=PNPN1OC1=CC=CC=C1 UADBQCGSEHKIBH-UHFFFAOYSA-N 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims description 3
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical compound N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 claims description 3
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 claims description 3
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 3
- 229920000388 Polyphosphate Polymers 0.000 claims description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 3
- WARQUFORVQESFF-UHFFFAOYSA-N isocyanatoethene Chemical compound C=CN=C=O WARQUFORVQESFF-UHFFFAOYSA-N 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000001205 polyphosphate Substances 0.000 claims description 3
- 235000011176 polyphosphates Nutrition 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- XVYLTEAMNFTUEW-UHFFFAOYSA-N 2,2,4,4,6,6-hexakis(4-nitrophenoxy)-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound C1=CC([N+](=O)[O-])=CC=C1OP1(OC=2C=CC(=CC=2)[N+]([O-])=O)=NP(OC=2C=CC(=CC=2)[N+]([O-])=O)(OC=2C=CC(=CC=2)[N+]([O-])=O)=NP(OC=2C=CC(=CC=2)[N+]([O-])=O)(OC=2C=CC(=CC=2)[N+]([O-])=O)=N1 XVYLTEAMNFTUEW-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- LZEGXQIZUUMCJZ-UHFFFAOYSA-N C(C=C1)=CC=C1OP([N]P(OC1=CC=CC=C1)(OC1=CC=CC=C1)=N1)N=P1(OC1=CC=CC=C1)OC1=CC=CC=C1 Chemical compound C(C=C1)=CC=C1OP([N]P(OC1=CC=CC=C1)(OC1=CC=CC=C1)=N1)N=P1(OC1=CC=CC=C1)OC1=CC=CC=C1 LZEGXQIZUUMCJZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 2
- 150000004696 coordination complex Chemical class 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- CWIPUXNYOJYESQ-UHFFFAOYSA-N oxaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=CC=O.NC1=NC(N)=NC(N)=N1 CWIPUXNYOJYESQ-UHFFFAOYSA-N 0.000 claims description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 238000004080 punching Methods 0.000 abstract description 24
- 238000007598 dipping method Methods 0.000 abstract description 10
- 238000013461 design Methods 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 25
- 239000000463 material Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 239000004744 fabric Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000011162 core material Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 230000008646 thermal stress Effects 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- LEHNQGSPRXHYRT-UHFFFAOYSA-N 2-dodecyl-1h-imidazole Chemical compound CCCCCCCCCCCCC1=NC=CN1 LEHNQGSPRXHYRT-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920003274 CYMEL® 303 LF Polymers 0.000 description 1
- 244000179970 Monarda didyma Species 0.000 description 1
- 235000010672 Monarda didyma Nutrition 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
- D21H27/22—Structures being applied on the surface by special manufacturing processes, e.g. in presses
- D21H27/26—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures
- D21H27/28—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures treated to obtain specific resistance properties, e.g. against wear or weather
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/10—Phosphorus-containing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/11—Halides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/48—Condensation polymers of aldehydes or ketones with phenols
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
- D21H17/51—Triazines, e.g. melamine
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/52—Epoxy resins
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/66—Salts, e.g. alums
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/34—Ignifugeants
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/32—Addition to the formed paper by contacting paper with an excess of material, e.g. from a reservoir or in a manner necessitating removal of applied excess material from the paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/70—Multistep processes; Apparatus for adding one or several substances in portions or in various ways to the paper, not covered by another single group of this main group
- D21H23/72—Plural serial stages only
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a bonding sheet, a preparation method and application thereof, wherein the bonding sheet comprises a reinforcing material and a resin composition adhered to the reinforcing material through twice dipping and drying; the resin composition comprises a first resin composition attached after the first impregnation drying and a second resin composition attached after the second impregnation drying; the first resin composition includes a combination of a phenolic resin, a nitrogen-containing flame retardant, and a phosphorus-containing flame retardant; the second resin composition includes a combination of an epoxy resin, a curing agent, a halogen-based flame retardant, an antimony-based flame retardant, and a phosphorus-nitrogen flame retardant. Through the design and the compounding coordination of the first resin composition and the second resin composition, the bonding sheet has excellent flame retardance, heat resistance and processability, and the metal foil-clad laminated plate containing the bonding sheet has excellent flame retardance, heat resistance and punching property, and has remarkably improved comprehensive performance.
Description
Technical Field
The invention belongs to the technical field of copper-clad plates, and particularly relates to a bonding sheet and a preparation method and application thereof.
Background
The CEM-1 copper-clad laminate is prepared by taking electronic grade glass fiber cloth and bleached wood pulp paper as reinforcing materials, respectively soaking the electronic grade glass fiber cloth and the bleached wood pulp paper in a resin composition for the copper-clad laminate to prepare a fabric taking the electronic grade glass fiber cloth as the reinforcing material and a core taking the bleached wood pulp paper as the reinforcing material, covering the fabric with the copper foil, and carrying out hot pressing. The CEM-1 copper-clad laminate has better performance than the paper-based copper-clad laminate, lower cost than the glass fiber cloth-based copper-clad laminate, and better competitiveness in the aspects of mechanical property, electrical property, cost and processability. In recent years, with the development of lead-free and functional integration of end products, corresponding circuits are more complex, and higher requirements are also put on heat resistance, flame retardance and punching performance of CEM-1 copper clad laminates.
