CN115537012A - Resin composition, prepreg, circuit board and printed circuit board - Google Patents
Resin composition, prepreg, circuit board and printed circuit board Download PDFInfo
- Publication number
- CN115537012A CN115537012A CN202211220069.6A CN202211220069A CN115537012A CN 115537012 A CN115537012 A CN 115537012A CN 202211220069 A CN202211220069 A CN 202211220069A CN 115537012 A CN115537012 A CN 115537012A
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- Prior art keywords
- resin composition
- coupling agent
- unsaturated double
- double bond
- hyperbranched polysiloxane
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- 239000011342 resin composition Substances 0.000 title claims abstract description 93
- -1 polysiloxane Polymers 0.000 claims abstract description 145
- 239000007822 coupling agent Substances 0.000 claims abstract description 120
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 119
- 239000000758 substrate Substances 0.000 claims abstract description 65
- 239000000945 filler Substances 0.000 claims abstract description 63
- 238000004132 cross linking Methods 0.000 claims abstract description 20
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 64
- 125000003545 alkoxy group Chemical group 0.000 claims description 47
- 229920001955 polyphenylene ether Polymers 0.000 claims description 39
- 239000000377 silicon dioxide Substances 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 239000011888 foil Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 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 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000003063 flame retardant Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 5
- 239000012779 reinforcing material Substances 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 26
- 229920005989 resin Polymers 0.000 abstract description 26
- 238000004381 surface treatment Methods 0.000 abstract description 7
- 238000003756 stirring Methods 0.000 description 30
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 27
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 21
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 19
- 235000012239 silicon dioxide Nutrition 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 239000011889 copper foil Substances 0.000 description 13
- 239000008096 xylene Substances 0.000 description 11
- 238000010030 laminating Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000004721 Polyphenylene oxide Substances 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
- 229920006380 polyphenylene oxide Polymers 0.000 description 9
- 230000009471 action Effects 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- CWJHMZONBMHMEI-UHFFFAOYSA-N 1-tert-butylperoxy-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1 CWJHMZONBMHMEI-UHFFFAOYSA-N 0.000 description 1
- WTFUTSCZYYCBAY-SXBRIOAWSA-N 6-[(E)-C-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-N-hydroxycarbonimidoyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C/C(=N/O)/C1=CC2=C(NC(O2)=O)C=C1 WTFUTSCZYYCBAY-SXBRIOAWSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 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
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention relates to a resin composition, a prepreg, a circuit substrate and a printed circuit board. The resin composition comprises the following components in parts by weight: 100 parts of polyphenyl ether with unsaturated double bond end capping, 0.1-35 parts of hyperbranched polysiloxane coupling agent, 150-350 parts of filler and solvent; the structural general formula of the hyperbranched polysiloxane coupling agent is shown as a formula (I). According to the resin composition, the hyperbranched polysiloxane coupling agent with the structure shown in the formula (I) is adopted to replace the traditional coupling agent to carry out surface treatment on the filler, so that the filler has better dispersibility in a resin system, and has high crosslinking density with resin, and a circuit substrate has excellent dielectric property, good heat resistance, low thermal expansion coefficient and good apparent property.
Description
Technical Field
The invention relates to the technical field of electronic products, in particular to a resin composition, a prepreg, a circuit substrate and a printed circuit board.
Background
In recent years, with the development of communication technology, high speed of information processing and transmission and high frequency of wireless communication have been required, and electronic materials used therein are required to have excellent dielectric properties, low thermal expansion coefficient and the like. Among them, polyphenylene ether (PPE) is commonly used in the field of circuit board fabrication because of its excellent dielectric properties. However, in practical applications, polyphenylene ether resins have a problem of poor Coefficient of Thermal Expansion (CTE) although they have good dielectric characteristics, making it difficult for polyphenylene ether resins to meet higher requirements in terms of CTE.
In response to this problem, the conventional art mainly increases the content of the filler in the polyphenylene ether resin system, thereby lowering the thermal expansion coefficient of the polyphenylene ether resin system. However, in this way of increasing the CTE performance by increasing the amount of the filler, the problem of non-uniform dispersion of the filler in the polyphenylene ether resin, agglomeration and the like is easily caused due to a large increase in the filler content, so that the circuit substrate made of the resin composition has poor heat resistance and is prone to appearance defects such as dry marks, resin lines and the like.
Disclosure of Invention
In view of the above, it is necessary to provide a resin composition, a prepreg, a circuit board and a printed circuit board, which can provide a circuit board prepared from the resin composition with excellent dielectric properties, good heat resistance, low thermal expansion coefficient and good appearance.
