CN114085436B - Glue solution, prepreg, circuit substrate and printed circuit board - Google Patents
Glue solution, prepreg, circuit substrate and printed circuit board Download PDFInfo
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- CN114085436B CN114085436B CN202111471357.4A CN202111471357A CN114085436B CN 114085436 B CN114085436 B CN 114085436B CN 202111471357 A CN202111471357 A CN 202111471357A CN 114085436 B CN114085436 B CN 114085436B
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- 239000003292 glue Substances 0.000 title claims abstract description 89
- 239000000758 substrate Substances 0.000 title claims abstract description 51
- 239000004094 surface-active agent Substances 0.000 claims abstract description 83
- 239000000945 filler Substances 0.000 claims abstract description 60
- 239000003960 organic solvent Substances 0.000 claims abstract description 50
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 239000004593 Epoxy Substances 0.000 claims abstract description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 13
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 7
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 25
- 229920002857 polybutadiene Polymers 0.000 claims description 25
- 239000012779 reinforcing material Substances 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 6
- 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 description 5
- 239000003063 flame retardant Substances 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920001195 polyisoprene Polymers 0.000 claims description 4
- 239000004643 cyanate ester Substances 0.000 claims description 3
- 238000010030 laminating Methods 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000004513 sizing Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 83
- 239000000377 silicon dioxide Substances 0.000 description 41
- 239000011248 coating agent Substances 0.000 description 29
- 238000000576 coating method Methods 0.000 description 29
- 239000004744 fabric Substances 0.000 description 25
- 239000003365 glass fiber Substances 0.000 description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 24
- 239000011889 copper foil Substances 0.000 description 22
- 238000007598 dipping method Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 17
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 14
- 239000008096 xylene Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 239000003822 epoxy resin Substances 0.000 description 11
- 229920000647 polyepoxide Polymers 0.000 description 11
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 7
- 238000000465 moulding Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- -1 2-ethylhexyl Chemical group 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920013638 modified polyphenyl ether Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NDRKXFLZSRHAJE-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4-tribromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=CC=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br NDRKXFLZSRHAJE-UHFFFAOYSA-N 0.000 description 1
- FIAXCDIQXHJNIX-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-ethylbenzene Chemical compound CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br FIAXCDIQXHJNIX-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 1
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-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
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- KQNZLOUWXSAZGD-UHFFFAOYSA-N benzylperoxymethylbenzene Chemical compound C=1C=CC=CC=1COOCC1=CC=CC=C1 KQNZLOUWXSAZGD-UHFFFAOYSA-N 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 1
- FMWLUWPQPKEARP-UHFFFAOYSA-N bromodichloromethane Chemical compound ClC(Cl)Br FMWLUWPQPKEARP-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 125000000113 cyclohexyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- JZZBTMVTLBHJHL-UHFFFAOYSA-N tris(2,3-dichloropropyl) phosphate Chemical compound ClCC(Cl)COP(=O)(OCC(Cl)CCl)OCC(Cl)CCl JZZBTMVTLBHJHL-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- NWIKMSABBNGQRG-UHFFFAOYSA-N tris(3,3-dibromopropyl) phosphate Chemical compound BrC(Br)CCOP(=O)(OCCC(Br)Br)OCCC(Br)Br NWIKMSABBNGQRG-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a glue solution, which comprises resin, filler, surfactant, curing agent and organic solvent, wherein the resin is provided with a first reactive group, and the structural formula of the surfactant is shown as formula (1):
Description
Technical Field
The invention relates to the technical field of electronic industry, in particular to glue solution, prepreg, circuit substrate and printed circuit board.
Background
Based on the requirement of the 5G communication application scene on the dielectric property of the circuit substrate, in the traditional method, some surfactants are usually added into the glue solution to optimize the interfacial tension so as to improve the binding force, dispersibility or compatibility of each phase in the glue solution and improve the dielectric property of the circuit substrate.