CN111806001a discloses a preparation method of a CEM-1 copper-clad plate, which comprises the following steps: (1) preparing surface material prepreg glue solution; (2) preparing lining one-dipping resin glue solution: uniformly mixing 5-10 parts by weight of phosphorus-containing flame retardant, 1-10 parts by weight of low-molecular thermosetting resin and 80-90 parts by weight of solvent; (3) preparing lining secondary resin dipping glue solution: uniformly mixing 20-35 parts by weight of low-molecular phosphorus-containing epoxy, 5-15 parts by weight of low-molecular common epoxy, 10-20 parts by weight of nitrogenous phenolic aldehyde, 1-5 parts by weight of modified phenolic aldehyde, 10-20 parts by weight of flame retardant filler, 1-10 parts by weight of lining filler and 20-30 parts by weight of solvent; (4) Dipping the electronic grade glass fiber cloth in the glue solution prepared in the step (1), and drying to obtain a surface material prepreg; dipping the wet-strength wood pulp paper into the glue solution prepared in the step (2), and drying to obtain a lining prepreg; and superposing the prepared lining prepreg and the surface prepreg, and covering with copper foil for hot pressing to obtain the CEM-1 copper-clad plate. As the phosphorus-containing flame retardant is added into the lining one-dipping resin glue solution, and the phosphorus-containing epoxy, the nitrogen-containing phenolic aldehyde and the phosphorus-containing nitrogen-containing flame retardant are added into the lining two-dipping resin glue solution, the CEM-1 copper-clad plate has FV0 level flame retardance, but the addition amount of the flame retardant in the plate is large, the heat resistance and the punching performance are poor, and the resistance to dip soldering at 288 ℃ is only 24s-26s.
CN111572131a discloses a preparation method of a CEM-1 copper-clad plate, which comprises the steps of preparing surface material resin, preparing lining primary impregnating resin, preparing lining secondary impregnating resin, preparing prepreg and hot-press molding; wherein the medium resin contains one or more than two of magnesium hydroxide, antimonous oxide and aluminum hydroxide, and the lining secondary resin contains one or two of magnesium hydroxide and antimonous oxide and is mixed, so that the board has good flame retardance; meanwhile, the secondary impregnating resin of the lining contains polyvinyl formal-polyvinyl alcohol-polyacrylic acid copolymer and cyanate ester modified resin, so that the heat resistance of the board is improved to some extent, but the 288 ℃ dip soldering resistance of the board is less than 70s, the obvious defect still exists, and the punching performance of the board cannot meet the processing requirement of a high-performance circuit board.
CN109233209a discloses a halogen-free antimony-free resin composition, which comprises the following components: 25-70 parts by weight of flame-retardant epoxy resin, 10-40 parts by weight of non-flame-retardant epoxy resin, 20-60 parts by weight of composite curing agent and 0.05-1.0 part by weight of curing accelerator; the flame-retardant epoxy resin comprises a composition of phosphorus-containing epoxy resin, brominated epoxy resin and nitrogen-containing epoxy resin, and the composition is matched with non-flame-retardant epoxy resin, so that the flame retardance, dip soldering resistance and heat resistance of the CEM-1 copper clad laminate can be enhanced, but due to the fact that more flame-retardant components are added into a resin system, the punching performance of the copper clad laminate is poor, and the heat resistance is also improved greatly.
At present, the improvement of the flame retardance of the CEM-1 copper clad laminate is mainly realized by adding a large amount of flame retardant, and the heat resistance and punching performance of the CEM-1 copper clad laminate are poor due to the large amount of flame retardant, so that the comprehensive performance is difficult to improve. Therefore, development of copper clad laminates having excellent flame retardancy, heat resistance and punching processability is an important research in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a bonding sheet, a preparation method and application thereof, and the bonding sheet has excellent flame retardance, heat resistance and processability through the design and compounding cooperation of a first resin composition and a second resin composition, and a metal foil-clad laminated plate comprising the bonding sheet has excellent flame retardance, heat resistance and punching processability and has obviously improved comprehensive performance.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an adhesive sheet comprising a reinforcing material, and a resin composition attached to the reinforcing material by two impregnation drying;
the resin composition comprises a first resin composition attached after the first impregnation drying and a second resin composition attached after the second impregnation drying;
the first resin composition includes a combination of a phenolic resin, a nitrogen-containing flame retardant, and a phosphorus-containing flame retardant;
the second resin composition includes a combination of an epoxy resin, a curing agent, a halogen-based flame retardant, an antimony-based flame retardant, and a phosphorus-nitrogen flame retardant.