The resin composition comprises the following components in parts by weight: 100 parts of polyphenyl ether with unsaturated double bond end capping, 0.1-35 parts of hyperbranched polysiloxane coupling agent, 150-350 parts of filler and solvent;
the hyperbranched polysiloxane coupling agent has a structural general formula shown in formula (I):
wherein R is 1 Selected from hydrocarbyl groups; r 2 、R 3 And R 4 Each independently selected from alkoxy or unsaturated double bond containing group A, and R 2 、R 3 And R 4 At least one of them is selected from alkoxy; r 5 Selected from groups A containing unsaturated double bonds.
In one embodiment, R 1 Selected from straight chain alkyl with 2-10 carbon atoms;
and/or, R 2 、R 3 And R 4 Each independently selected from alkoxy with 2-9 carbon atoms or unsaturated double bond-containing group A with 2-6 carbon atoms, and R 2 、R 3 And R 4 At least one of them is selected from alkoxy;
and/or, R 5 Is a group A containing unsaturated double bonds and having 2-6 carbon atoms.
In one embodiment, the unsaturated double bond-containing group a includes one of an acrylate group, a methacrylate group, and a vinyl group.
In one embodiment, the alkoxy group accounts for 10% -70% of the terminal group in the hyperbranched polysiloxane coupling, and the group A containing the unsaturated double bond accounts for 30% -90% of the terminal group in the hyperbranched polysiloxane coupling agent.
In one embodiment, the hyperbranched polysiloxane coupling agent has a number average molecular weight of 1500 to 4500.
In one embodiment, the unsaturated double bond-containing end-capped polyphenylene ether has a number average molecular weight of 1000 to 3000;
and/or the polyphenylene ether containing the unsaturated double bond end-capping comprises one or more of vinyl polyphenylene ether, vinyl benzyl polyphenylene ether, acrylate-based polyphenylene ether, methacrylate-based polyphenylene ether and allyl polyphenylene ether.
In one embodiment, the number of the unsaturated double bond-containing groups B in the terminal group of the unsaturated double bond-containing capped polyphenylene ether is 1 to 3.
In one embodiment, the resin composition further comprises one or more of a crosslinking curing agent, an initiator, and a flame retardant.
In one embodiment, the filler comprises one or more of silica, talc, mica, or metal hydroxide.
The prepreg is obtained by coating the resin composition on a reinforcing material and drying.
A circuit substrate comprises a dielectric layer and a metal foil arranged on at least one surface of the dielectric layer; wherein the dielectric layer comprises at least one prepreg as described above.
A printed circuit board is made of the circuit substrate.
In the resin composition, the hyperbranched polysiloxane coupling agent with the structure shown in the formula (I) is adopted to replace the traditional coupling agent to carry out surface treatment on the filler, and because the end group of the hyperbranched polysiloxane coupling agent structure simultaneously has alkoxy and a group A containing unsaturated double bonds, and the alkoxy and the group A containing unsaturated double bonds have a synergistic interaction effect, on one hand, the hyperbranched polysiloxane coupling agent can form efficient coating on the surface of the filler, so that the combination stability between the hyperbranched polysiloxane coupling agent and the filler is improved, the dispersibility of the filler in the resin composition is better, and a circuit substrate prepared by the resin composition has good appearance performance; on the other hand, the hyperbranched polysiloxane coupling agent and the resin have high crosslinking density, so that the bonding strength between the hyperbranched polysiloxane coupling agent and the resin is improved, the bonding strength between the filler and the resin is further improved, the dispersibility of the filler in the resin composition is further better, and the thermal expansion coefficient of a circuit substrate prepared by the resin composition is greatly reduced; and the heat resistance of the circuit substrate prepared by the resin composition is effectively improved.
Therefore, in the resin composition, the hyperbranched polysiloxane coupling agent with the structure shown in the formula (I) is adopted, so that the dispersibility of the filler in the resin composition is better, the filler and the resin have high crosslinking density, and the circuit substrate has excellent dielectric property, good heat resistance, low thermal expansion coefficient and good apparent property.
Drawings
FIG. 1 is a reaction scheme of a hyperbranched polysiloxane coupling agent prepared in example 1 of the present invention;
FIG. 2 is an electron micrograph of a circuit substrate prepared in example 1 of the present invention;
FIG. 3 is an electron micrograph of a circuit substrate according to comparative example 3 of the present invention;
FIG. 4 is a structural formula of the hyperbranched coupling agent of the present invention in comparative example 5.
Detailed Description
The resin composition, prepreg, circuit board and printed circuit board provided by the present invention will be further described below.