However, when the glue solution of the aqueous system is adopted, the temperature is higher than 380 ℃ when reinforcing materials such as glass fiber cloth are immersed and sized, so that the surfactant can be decomposed and volatilized, and finally no surfactant remains in the pressed circuit substrate; however, when the glue solution of the organic solvent system is adopted, the temperature is below 200 ℃ when the reinforcing material such as glass fiber cloth is used for dipping and sizing, and the decomposition temperature of the surfactant is not reached, so that the surfactant remains in the prepreg, and free surfactant exists in the circuit substrate synthesized by pressing, and the thermal stability and reliability of the circuit substrate are further affected.
Disclosure of Invention
In view of the above, it is necessary to provide a glue solution, a prepreg, a circuit board, and a printed circuit board, and a circuit board manufactured using the glue solution has excellent thermal stability and reliability.
The glue solution comprises resin, filler, surfactant, curing agent and organic solvent, wherein the molecular chain of the resin is provided with a first reactive group, and the structural formula of the surfactant is shown as formula (1):
in the formula (1), R is a second reactive group, and the molecular weight of the surfactant is 2000-3500;
wherein the first reactive group is selected from vinyl, epoxy, cyanate, amino or anhydride and the second reactive group is selected from vinyl or epoxy.
In one embodiment, in formula (1), m=12-17, n=4 or 5, x=1-5, y=6-20, z=4-7.
In one embodiment, the first reactive group and the second reactive group are the same cure system reactive group.
In one embodiment, the contact angle of the glue solution on the molding plate is 0-50 degrees at 25+/-1 ℃, wherein the molding plate is made of the filler.
In one embodiment, the resin comprises at least one of polybutadiene, a copolymer of polybutadiene and styrene, polyisoprene, modified polybutadiene, polyphenylene oxide, modified polyphenylene oxide, polyimide, epoxy resin, modified epoxy resin, cyanate ester, isocyanate.
In one embodiment, the filler is used in an amount of 150 to 350 parts by weight, the surfactant is used in an amount of 0.5 to 3 parts by weight, and the curing agent is used in an amount of 1 to 20 parts by weight, based on 100 parts by weight of the resin.
In one embodiment, the glue solution further comprises a flame retardant.
A prepreg comprising a reinforcing material and said glue solution after drying attached to said reinforcing material.
A circuit substrate comprises an insulating layer and a conductive layer arranged on at least one surface of the insulating layer, wherein the insulating layer is formed by pressing one or at least two overlapped prepregs.
A printed circuit board is made of the circuit substrate.
In the glue solution, the surfactant with the structural formula shown in the formula (1) is adopted, and the surfactant has a hydrophilic end and an oleophylic end, so that the surfactant can be combined with the filler through the hydrophilic end, and the filler is uniformly dispersed in the glue solution by utilizing good compatibility of the oleophylic end with resin and an organic solvent, and meanwhile, the surfactant can also provide electrostatic repulsion and steric hindrance to effectively prevent collision and agglomeration among the fillers. Furthermore, the surface tension of the glue solution can be regulated by the surfactant with the structural formula shown in the formula (1), so that each component in the glue solution can be quickly and uniformly distributed and stable in the mixing process, and therefore, the glue solution has better glue coating manufacturability.
In addition, in the glue solution, the molecular chain of the resin is provided with the first reactive group, and the surfactant with the structural formula shown in the formula (1) is provided with the second reactive group, so that the second reactive group in the molecular chain of the surfactant can react with the first reactive group in the molecular chain of the resin in the lamination and solidification process of the prepreg into the insulating layer, so that the two can form chemical combination, the surfactant can be locked in a solidified molecular network in a chemical combination mode, and the surfactant is prevented from being released in a circuit substrate, and therefore, the thermal stability and reliability of the circuit substrate can be effectively improved.
Detailed Description
The glue solution, the prepreg, the circuit substrate and the printed circuit board provided by the invention are further described below.
The glue solution provided by the invention comprises resin, filler, surfactant, curing agent and organic solvent.