In the adhesive sheet provided by the invention, the resin composition is adhered to the reinforcing material through two times of dipping and drying, wherein the first time of dipping and drying is used for adhering the first resin composition containing phenolic resin, a nitrogen-containing flame retardant and a phosphorus-containing flame retardant to the reinforcing material; then, the second impregnation drying is performed to achieve adhesion of the second resin composition. The invention is based on the principle that the CEM-1 copper-clad plate selects different flame-retardant systems for flame retardance in different combustion processes, selects the halogen-antimony flame-retardant system for flame retardance in the first combustion stage, selects the phosphorus-nitrogen flame-retardant system for flame retardance in the second combustion stage, and mutually cooperates the flame-retardant systems to achieve the effect of high-efficiency flame retardance in different combustion stages, thereby remarkably reducing the consumption of halogen-antimony flame retardant, solving the problems that the heat resistance and punching property of the CEM-1 copper-clad plate are poor and the comprehensive performance is difficult to improve by adding a large amount of flame retardant (such as a large amount of halogen-antimony flame retardant) in the prior art, and enabling the bonding sheet to have excellent heat resistance, flame retardance and processability. The metal foil-clad laminated board containing the bonding sheet has excellent flame retardant property, obviously improved heat resistance, punching property and processability, and excellent comprehensive performance, and fully meets the application requirements of a high-performance circuit board.
The following is a preferred technical scheme of the present invention, but not a limitation of the technical scheme provided by the present invention, and the following preferred technical scheme can better achieve and achieve the objects and advantages of the present invention.
Preferably, the phenolic resin is an aqueous phenolic resin, more preferably a small molecule water soluble phenolic resin.
Preferably, the phenolic resin has a number average molecular weight of 100-2000g/mol, for example, 200g/mol, 500g/mol, 800g/mol, 1000g/mol, 1200g/mol, 1500g/mol or 1800g/mol, and specific point values between the above point values, are limited in length and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values included in the range.
Preferably, the nitrogen-containing flame retardant is 5 to 10 parts by mass, for example, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts or 9.5 parts, based on 100 parts by mass of the phenolic resin, and specific point values among the above point values are limited in terms of space and for brevity, and the present invention is not exhaustive of the specific point values included in the range.
Preferably, the nitrogen-containing flame retardant comprises any one or a combination of at least two of vinyl isocyanate, melamine glyoxal resin, melamine formaldehyde resin, methylated melamine resin, butylated melamine resin, triisocyanurate modified melamine resin, and silicone modified melamine resin.
Preferably, the phosphorus-containing flame retardant is 10 to 20 parts by mass, for example, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts or 19 parts, based on 100 parts by mass of the phenolic resin, and specific point values between the above point values are limited in length and are not exhaustive for the sake of brevity.
Preferably, the phosphorus-containing flame retardant comprises an aqueous phosphorus-containing flame retardant.
Preferably, the phosphorus-containing flame retardant comprises any one or at least two of alkoxy cyclotriphosphazene, phenoxy cyclotriphosphazene, hexa-p-aldehyde phenoxy cyclotriphosphazene, hexa (4-DOPO methylolphenoxy) cyclotriphosphazene, (2-allylphenoxy) pentaphenoxy cyclotriphosphazene and hexa (4-nitrophenoxy) cyclotriphosphazene
In the present invention, "DOPO" means 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
Preferably, the epoxy resin includes any one or a combination of at least two of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin.
Preferably, the epoxy resin has an epoxy equivalent of 150 to 800g/eq, for example, 180g/eq, 200g/eq, 250g/eq, 300g/eq, 350g/eq, 400g/eq, 450g/eq, 500g/eq, 550g/eq, 600g/eq, 650g/eq, 700g/eq or 750g/eq, and specific point values between the above point values, are limited in length and for the sake of brevity, the invention is not exhaustive of the specific point values included in the range.
Preferably, the curing agent is 20-80 parts by mass, for example, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts or 75 parts, based on 100 parts by mass of the epoxy resin, and specific point values between the above point values are limited in scope and for brevity, the present invention is not exhaustive.
Preferably, the curing agent comprises any one or a combination of at least two of vegetable oil modified phenolic resin, linear phenolic resin and thermosetting phenolic resin.
Preferably, the halogen flame retardant is 5 to 15 parts by mass based on 100 parts by mass of the epoxy resin, for example, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts or 14 parts, and specific point values among the above point values are limited in terms of space and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the halogen-based flame retardant comprises a brominated flame retardant.
Preferably, the halogen flame retardant comprises any one or a combination of at least two of tetrabromobisphenol A, tribromophenol, decabromodiphenylethane and octabromodiphenylethane.
Preferably, the mass of the antimony-based flame retardant is 2 to 8 parts, for example, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts or 7.5 parts, based on 100 parts by mass of the epoxy resin, and specific point values between the above point values are limited in space and for brevity, the present invention is not exhaustive list of specific point values included in the range.
Preferably, the antimony-based flame retardant comprises any one or a combination of at least two of antimony oxide, antimony halide and antimonate.
Preferably, the mass of the phosphorus-nitrogen flame retardant is 5 to 10 parts, for example, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts or 9.5 parts, based on 100 parts of the mass of the epoxy resin, and specific point values among the above point values are limited in space and for brevity, the present invention is not exhaustive to list the specific point values included in the range.
Preferably, the phosphorus nitrogen flame retardant comprises any one or a combination of at least two of ammonium polyphosphate, melamine polyphosphate, phosphazene compound.
Preferably, a curing accelerator is further included in the second resin composition.
Preferably, the curing accelerator may be 0, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9 parts by mass of the epoxy resin based on 100 parts by mass of the epoxy resin, and specific point values between the above point values are limited in length and for brevity, and the present invention is not exhaustive.