The resin composition provided by the invention comprises the following components in parts by weight: 100 parts of polyphenyl ether containing unsaturated double bond end capping, 0.1-35 parts of hyperbranched polysiloxane coupling agent, 150-350 parts of filler and solvent; preferably, the hyperbranched polysiloxane coupling agent is 10 to 20 parts by weight. The hyperbranched polysiloxane coupling agent has a structural general formula shown in formula (I):
wherein R is 1 Selected from hydrocarbyl groups; r 2 、R 3 And R 4 Each independently selected from alkoxy or unsaturated double bond containing group A, and R 2 、R 3 And R 4 At least one of them is selected from alkoxy; r is 5 Selected from groups A containing unsaturated double bonds.
Specifically, R is preferred 1 The resin composition is straight-chain hydrocarbon, so that on one hand, thermal oxidation and thermal degradation can be effectively avoided, and the heat resistance and dielectric stability of the circuit substrate made of the resin composition are ensured; on the other hand, the method can reduce the reaction steric hindrance and improve the synthesis rate of the hyperbranched polysiloxane coupling agent. Meanwhile, R is preferred 1 The straight-chain alkyl group can make the prepared hyperbranched polysiloxane coupling agent have better fluidity, thereby further improving the apparent performance of the circuit substrate made of the resin composition.
Further, R is preferred in the present invention 1 The hyperbranched polysiloxane coupling agent is straight-chain alkyl with 2-10 carbon atoms, and the length of the carbon chain is moderate, so that the hyperbranched polysiloxane coupling agent can be ensured to better treat and coat the surface of the filler, and better compatibility between the filler and resin is ensured, thereby improving the apparent performance of the circuit substrate prepared by using the resin composition and reducing the risk of appearance defects of the circuit substrate.
Considering the influence of the carbon chain length on the activity of the terminal group of the hyperbranched polysiloxane coupling agent, the carbon atom number of the alkoxy group is preferably 2-9, and the carbon atom number is further preferably 2-3.
In order to satisfy the terminal group (R) of the polysiloxane coupling agent 2 、R 3 、R 4 And R 5 ) The carbon number of the unsaturated double bond-containing group A is preferably 2 to 6, so that the hyperbranched polysiloxane coupling agent and the poly (siloxane) can be reactedThe crosslinking density of the phenylate is ensured; and is selected from the R of the unsaturated double bond-containing group A of the carbon chain length 5 Besides the requirement of the reactivity, the steric hindrance can be increased, so that the hyperbranched polysiloxane coupling agent disclosed by the invention has higher density and a more compact structure, no intermolecular winding and better fluidity, the viscosity of the resin composition is further reduced, and a circuit substrate prepared from the resin composition has good apparent performance.
Further, the unsaturated double bond-containing group a includes one of an acrylate group, a methacrylate group and a vinyl group; furthermore, the vinyl group is preferred, so that the reactivity of the hyperbranched polysiloxane coupling agent is higher, the reaction crosslinking density of the resin composition can be improved, and the heat resistance of the circuit substrate prepared by the resin composition is improved.
In the present invention, R is 2 、R 3 And R 4 One or two of the coupling agents can also be selected from polysiloxane, so that further grafting of the coupling agent is realized, and the stability of the hyperbranched structure is improved.
Optionally, the alkoxy group accounts for 10-70% of the terminal group in the hyperbranched polysiloxane coupling agent, and the group A containing unsaturated double bond accounts for 30-90% of the terminal group in the hyperbranched polysiloxane coupling agent; the alkoxy with the content in the range can fully react with the hydroxyl on the surface of the filler to better coat the surface of the filler, so that the compatibility of the resin is improved, the filler is better dispersed in the resin, the bonding stability between the filler and the filler is improved, and the apparent performance of the circuit substrate is improved; and the resin composition has redundant alkoxy groups to be combined with water molecules in the air, a low surface energy layer can be formed after hydrolytic polycondensation, and the resin composition has a non-hydrophilic effect, so that a circuit substrate made of the resin composition has excellent heat resistance and good water resistance.
Meanwhile, the unsaturated double bond-containing group A in the range can ensure that the hyperbranched polysiloxane coupling agent has enough end group activity, so that the hyperbranched polysiloxane coupling agent and resin can generate crosslinking reaction, and the compatibility and the crosslinking density between the hyperbranched polysiloxane coupling agent and the resin are improved; and is not full ofAnd arrangement of the radicals A containing double bonds, in particular the unsaturated double bond-containing radicals A being R 5 When the hyperbranched polysiloxane is used as a group, the steric hindrance between molecules can be increased, so that the free movement of a chain segment of the hyperbranched polysiloxane coupling agent is limited, the winding between molecules is reduced, alkoxy is not wrapped in the chain segment of the hyperbranched polysiloxane coupling agent, the branching degree of the hyperbranched polysiloxane coupling agent is increased, the stability of hyperbranched polysiloxane is improved, the surface treatment capacity of alkoxy on a filler can be promoted, the synergistic effect between alkoxy and unsaturated double bond groups is achieved when the surface treatment is carried out on the filler, the dispersion effect of the filler in resin is improved, and the apparent performance and the heat resistance of a circuit substrate are improved.