Wherein the resin has a first reactive group selected from vinyl, epoxy, cyanate, amino, or anhydride groups.
Optionally, the resin comprises at least one of polybutadiene, a copolymer of polybutadiene and styrene, polyisoprene, modified polybutadiene, polyphenylene oxide, modified polyphenylene oxide, polyimide, epoxy resin, modified epoxy resin, cyanate ester, isocyanate.
Optionally, the filler comprises at least one of titanium dioxide, barium titanate, strontium titanate, silica, corundum, wollastonite, solid glass microspheres, synthetic glass, quartz, boron nitride, aluminum nitride, silicon carbide, aluminum carbide, beryllium oxide, aluminum hydroxide, magnesium oxide, mica, talc, or magnesium hydroxide.
The structural formula of the surfactant is shown as formula (1):
in formula (1), R is a second reactive group selected from vinyl or epoxy.
In order to make the surfactant have good compatibility in the glue solution, the molecular weight of the surfactant shown in the formula (1) is preferably 2000-3500.
In the surfactant represented by the formula (1), m, n, x, y and z are not limited, and the use effect of the surfactant is not affected.
Since the more x and m, the better the lipophilicity of the surfactant, the more z and n, the better the hydrophilicity of the surfactant, the more m and n, the longer the branches, the higher the degree of freedom of the surfactant, but also the lower the thermal stability and compatibility, the more y, the better the reactivity of the surfactant, but too much also the compatibility. Thus, in formula (1), m is preferably an integer of 12 to 17, n is preferably 4 or 5, x is preferably an integer of 1 to 5, y is preferably an integer of 6 to 20, and z is preferably an integer of 4 to 7, so that the molecular weight of the surfactant is in the range of 2000 to 3500, and at the same time, excellent thermal stability and compatibility are provided.
Taking the second reactive group as vinyl as an example, the surfactant can be prepared by reacting octadecyl methacrylate, polyethylene glycol methacrylate and 1, 4-pentadiene, wherein the structural formula is shown as formula (1-1),
when the second reactive group is an epoxy group, the epoxy group may be directly epoxidized from a vinyl group, for example, the surfactant having the structural formula (1-1) may be epoxidized to obtain the surfactant having the structural formula (1-2).
Of course, when the second reactive group is an epoxy group, the surfactant may be synthesized by a polymerization method.
Optionally, the curing agent comprises at least one of dicyandiamide, diaminodiphenyl sulfone, diaminodiphenyl methane, styrene-maleic anhydride copolymer, phenolic resin, active ester, benzoxazine, 2, 5-dimethyl-2, 5-di (benzyl peroxide) hexane, di-tert-butyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di-tert-butylperoxy-3-hexyne, dicumyl peroxide.
Optionally, the organic solvent comprises at least one of toluene, xylene, butanone, acetone, dichloromethane, N-dimethylformamide and propylene glycol monomethyl ether.
Optionally, the glue solution further comprises a flame retardant to enable the circuit substrate to have flame retardant performance, wherein the flame retardant comprises at least one of tributyl phosphate, tri (2-ethylhexyl) phosphate, tri (2-chloroethyl) phosphate, tri (2, 3-dichloropropyl) phosphate, tri (2, 3-dibromopropyl) phosphate, pyrol99, toluene-diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, (2-ethylhexyl) -diphenyl phosphate, chlordane anhydride, dibromomethane, trichlorobromomethane, dichlorobromomethane, octabromodiphenyl oxide, pentabromoethyl benzene, tetrabromobisphenol A, tri (dibromopropyl) phosphate, halogenated cyclohexane and derivatives thereof, decabromodiphenyl ether and derivatives thereof.
Alternatively, the filler is used in an amount of 150 to 350 parts by weight, the surfactant is used in an amount of 0.5 to 3 parts by weight, and the curing agent is used in an amount of 1 to 20 parts by weight, based on 100 parts by weight of the resin.