Preferably, the curing accelerator comprises any one or a combination of at least two of tertiary amine, tertiary phosphine, organic metal complex, imidazole compound and quaternary ammonium salt, and more preferably imidazole compound.
Preferably, the imidazole compound comprises any one or a combination of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-dodecylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4-methylimidazole and 1-cyanoethyl-2-methylimidazole.
As a preferred technical scheme of the present invention, the first resin composition comprises the following components in parts by mass:
phenolic resin 100 parts
5-10 parts of nitrogen-containing flame retardant
10-20 parts of phosphorus-containing flame retardant;
the second resin composition comprises the following components in parts by mass:
preferably, the mass ratio of the first resin composition to the second resin composition is 1 (8-12), for example, may be 1:8.5, 1:9, 1:9.5, 1:10, 1:10.5, 1:11 or 1:11.5, etc., and further preferably 1:10.
Preferably, the reinforcing material comprises at least one of wood pulp paper, cotton pulp paper or non-woven fabric, further preferably wood pulp paper and/or cotton pulp paper.
Preferably, the mass percentage of the resin composition in the adhesive sheet is 40% -70%, for example, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65% or 68%, and specific point values between the above point values, which are limited in space and for the sake of brevity, the present invention is not exhaustive.
In a second aspect, the present invention provides a method for producing the adhesive sheet according to the first aspect, the method comprising:
placing the reinforcing material into glue solution of a first resin composition for first impregnation and then carrying out first drying to obtain prepreg;
and (3) placing the prepreg in a glue solution of a second resin composition for second impregnation and then carrying out second drying to obtain the bonding sheet.
Preferably, the solvent of the dope of the first resin composition includes water.
Preferably, the glue solution of the first resin composition has a solids content of 10% to 30%, for example 12%, 15%, 18%, 20%, 22%, 25% or 28%, and specific point values between the above point values, which are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values comprised in the range.
Preferably, the solvent of the dope of the second resin composition includes any one or a combination of at least two of a ketone solvent, an aromatic hydrocarbon solvent, and an ester solvent, and further preferably a ketone solvent and/or an aromatic hydrocarbon solvent.
Preferably, the ketone solvent comprises any one or a combination of at least two of acetone, butanone and cyclohexanone.
Preferably, the aromatic hydrocarbon solvent comprises any one or a combination of at least two of toluene, xylene and trimethylbenzene.
Preferably, the ester solvent comprises ethyl acetate and/or butyl acetate.
Preferably, the glue solution of the second resin composition has a solids content of 50% -70%, for example 52%, 55%, 58%, 60%, 62%, 65% or 68%, and specific point values between the above point values, which are limited in space and for the sake of brevity, the present invention is not exhaustive list of specific point values comprised in the range.
Preferably, the time of the first impregnation and the second impregnation is 5 to 60s independently, for example, may be 6s, 8s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s or 55s, and specific point values among the above point values, which are limited in length and for brevity, the present invention is not exhaustive to list the specific point values included in the range.
Preferably, the temperatures of the first drying and the second drying are each independently 100-220 ℃, such as 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ or 210 ℃, and specific point values between the above point values, which are limited in space and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.
Preferably, the time of the first drying and the second drying is 1-30min independently, for example, may be 2min, 5min, 8min, 10min, 15min, 20min or 25min, and specific point values among the above point values, which are limited in space and for simplicity, the present invention does not exhaustively list specific point values included in the range, and further preferably 1-10min.
Preferably, the first drying time is 3-5min.
Preferably, the second drying time is 2-4min.
In a third aspect, the present invention provides a metal foil-clad laminate comprising a metal foil and at least one adhesive sheet as described in the first aspect.
Preferably, the metal foil includes copper foil, aluminum foil, nickel foil, SUS foil, or the like, and further preferably copper foil.
Preferably, the metal foil-clad laminate is a CEM-1 copper-clad plate, and the CEM-1 copper-clad plate comprises a laminate and copper foils arranged on one side or two sides of the laminate; the laminate comprises a facing and a core comprising at least one adhesive sheet according to the first aspect.
Preferably, the number of the bonding sheets in the core material is 1-20, for example, 2, 3, 5, 6, 8, 10, 12, 15 or 18 sheets, etc.
Illustratively, the preparation method of the CEM-1 copper-clad plate comprises the following steps: respectively attaching fabrics on two sides of the core material to obtain a laminated board; and pressing copper foil on one side or two sides of the laminated board, and curing to obtain the CEM-1 copper-clad plate.
Preferably, the curing temperature is 130-190 ℃, such as 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, or 185 ℃, and specific point values between the above point values, are limited in space and for simplicity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the curing pressure is 4-8MPa, for example, 4.5MPa, 5MPa, 5.5MPa, 6MPa, 6.5MPa, 7MPa or 7.5MPa, and specific point values between the above point values, are limited in length and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the curing time is 30-300min, for example, 40min, 60min, 80min, 100min, 120min, 140min, 150min, 160min, 180min, 200min, 220min, 240min, 260min or 280min, and specific point values among the above point values, which are limited in space and for brevity, the present invention is not exhaustive.