In the present invention, the ratio of the alkoxy group and the group a containing an unsaturated double bond to the terminal group in the hyperbranched polysiloxane coupling agent is the ratio of the number of the alkoxy group and the group a containing an unsaturated double bond to the number of the terminal group R in the hyperbranched polysiloxane coupling agent, respectively 2 、R 3 、R 4 And R 5 The total number of (c).
In one or more embodiments, the present invention prefers that the hyperbranched polysiloxane coupling agent has a number average molecular weight of 1500 to 4500. The hyperbranched polysiloxane coupling agent in the range is not easy to volatilize, can better play a role in dispersing the filler, and enables the circuit substrate prepared by the resin composition to have good apparent performance.
In one or more embodiments, the hyperbranched polysiloxane coupling agent provided by the invention is obtained by performing ester exchange polycondensation reaction on alkoxysilane containing an unsaturated double bond and compounds with hydroxyl groups at two ends as raw materials at the temperature of 80-160 ℃ for 2-8 h under the action of an acidic catalyst.
Specifically, the molar ratio of the hydroxyl compound at two ends to the alkoxysilane containing an unsaturated double bond is 0.1-1.5, and the set proportion range can simultaneously have alkoxy and unsaturated double bond groups in the terminal group of the obtained hyperbranched polysiloxane coupling agent, so that the alkoxy group accounts for 10% -70% of the terminal group in the hyperbranched polysiloxane coupling agent, and the group A containing an unsaturated double bond accounts for 30% -90% of the terminal group in the hyperbranched polysiloxane coupling agent, thereby ensuring that the alkoxy group can be effectively coated on the surface of the filler, better realizing the dispersibility of the filler, simultaneously improving the reaction activity with the matrix resin, obtaining a crosslinking structure with high crosslinking density and more compact structure, further improving the bonding strength between the filler and the matrix resin, further better dispersing the filler in the resin, and further improving the heat resistance and the apparent performance of the circuit substrate prepared by using the resin composition.
Further, the unsaturated double bond-containing alkoxysilane includes any one of vinyltrimethoxysilane, methacryloxypropyltrimethoxysilane (KH 570), and vinyltriethoxysilane; the compound with two hydroxyl groups comprises one or more of 1, 3-propylene glycol, neopentyl glycol, butanediol, ethylene glycol, hexanediol and 1, 12-dodecanediol; the acidic catalyst comprises one or more of p-toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, stannic chloride, hydrochloric acid and sulfuric acid.
In view of the viscosity and fluidity of the resin composition, it is further preferable in the present invention that the unsaturated double bond-containing capped polyphenylene ether has a number average molecular weight of 1000 to 3000, and that the unsaturated double bond-containing capped polyphenylene ether in this molecular range not only effectively improves the dielectric characteristics and heat resistance of the circuit board produced using the resin composition, but also has good appearance properties.
In one or more of the embodiments, in the unsaturated double bond containing end-capped polyphenylene ether terminal group, the number of unsaturated double bond containing groups B is 1 to 3; the polyphenylene ether capped with unsaturated double bonds in the range has sufficient reactivity, so that good crosslinking density is obtained, and the heat resistance of a circuit substrate prepared from the resin composition is improved. Preferably, the unsaturated double bond-containing group B includes one of allyl, acrylate, methacrylate, vinyl and vinylbenzyl. Further, the polyphenylene ether having an unsaturated double bond-terminated group includes one or more of a vinyl polyphenylene ether, a vinylbenzyl polyphenylene ether, an acrylate-based polyphenylene ether, a methacrylate-based polyphenylene ether and an allyl polyphenylene ether.
In order to make the surface of the filler have hydroxyl groups, so that the filler can better react with alkoxy groups in the coupling agent, the filler can be uniformly dispersed in the resin and can not agglomerate, and the appearance performance of the circuit substrate made of the resin composition is further improved, the filler preferably comprises one or more of silica, talcum powder, mica and metal hydroxide. Wherein the silica is one or more of crystalline silica, spherical silica and fused silica.