As shown in formula (1), the surfactant adopted in the glue solution has a hydrophilic end and an oleophylic end, so that the surfactant can be combined with the filler through the hydrophilic end, and the filler is uniformly dispersed in the glue solution by utilizing good compatibility of the oleophylic end with resin and an organic solvent, and meanwhile, the surfactant can also provide electrostatic repulsive force and steric hindrance, so that collision aggregation among the fillers is effectively prevented. Furthermore, the surface tension of the glue solution can be regulated through the surfactant, so that each component in the glue solution can be quickly and uniformly distributed and stable in the mixing process, and therefore, the glue solution has better manufacturability, and the prepared circuit substrate has excellent thermal stability and reliability.
Optionally, by selecting and controlling the dosage of the surfactant, the contact angle of the glue solution on the molding plate is 0-50 degrees, preferably 0-30 degrees, at 25+/-1 ℃, so that each component in the glue solution can be in a uniformly distributed and stable state.
The contact angle of the glue solution on the molding plate is tested by the following method: the filler is pressed into a molding plate by a precision press, the glue solution is dripped on the molding plate, and then a contact angle measuring device is used for measuring the contact angle at the temperature of 25+/-1 ℃.
Most importantly, the invention is a glue solution of an organic solvent system, the molecular chain of resin in the glue solution is provided with a first reactive group, and the molecular chain of the surfactant is provided with a second reactive group, so that the temperature is below 200 ℃ when reinforcing materials such as glass fiber cloth are impregnated and sized in the preparation process of the prepreg, the surfactant is not decomposed in the prepreg, and the second reactive group in the molecular chain of the surfactant can react with the first reactive group in the molecular chain of the resin in the lamination curing process of the prepreg to form chemical combination, so that the surfactant can be locked in the cured molecular network in a chemical combination mode to avoid the dissociation of the surfactant in a circuit substrate, and the thermal stability and reliability of the circuit substrate can be effectively improved.
In order to allow the second reactive group in the molecular chain of the surfactant to react better with the first reactive group in the molecular chain of the resin, the first reactive group and the second reactive group are preferably reactive groups of the same curing system.
For example, the first reactive group and the second reactive group are each selected from vinyl groups, and in this case, the resin is preferably at least one selected from polybutadiene, a copolymer of polybutadiene and styrene, polyisoprene, and modified polybutadiene.
When the second reactive group is selected from epoxy, the first reactive group is selected from cyanate, amino, anhydride or epoxy, and at this time, the resin comprises at least one of polyphenyl ether, modified polyphenyl ether, polyimide, epoxy, modified epoxy, cyanate and isocyanate.
The invention also provides a prepreg which comprises a reinforcing material and the dried glue solution attached to the reinforcing material.
The glue solution is formed on the reinforcing material in a coating, dipping and other modes, and the organic solvent in the glue solution is removed through drying, so that the prepreg is obtained.
Wherein the reinforcing material is used for controlling the curing shrinkage of the circuit substrate in the manufacture and providing the circuit substrate with certain mechanical strength, and the reinforcing material is preferably glass fiber cloth, including non-woven fabrics or woven fabrics, such as natural fibers, organic synthetic fibers and inorganic fibers, preferably electronic grade glass fiber cloth.
The invention also provides a circuit substrate which comprises an insulating layer and a conductive layer arranged on at least one surface of the insulating layer, wherein the insulating layer is formed by pressing one or at least two overlapped prepregs.
Wherein in the pressing step, the temperature is 120-250 ℃ and the pressure is 10kg/cm 2 -80kg/cm 2 In the pressing step, the second reactive group in the molecular chain of the surfactant chemically reacts with the first reactive group in the molecular chain of the resin, thereby locking the surfactant in the cured molecular network in a chemically bound form.
It should be noted that the surfactant and the resin in the prepreg are partially reacted, and are completely cured and reacted in the pressing step.
Optionally, the conductive layer is copper foil, and the circuit substrate is a copper-clad plate.
The invention also provides a printed circuit board which is mainly manufactured by the processes of drilling, hole finishing, microetching, presoaking, activating, accelerating, chemical copper and copper thickening and the like of the circuit substrate.