In a fourth aspect, the present invention provides a printed circuit board comprising an adhesive sheet according to the first aspect and/or a metal foil-clad laminate according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the bonding sheet provided by the invention, the components of the first resin composition and the second resin composition are designed and compounded to be cooperated, so that the bonding sheet is obviously improved in flame retardance, heat resistance and processability, the problem that the CEM-1 copper-clad plate is poor in heat resistance and punching property due to the addition of a large amount of flame retardants in the prior art is solved, and the metal foil-clad laminated plate comprising the bonding sheet is excellent in flame retardance, and meanwhile, has obviously improved heat resistance and punching processability, low in water absorption rate and excellent in comprehensive performance.
(2) According to the invention, through the design and optimization of the first resin composition and the second resin composition in the bonding sheet, the flame retardance of the CEM-1 copper-clad plate containing the first resin composition and the second resin composition is UL-94V-0 level, the thermal stress (288 ℃ and the float welding) is more than or equal to 162s, the thermal stress (288 ℃ and the dip welding) is more than or equal to 108s, the T260 is more than or equal to 83min, the punching performance is 5 level, the high-performance circuit board has excellent flame retardance, heat resistance and punching processability, the water absorption rate is low, and the application requirement of the high-performance circuit board is fully met.
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.
In the following specific embodiments of the present invention, the materials involved are as follows:
(1) Phenolic resin
The aqueous phenolic resin, SQ-9322, has a number average molecular weight of 300-500g/mol and is available from Santa Classification, inc.
(2) Nitrogen-containing flame retardant
B1: melamine formaldehyde resin, JX-2533, available from Dalian Jinxin chemical Co., ltd;
b2: vinyl isocyanate, JS-5634, available from Hubei Jusheng technology Co., ltd;
b3: methylated melamine resin, CYMEL 303LF, purchased from bergamot Weng Kaier.
(3) Phosphorus-containing flame retardant
C1: phenoxy cyclotriphosphazene, SPB-100, purchased from foodless siren technologies limited, hubei;
c2: six pairs of aldehyde phenoxy cyclotriphosphazene, TC-130, purchased from Jiangsu Tiancheng chemical industry Co., ltd;
and C3: hexa (4-DOPO methylolphenoxy) cyclotriphosphazene, GC-PNP, available from Wuhan Haishan technologies Co.
(4) Epoxy resin
D1: biphenyl type phenolic epoxy resin, GELR134, available from macro-chang electronics materials, inc;
d2: phenol novolac type epoxy resin, BN-57, purchased from Jinan Kangyu New Material Co., ltd;
d3: o-cresol novolac epoxy resin, LP-39, available from wuhanji industrial chemicals limited.
(5) Curing agent
Phenolic novolac resin, ZP150, available from tense home harbor elegance chemical company.
(6) Halogen flame retardant
F1: decabromodiphenylethane, ZK-500, available from chengdoujia leaf biotechnology limited;
f2: tetrabromobisphenol A, BC-52, available from Dilong chemical Co., ltd;
f3: tribromophenol, ZX-45, available from the chemical technology of front-end diffraction (Wuhan Co., ltd.);
(7) Antimony-based flame retardant
G1: antimony pentoxide, SD-405, available from Wuhan Xinghe chemical Co., ltd;
and G2: antimony pentoxide, ZP530, available from tensor harbor elegance chemical company, inc;
and G3: sodium antimonate, YC-278, purchased from Hubei Yonggong real Co., ltd.
(8) Phosphorus-nitrogen flame retardant
H1: ammonium polyphosphate, XS-APPII-040, available from Shanghai Xudian non-halogen smoke abatement flame retardant Co., ltd;
h2: melamine polyphosphate, XS-MPP, available from shanghai with non-halogen smoke abatement flame retardants limited;
and H3: phosphazene compound, TP100, was purchased from Hubei Xinyu macro biological medicine technologies Co.
(9) Curing accelerator
2-methylimidazole, TD-230, was purchased from Hubei Xinghui chemical Co., ltd.
Example 1
An adhesive sheet comprising a reinforcing material, and a resin composition attached to the reinforcing material by two impregnation drying; the resin composition comprises a first resin composition attached after the first impregnation drying and a second resin composition attached after the second impregnation drying; the first resin composition comprises the following components in parts by mass: 100 parts of aqueous phenolic resin, 8 parts of nitrogen-containing flame retardant B1 and 15 parts of phosphorus-containing flame retardant C1; the second resin composition comprises the following components in parts by mass: 100 parts of epoxy resin D1, 50 parts of linear phenolic resin, 5 parts of halogen flame retardant F1,5 parts of antimony flame retardant G1,8 parts of phosphorus-nitrogen flame retardant H1 and 0.1 part of curing accelerator.
The preparation method of the bonding sheet comprises the following steps:
(1) Adding the water-based phenolic resin, the nitrogen-containing flame retardant, the phosphorus-containing flame retardant and water into a container according to the formula amount, stirring to uniformly mix the materials, and finally adjusting the solid content to 20% by using water to obtain a first glue solution; impregnating the first glue solution with wood pulp fiber paper for 10s, and then drying at 220 ℃ for 4min to obtain prepreg;
(2) According to the formula amount, adding epoxy resin, linear phenolic resin, halogen flame retardant, antimony flame retardant, phosphorus-nitrogen flame retardant, curing accelerator and acetone into a container, stirring to uniformly mix the materials, and finally adjusting the solid content to 60% by using acetone to obtain a second glue solution; and (3) impregnating the second glue solution with the prepreg obtained in the step (1) for 12s, and then drying at 180 ℃ for 3min to obtain the bonding sheet.
The CEM-1 copper-clad plate comprises a laminated plate and copper foils arranged on two sides of the laminated plate, wherein the laminated plate comprises a fabric and a core material, and the core material adopts the bonding sheet provided by the embodiment; the preparation method comprises the following steps: 5 bonding sheets provided in the embodiment are overlapped to be used as core materials, two sides of the core material lamination are matched with face materials (glass fiber cloth base prepregs), copper foils are covered on two outer sides of the face materials, and the face materials are hot-pressed for 120min at 160 ℃ under 5MPa in a press to prepare a CEM-1 copper-clad plate with the thickness of 1.6 mm.
Examples 2 to 13, comparative examples 1 to 3
An adhesive sheet differing from example 1 only in the components of the first resin composition and/or the second resin composition, and specific formulations are shown in tables 1 and 2; the amount units of each component in tables 1 and 2 are parts; the adhesive sheet was prepared in the same manner as in example 1.
The adhesive sheets provided in examples 2 to 13 and comparative examples 1 to 3 were prepared into CEM-1 copper-clad plates in the manner described in example 1, and were subjected to the following physical property evaluation tests:
(1) Thermal stress: respectively measuring float welding and dip welding at 288 ℃ according to a thermal stress test method specified in GB/T4722-2017;
(2) Punching property: the punching performance is measured according to a punching performance test method specified in GB/T4722-2017; testing according to UL-94 standard;
(3) Flame retardancy: according to UL94"50W (20 mm) vertical burn test: v-0, V-1 and V-2' test methods;
(4) Thermal stratification time T260: at a set temperature of 260 ℃, the plate is layered under the action of heat, and the time lasts before layering;
(5) Water absorption rate: the measurement was performed according to the IPC-TM-6502.6.2.1 method.
The test results are shown in tables 1 and 2 below.
TABLE 1
TABLE 2
Comparative example 4
An adhesive sheet differing from example 1 only in that the first resin composition comprises, in parts by mass: 100 parts of aqueous phenolic resin; the second resin composition comprises the following components in parts by mass: 100 parts of epoxy resin D1, 50 parts of linear phenolic resin, 0.1 part of curing accelerator, 10 parts of halogen flame retardant F1,5 parts of antimony flame retardant G1,7.5 parts of phosphorus-nitrogen flame retardant H1,8 parts of nitrogen-containing flame retardant B1 and 15 parts of phosphorus-containing flame retardant C1.
The preparation method of the bonding sheet comprises the following steps:
(1) Adding water-based phenolic resin and water into a container according to the formula amount, stirring to uniformly mix the water-based phenolic resin and the water, and finally adjusting the solid content to 20% by using the water to obtain a first glue solution; impregnating the first glue solution with wood pulp fiber paper for 10s, and then drying at 220 ℃ for 4min to obtain prepreg;
(2) According to the formula amount, adding epoxy resin, linear phenolic resin, halogen flame retardant, antimony flame retardant, phosphorus-nitrogen flame retardant, curing accelerator, nitrogen-containing flame retardant, phosphorus-containing flame retardant and acetone into a container, stirring to uniformly mix the materials, and finally adjusting the solid content to 60% by using acetone to obtain a second glue solution; and (3) impregnating the second glue solution with the prepreg obtained in the step (1) for 18s, and then drying at 180 ℃ for 3min to obtain the bonding sheet.
Comparative example 5
An adhesive sheet differing from example 1 only in that the first resin composition comprises, in parts by mass: 100 parts of aqueous phenolic resin, 10 parts of halogen flame retardant F1,5 parts of antimony flame retardant G1 and 7.5 parts of phosphorus-nitrogen flame retardant H1; the second resin composition comprises the following components in parts by mass: 100 parts of epoxy resin D1, 50 parts of linear phenolic resin, 0.1 part of curing accelerator, 8 parts of nitrogen-containing flame retardant B1 and 15 parts of phosphorus-containing flame retardant C1.
The preparation method of the bonding sheet comprises the following steps:
(1) Adding water-based phenolic resin, halogen flame retardant, antimony flame retardant, phosphorus-nitrogen flame retardant and water into a container according to the formula amount, stirring to uniformly mix the materials, and finally adjusting the solid content to 20% by using water to obtain a first glue solution; impregnating the first glue solution with wood pulp fiber paper for 16s, and then drying at 220 ℃ for 4min to obtain prepreg;
(2) According to the formula amount, adding epoxy resin, linear phenolic resin, a curing accelerator, a nitrogen-containing flame retardant, a phosphorus-containing flame retardant and acetone into a container, stirring to uniformly mix the materials, and finally, regulating the solid content to be 60% by using acetone to obtain a second glue solution; and (3) impregnating the second glue solution with the prepreg obtained in the step (1) for 12s, and then drying at 180 ℃ for 3min to obtain the bonding sheet.