Hereinafter, the glue solution, the prepreg, the circuit board, and the printed circuit board will be further described by the following specific examples.
In the following examples, the surfactant formulas (1-1) to (1-2) used are shown below.
In the formula (1-1), n=4, x=2, y=10, z=4, and the molecular weight is 2404.
In the formula (1-2), n=4, x=2, y=10, z=4, and the molecular weight is 2564.
Example 1
100 parts by weight of polybutadiene, 250 parts by weight of a silica filler, 3 parts by weight of a surfactant represented by the structural formula (1-1), and 5 parts by weight of a dicumyl peroxide curing agent are mixed, and diluted with a xylene organic solvent to obtain a glue solution. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at a temperature of 25℃to be 31℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and heating at 60kg/cm 2 Is pressed for 3 hours at 230 ℃ to prepare the circuit substrate.
Example 2
100 parts by weight of polybutadiene and styrene copolymer, 250 parts by weight of silica filler, 2.5 parts by weight of surfactant with a structural formula shown as a formula (1-1) and 4 parts by weight of dicumyl peroxide curing agent are mixed, and diluted with a xylene organic solvent to obtain a glue solution. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at a temperature of 25℃to be 36℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and heating at 60kg/cm 2 Is pressed for 3 hours at 230 ℃ to prepare the circuit substrate.
Example 3
100 parts by weight of epoxy resin, 200 parts by weight of silica filler, 1.5 parts by weight of surfactant with a structural formula shown as a formula (1-2) and 12 parts by weight of diamino diphenyl sulfone curing agent are mixed, and the mixture is diluted with a butanone organic solvent to obtain a glue solution. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at a temperature of 25℃to 40℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and coating with 40kg/cm 2 Is pressed for 3 hours at 200 ℃ to prepare the circuit substrate.
Example 4
100 parts by weight of polybutadiene, 320 parts by weight of a silica filler, 3 parts by weight of a surfactant represented by the structural formula (1-1), and 5 parts by weight of a dicumyl peroxide curing agent are mixed, and diluted with a xylene organic solvent to obtain a glue solution. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at a temperature of 25℃to be 34℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and heating at 60kg/cm 2 Is pressed for 3 hours at 230 ℃ to prepare the circuit substrate.
Example 5
100 parts by weight of polybutadiene, 150 parts by weight of a silica filler, 2 parts by weight of a surfactant represented by the structural formula (1-1), and 5 parts by weight of a dicumyl peroxide curing agent are mixed, and diluted with a xylene organic solvent to obtain a glue solution. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at 25℃using a contact angle measuring device at 25 ℃.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and heating at 60kg/cm 2 Is pressed for 3 hours at 230 ℃ to prepare the circuit substrate.
Example 6
100 parts by weight of epoxy resin, 180 parts by weight of silica filler, 2 parts by weight of surfactant with a structural formula shown as a formula (1-2) and 12 parts by weight of diamino diphenyl sulfone curing agent are mixed, and the mixture is diluted by using a butanone organic solvent to obtain glue solution. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at a temperature of 25℃to be 30℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and coating with 40kg/cm 2 Is pressed for 3 hours at 200 ℃ to prepare the circuit substrate.
Example 7
50 parts by weight of epoxy resin, 50 parts by weight of epoxy modified polyphenyl ether, 180 parts by weight of silica filler, 2.5 parts by weight of surfactant with a structural formula shown as a formula (1-2), and 8 parts by weight of diamino diphenyl sulfone curing agent are mixed, and diluted with a butanone organic solvent to obtain a glue solution. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at 25℃to be 24℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and coating with 40kg/cm 2 Is pressed for 3 hours at 200 ℃ to prepare the circuit substrate.
Example 8
70 parts by weight of cyanate, 30 parts by weight of epoxy resin, 170 parts by weight of silica filler, 2 parts by weight of surfactant with a structural formula shown as formula (1-2) and diluting with DMF organic solvent to obtain a glue solution. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at a temperature of 25℃to be 33℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and coating with 50kg/cm 2 Is pressed for 3 hours at 230 ℃ to prepare the circuit substrate.