Comparative example 6
An adhesive sheet differing from example 1 only in that the first resin composition comprises, in parts by mass: 100 parts of aqueous phenolic resin, 8 parts of nitrogen-containing flame retardant B1, 15 parts of phosphorus-containing flame retardant C1, 10 parts of halogen flame retardant F1,5 parts of antimony flame retardant G1 and 7.5 parts of phosphorus-nitrogen flame retardant H1; the second resin composition comprises the following components in parts by mass: 100 parts of epoxy resin D1, 50 parts of phenolic novolac resin and 0.1 part of curing accelerator.
The preparation method of the bonding sheet comprises the following steps:
(1) Adding water-based phenolic resin, a nitrogen-containing flame retardant, a phosphorus-containing flame retardant, a halogen flame retardant, an antimony flame retardant, a phosphorus-nitrogen flame retardant and water into a container according to the formula amount, stirring to uniformly mix the materials, and finally adjusting the solid content to 20% by using water to obtain a first glue solution; impregnating the first glue solution with wood pulp fiber paper for 18s, and then drying at 220 ℃ for 4min to obtain prepreg;
(2) Adding epoxy resin, linear phenolic resin, a curing accelerator and acetone into a container according to the formula amount, stirring to uniformly mix the epoxy resin, the linear phenolic resin, the curing accelerator and the acetone, and finally, regulating the solid content to be 60% by using the acetone to obtain a second glue solution; and (3) impregnating the second glue solution with the prepreg obtained in the step (1) for 12s, and then drying at 180 ℃ for 3min to obtain the bonding sheet.
Comparative example 7
An adhesive sheet differing from example 1 only in that the first resin composition comprises, in parts by mass: 100 parts of aqueous phenolic resin, 8 parts of nitrogen-containing flame retardant B1, 15 parts of phosphorus-containing flame retardant C1 and 7.5 parts of phosphorus-nitrogen flame retardant H1; the second resin composition comprises the following components in parts by mass: 100 parts of epoxy resin D1, 50 parts of phenolic novolac resin, 10 parts of halogen flame retardant F1,5 parts of antimony flame retardant G1 and 0.1 part of curing accelerator.
The preparation method of the bonding sheet comprises the following steps:
(1) Adding the water-based phenolic resin, the nitrogen-containing flame retardant, the phosphorus-nitrogen flame retardant and water into a container according to the formula amount, stirring to uniformly mix the materials, and finally adjusting the solid content to 20% by using water to obtain a first glue solution; impregnating the first glue solution with wood pulp fiber paper for 16s, and then drying at 220 ℃ for 4min to obtain prepreg;
(2) According to the formula amount, adding epoxy resin, linear phenolic resin, halogen flame retardant, antimony flame retardant, curing accelerator and acetone into a container, stirring to uniformly mix, and finally regulating the solid content to 60% by using acetone to obtain a second glue solution; and (3) impregnating the second glue solution with the prepreg obtained in the step (1) for 13s, and then drying at 180 ℃ for 3min to obtain the bonding sheet.
The adhesive sheets provided in comparative examples 4 to 7 were prepared into CEM-1 copper-clad plates in the same manner as described in example 1, and performance tests were performed by the same method, and the test results are shown in Table 3.
TABLE 3 Table 3
As can be seen from the performance data in Table 1, table 2 and Table 3, the invention improves the fire resistance, heat resistance and workability of the adhesive sheet by the design and mutual cooperation of the first resin composition and the second resin composition, and further optimizes each component in the resin composition to ensure that the CEM-1 copper-clad plate provided in examples 1 to 9 has the fire resistance of V-0 grade, the punching workability of 5 grade, the thermal stress (288 ℃) of 162 to 205 seconds, the thermal stress (288 ℃) of 108 to 137 seconds, the T260 of 83 to 97 minutes, the water absorption of 0.08 to 0.1 percent, and has excellent fire resistance, heat resistance and punching workability, low water absorption and better comprehensive performance.
Further, as is clear from analysis of examples 1 to 9 and examples 10 to 13, the heat resistance of example 10 was significantly reduced, the punching workability of examples 11 and 13 was significantly insufficient, and the flame retardancy of example 12 was low; therefore, in the second resin composition, when the halogen flame retardant is 5-15 parts, the antimony flame retardant is 2-8 parts and the phosphorus-nitrogen flame retardant is 5-10 parts, the components are mutually cooperated, so that the copper-clad plate can obtain better balance effect among heat resistance, punching processability and flame retardance.
Analysis of examples 1 to 9 and comparative examples 1 to 3 revealed that the flame retardancy of comparative example 1 was significantly reduced, the heat resistance of comparative example 2 was poor, and the heat resistance and punching properties of comparative example 3 were both reduced. Therefore, according to the invention, through the design and the compounding of the first resin composition and the second resin composition, especially the phosphorus-nitrogen flame retardant, the antimony flame retardant and the halogen flame retardant are introduced into the second resin composition to construct a compound flame retardant system, the flame retardance of the copper-clad plate is remarkably contributed, the consumption of the halogen flame retardant is greatly reduced, and the heat resistance and the processability are remarkably improved.
Analysis example 1 and comparative examples 4 to 7 show that the heat resistance, flame retardance and punching property of comparative examples 4 to 7 are reduced to different degrees, and the water absorption is improved, which shows that the copper-clad plate has excellent heat resistance, flame retardance, punching property and lower water absorption by the specific design of the dipping sequence of the primary glue solution and the secondary glue solution by respectively using the first resin, the nitrogen-containing flame retardant and the phosphorus-containing flame retardant and the second resin, and the antimony-based flame retardant, the halogen-based flame retardant and the phosphorus-nitrogen flame retardant.
The applicant states that the present invention is illustrated by the above examples as well as the method of making and using the same, but the present invention is not limited to, i.e., does not mean that the present invention must be practiced in dependence upon 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. An adhesive sheet, characterized in that the adhesive sheet comprises a reinforcing material, and a resin composition attached to the reinforcing material by two impregnation drying;
the resin composition comprises a first resin composition attached after the first impregnation drying and a second resin composition attached after the second impregnation drying;
the first resin composition includes a combination of a phenolic resin, a nitrogen-containing flame retardant, and a phosphorus-containing flame retardant;
the second resin composition includes a combination of an epoxy resin, a curing agent, a halogen-based flame retardant, an antimony-based flame retardant, and a phosphorus-nitrogen flame retardant.
2. The bonding sheet according to claim 1, wherein the phenolic resin is an aqueous phenolic resin;
preferably, the phenolic resin has a number average molecular weight of 100-2000g/mol.
3. The adhesive sheet according to claim 1 or 2, wherein the nitrogen-containing flame retardant is 5 to 10 parts by mass based on 100 parts by mass of the phenolic resin;
preferably, the nitrogen-containing flame retardant comprises any one or a combination of at least two of vinyl isocyanate, melamine glyoxal resin, melamine formaldehyde resin, methylated melamine resin, butylated melamine resin, triisocyanurate modified melamine resin and organosilicon modified melamine resin;
preferably, the mass of the phosphorus-containing flame retardant is 10-20 parts based on 100 parts of the mass of the phenolic resin;
preferably, the phosphorus-containing flame retardant comprises any one or a combination of at least two of alkoxycyclotriphosphazene, phenoxycyclotriphosphazene, hexa-para-aldehyde phenoxycyclotriphosphazene, hexa (4-DOPO methylolphenoxy) cyclotriphosphazene, (2-allylphenoxy) pentaphenoxy cyclotriphosphazene and hexa (4-nitrophenoxy) cyclotriphosphazene.
4. A bonding sheet according to any one of claims 1-3, wherein the epoxy resin comprises any one or a combination of at least two of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin;
preferably, the mass of the curing agent is 20-80 parts based on 100 parts of the mass of the epoxy resin;
preferably, the curing agent comprises any one or a combination of at least two of vegetable oil modified phenolic resin, linear phenolic resin and thermosetting phenolic resin.
5. The adhesive sheet according to any one of claims 1 to 4, wherein the halogen-based flame retardant is 5 to 15 parts by mass based on 100 parts by mass of the epoxy resin;
preferably, the halogen flame retardant comprises any one or a combination of at least two of tetrabromobisphenol A, tribromophenol, decabromodiphenylethane and octabromodiphenylethane;
preferably, the mass of the antimony-based flame retardant is 2-8 parts based on 100 parts by mass of the epoxy resin;
preferably, the antimony-based flame retardant comprises any one or a combination of at least two of antimony oxide, antimony halide and antimonate;
preferably, the mass of the phosphorus-nitrogen flame retardant is 5-10 parts based on 100 parts of the mass of the epoxy resin;
preferably, the phosphorus nitrogen flame retardant comprises any one or a combination of at least two of ammonium polyphosphate, melamine polyphosphate, phosphazene compound.
6. The adhesive sheet according to any one of claims 1 to 5, wherein the second resin composition further comprises a curing accelerator;
preferably, the mass of the curing accelerator is less than or equal to 1 part based on 100 parts by mass of the epoxy resin;
preferably, the curing accelerator comprises any one or a combination of at least two of tertiary amine, tertiary phosphine, organic metal complex, imidazole compound and quaternary ammonium salt.
7. The bonding sheet of any of claims 1-6, wherein the reinforcing material comprises at least one of wood pulp paper, cotton pulp paper, or nonwoven fabric.
8. A method of producing the adhesive sheet according to any one of claims 1 to 7, comprising:
placing the reinforcing material into glue solution of a first resin composition for first impregnation and then carrying out first drying to obtain prepreg;
and (3) placing the prepreg in a glue solution of a second resin composition for second impregnation and then carrying out second drying to obtain the bonding sheet.
9. A metal foil-clad laminate, characterized in that the metal foil-clad laminate comprises a metal foil and at least one adhesive sheet according to any one of claims 1-7;
preferably, the metal foil-clad laminate is a CEM-1 copper-clad plate, and the CEM-1 copper-clad plate comprises a laminate and copper foils arranged on one side or two sides of the laminate; the laminate comprises a facing and a core comprising at least one adhesive sheet according to any one of claims 1-7.
10. A printed circuit board, characterized in that the printed circuit board comprises an adhesive sheet according to any one of claims 1-7 and/or a metal foil-clad laminate according to claim 9.
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| CN202311620824.4A CN117604827A (en) | 2023-11-30 | 2023-11-30 | Adhesive sheet and preparation method and application thereof |
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