Example 9
100 parts by weight of polybutadiene, 250 parts by weight of a silica filler, 3 parts by weight of a surfactant (R is vinyl, m=14, n=4, x=2, y=6, z=7, molecular weight is 2834) represented by the structural formula (1), 5 parts by weight of a dicumyl peroxide curing agent, and diluting with a xylene organic solvent to obtain a gum solution. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at a temperature of 25℃to be 32℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and heating at 60kg/cm 2 Is pressed for 3 hours at 230 ℃ to prepare the circuit substrate.
Example 10
100 parts by weight of polybutadiene, 250 parts by weight of a silica filler, 3 parts by weight of a surfactant (R is vinyl, m=12, n=5, x=4, y=17, z=4, molecular weight is 3452) represented by the structural formula (1), 5 parts by weight of a dicumyl peroxide curing agent, and diluted with a xylene organic solvent to obtain a gum solution. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at a temperature of 25℃to be 31℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and heating at 60kg/cm 2 Is pressed for 3 hours at 230 ℃ to prepare the circuit substrate.
In the following comparative examples, the surfactant formulas (2) to (3) used are shown below.
In the formula (2), n=4, x=2, y=10, z=4, and the molecular weight is 2134.
In formula (3), n=4, x=2, y=10, z=4, and the molecular weight is 2464.
Comparative example 1
100 parts by weight of polybutadiene, 200 parts by weight of a silica filler, 2 parts by weight of a surfactant represented by the structural formula (2), and 5 parts by weight of a dicumyl peroxide curing agent are diluted with a xylene organic solvent to obtain a glue solution. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at a temperature of 25℃to be 34℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and heating at 60kg/cm 2 Is pressed for 3 hours at 230 ℃ to prepare the circuit substrate.
Comparative example 2
100 parts by weight of polybutadiene and styrene copolymer, 210 parts by weight of silica filler, 2.5 parts by weight of surfactant with a structural formula shown as a formula (2), and 5 parts by weight of dicumyl peroxide curing agent are diluted with a xylene organic solvent to obtain a glue solution. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at a temperature of 25℃to be 32℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and heating at 60kg/cm 2 Is pressed for 3 hours at 230 ℃ to prepare the circuit substrate.
Comparative example 3
100 parts by weight of epoxy resin, 200 parts by weight of silica filler, 1.5 parts by weight of surfactant with a structural formula shown as a formula (2), and 12 parts by weight of diamino diphenyl sulfone curing agent are diluted by a butanone organic solvent to obtain a glue solution. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at a temperature of 25℃to be 41℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and coating with 40kg/cm 2 Is pressed for 3 hours at 200 ℃ to prepare the circuit substrate.
Comparative example 4
100 parts by weight of epoxy resin, 180 parts by weight of silica filler, 2.5 parts by weight of surfactant with a structural formula shown as a formula (3), and 12 parts by weight of diamino diphenyl sulfone curing agent are diluted by a butanone organic solvent to obtain a glue solution. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at 25℃to be 24℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and coating with 40kg/cm 2 Is pressed for 3 hours at 200 ℃ to prepare the circuit substrate.
Comparative example 5
100 parts by weight of polybutadiene, 250 parts by weight of a silica filler and 5 parts by weight of dicumyl peroxide curing agent are diluted with a xylene organic solvent to obtain a glue solution. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at 25℃to be 68℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and heating at 60kg/cm 2 Is pressed for 3 hours at 230 ℃ to prepare the circuit substrate.
Comparative example 6
100 parts by weight of epoxy resin, 180 parts by weight of silica filler and 12 parts by weight of diaminodiphenyl sulfone curing agent are diluted with a butanone organic solvent to obtain a glue solution. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at 25℃to be 63℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and coating with 40kg/cm 2 Is pressed for 3 hours at 200 ℃ to prepare the circuit substrate.
Comparative example 7
100 parts by weight of polybutadiene, 220 parts by weight of a silica filler, 1.5 parts by weight of a surfactant (n=4, x=2, y=2, z=2, molecular weight 1336) represented by the structural formula (1-1), 5 parts by weight of a dicumyl peroxide curing agent, and diluting with a xylene organic solvent to obtain a gum solution. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at a temperature of 25℃to be 52℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and heating at 60kg/cm 2 Is pressed for 3 hours at 230 ℃ to prepare the circuit substrate.
Comparative example 8
100 parts by weight of polybutadiene, 220 parts by weight of a silica filler, 1.5 parts by weight of a surfactant (n=4, x=2, y=20, z=8, molecular weight 4132) represented by the structural formula (1-1), and 5 parts by weight of a dicumyl peroxide curing agent were diluted with a xylene organic solvent to obtain a dope. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at a temperature of 25℃to be 48℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and heating at 60kg/cm 2 Is pressed for 3 hours at 230 ℃ to prepare the circuit substrate.
Comparative example 9
100 parts by weight of polybutadiene, 220 parts by weight of a silica filler, 1.5 parts by weight of a surfactant (R is vinyl, m=20, n=7, x=2, y=10, z=6, molecular weight is 4564) represented by the structural formula (1), 5 parts by weight of a dicumyl peroxide curing agent, and diluted with a xylene organic solvent to obtain a dope. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at a temperature of 25℃to be 45℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and heating at 60kg/cm 2 Is pressed for 3 hours at 230 ℃ to prepare the circuit substrate.
Comparative example 10
100 parts by weight of polybutadiene, 220 parts by weight of a silica filler, 1.5 parts by weight of a surfactant (R is vinyl, m=12, n=4, x=6, y=10, z=8, molecular weight is 4384) represented by the structural formula (1), 5 parts by weight of a dicumyl peroxide curing agent, and diluted with a xylene organic solvent to obtain a dope. The silica filler was pressed into a mold plate by a precision press, the obtained dope was dropped on the mold plate, and the contact angle was measured at a temperature of 25℃to be 43℃by using a contact angle measuring device.
And (3) dipping the glue solution into glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, coating copper foil on upper and lower sides, and heating at 60kg/cm 2 Is pressed for 3 hours at 230 ℃ to prepare the circuit substrate.
The glue solutions of examples 1 to 10 and comparative examples 1 to 10 and the properties of the resulting circuit substrates were tested, the specific test contents and standards are shown below, and the test results are shown in table 1.
Viscosity was measured using 3# Cai Enbei, and the viscosities of all examples and comparative examples were measured by stirring for the same time under the same solids content.
Thermal stability Td the temperature at which the substrate loses 5wt% weight was measured using a thermogravimetric analyzer according to ASTM D3850 standard.
The peel strength was tested according to the IPC-TM-6502.4.8 standard.
TABLE 1
As is clear from comparison of examples 1 and 5, examples 6 and 6 in table 1, the same system has a larger decrease in contact angle and a smaller viscosity of the dope, indicating that the filler can be rapidly dispersed in the dope, and that the addition of a proper amount of the surfactant has no larger influence on Td and peel strength of the substrate due to reactivity of the surfactant.
Examples 1, 2, 4, 5 and comparative examples 1, 2, examples 3, 6 and comparative examples 3, 4 in comparative table 1 show that the surfactant with or without reactive groups can effectively reduce the contact angle, help the dispersion stability of the filler, and reduce the viscosity of the glue solution, but after further lamination, the surfactant is in a free state in the system due to the surfactant of comparative examples 1-4, which can reduce the thermal stability of the circuit substrate and the peeling reliability of the copper foil.
In addition, as is clear from table 1, the smaller the contact angle of the glue solution on the die plate at 25±1 ℃, the better the gram weight stability of the circuit substrate, which means that the smaller the contact angle, the more uniform the distribution of each component in the glue solution and the better the stability.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. The glue solution is characterized by comprising resin, filler, surfactant, curing agent and organic solvent, wherein the molecular chain of the resin is provided with a first reactive group, and the structural formula of the surfactant is shown as formula (1):
in the formula (1), R is a second reactive group, the molecular weight of the surfactant is 2000-3500, m=12-17, n=4 or 5, x=1-5, y=6-20, and z=4-7;
wherein the first reactive group is selected from vinyl, epoxy, cyanate, amino or anhydride and the second reactive group is selected from vinyl or epoxy.
2. The glue solution of claim 1, wherein the first reactive group and the second reactive group are the same cure system reactive group.
3. The glue of claim 1, wherein the glue has a contact angle of 0-50 ° on a die plate at 25±1 ℃, wherein the die plate is made of the filler.
4. A glue according to any of claims 1-3, wherein the resin comprises at least one of polybutadiene, a copolymer of polybutadiene and styrene, polyisoprene, modified polybutadiene, polyphenylene oxide, modified polyphenylene oxide, polyimide, epoxy, modified epoxy, cyanate ester, isocyanate.
5. A dope according to any one of claims 1 to 3, wherein the filler is used in an amount of 150 to 350 parts by weight, the surfactant is used in an amount of 0.5 to 3 parts by weight, and the curing agent is used in an amount of 1 to 20 parts by weight, based on 100 parts by weight of the resin.
6. A glue according to any of claims 1-3, wherein the glue further comprises a flame retardant.
7. A prepreg comprising a reinforcing material and a dried glue according to any one of claims 1-6 attached to the reinforcing material.
8. A circuit substrate comprising an insulating layer and a conductive layer disposed on at least one surface of the insulating layer, wherein the insulating layer is formed by pressing one or at least two stacked prepregs according to claim 7.
9. A printed circuit board made from the circuit substrate of claim 8.
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Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006028294A (en) * | 2004-07-14 | 2006-02-02 | Hitachi Chem Co Ltd | Solventless one-pack thermosetting epoxy resin composition for filling gap |
| JP2006286852A (en) * | 2005-03-31 | 2006-10-19 | Sumitomo Bakelite Co Ltd | Resin composition, resin layer, carrier material with resin layer and circuit board |
| CN101328277B (en) * | 2008-07-28 | 2010-07-21 | 广东生益科技股份有限公司 | Composite material, high-frequency circuit board made thereof and making method |
| CN102161823B (en) * | 2010-07-14 | 2012-09-26 | 广东生益科技股份有限公司 | Composite material, high-frequency circuit substrate therefrom and manufacture method thereof |
| US8404764B1 (en) * | 2011-09-22 | 2013-03-26 | Elite Material Co., Ltd. | Resin composition and prepreg, laminate and circuit board thereof |
| CN103937157A (en) * | 2014-03-05 | 2014-07-23 | 浙江华正新材料股份有限公司 | Halogen-free resin composition and method for manufacturing prepreg and laminated board by using halogen-free resin composition |
| CN111492006A (en) * | 2017-12-27 | 2020-08-04 | Ａｇｃ株式会社 | Dispersion liquid, metal laminate, and method for producing printed board |
| CN109852002B (en) * | 2019-01-02 | 2021-06-08 | 浙江华正新材料股份有限公司 | Preparation method of light high-strength laminated composite board |
| CN111849122B (en) * | 2019-04-25 | 2022-06-14 | 常熟生益科技有限公司 | Resin composition and application thereof |
| JP2021138947A (en) * | 2020-03-05 | 2021-09-16 | 東レ株式会社 | Resin composition, cured film, and resin-coated glass substrate |
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Denomination of invention: Glue, semi cured film, circuit substrate, printed circuit board Effective date of registration: 20231128 Granted publication date: 20230613 Pledgee: Agricultural Bank of China Limited Hangzhou Yuhang Branch Pledgor: ZHEJIANG HUAZHENG NEW MATERIAL GROUP Co.,Ltd. Registration number: Y2023980067733 |
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