Further, in order to make the circuit substrate made of the resin composition have a low coefficient of thermal expansion, the filler is preferably spherical silica; the amount of the spherical silica is 250 to 350 parts by weight.
In one or more embodiments, the resin composition of the present invention is prepared as follows: adding 100 parts by weight of polyphenylene oxide containing unsaturated double bond end capping into 100-200 parts by weight of solvent, and stirring and dispersing uniformly to obtain a polyphenylene oxide solution containing unsaturated double bond end capping; adding 0.1-35 parts by weight of hyperbranched polysiloxane coupling agent into a solvent, stirring at room temperature for 30-90 min, slowly adding 150-350 parts by weight of filler while stirring, and stirring for 0.5-1.5 h to obtain a filler mixture modified by the hyperbranched polysiloxane coupling agent; and slowly adding the filler mixture modified by the hyperbranched polysiloxane into the obtained polyphenylene ether solution containing the unsaturated double bond end capping, and stirring for 0.5-1.5 h to obtain the resin composition.
In order to better improve the curing rate of the resin composition, in the invention, the resin composition further comprises a crosslinking curing agent, wherein the amount of the crosslinking curing agent is 10-60 parts by weight; the crosslinking curing agent is mainly used for carrying out curing crosslinking reaction with the polyphenylene oxide containing unsaturated double bond capping. Further, it is preferable that the number average molecular weight of the crosslinking curing agent is 100 to 3000; the molecular weight in this range is excellent in fluidity, and a resin composition having higher heat resistance can be easily obtained after curing and crosslinking with polyphenylene ether. In the present invention, the crosslinking curing agent may contain a carbon-carbon unsaturated double bond in a molecule, and the specific type of the crosslinking curing agent is not limited and may be selected as needed.
In order to improve the flame retardancy of the resin composition, in the invention, the resin composition is further limited to further comprise a flame retardant; the type of the flame retardant is not particularly limited, and may be one or a mixture of two or more of a bromine-based flame retardant, a phosphate-based flame retardant, a phosphazene-based flame retardant, a bis-diphenylphosphine oxide-based flame retardant, and a hypophosphite-based flame retardant.
In order to promote the curing reaction of the resin composition, in the present invention, the resin composition further includes an initiator in an amount of 0.1 to 1 part by weight. The kind of the initiator is not particularly limited, and preferably, the initiator may be α, α' -bis (t-butylperoxy-m-isopropyl) benzene. In the present invention, the solvent is not particularly limited, and for example, the solvent may be toluene, acetone, propylene glycol methyl ether, N dimethylformamide, methyl ethyl ketone, or xylene.
The invention also provides a prepreg which is obtained by coating the resin composition on a reinforcing material and drying.
Specifically, the prepared resin composition is coated on a reinforcing material and baked for 1min to 10min at the temperature of 80 ℃ to 180 ℃; and obtaining the prepreg.
In the preparation process of the prepreg, due to the existence of the terminal alkoxy in the structure of the hyperbranched polysiloxane coupling agent, part of alkoxy generally remains after the resin composition is prepared, and the part of the remaining alkoxy can be combined with moisture in the air to react, so that the drying rate of the surface of the prepreg is promoted, and the adhesion between the prepregs is avoided; after the prepreg or the circuit substrate is prepared, the alkoxy group remained at the tail end can form a low surface energy layer after hydrolytic polycondensation, so that the hydrophilic effect is achieved, and the water resistance of the prepreg and the circuit substrate can be improved. Therefore, the prepreg prepared by the resin composition has excellent dielectric property, and not only the heat resistance is effectively improved, but also the water resistance is effectively improved.
In the present invention, the reinforcing material is not particularly limited, and is usually a glass fiber cloth, preferably an E glass fiber cloth.
The invention also provides a circuit substrate, which comprises a dielectric layer and a metal foil arranged on at least one surface of the dielectric layer; wherein the dielectric layer comprises at least one prepreg as described above.
For example, one or more prepregs are laminated and combined to obtain a dielectric layer, one or two surfaces of the dielectric layer are covered with metal foils, and the dielectric layer is laminated for 1h to 5h under the pressure of a hot press of 1.5MPa to 5.0MPa to obtain the circuit substrate.
In the present invention, the specific type of the metal foil is not particularly limited, and the metal foil may be, for example, a copper foil, an aluminum foil, or the like. Preferably, the metal foil is a copper foil.
In the production of a circuit board, a surface of a metal foil bonding surface (matte surface) matching with the polyphenylene ether system is chemically treated, and the surface of the metal foil after the surface chemical treatment has a certain amount of hydroxyl groups and double bond groups. The hyperbranched polysiloxane coupling agent adopted in the resin composition has a structure containing alkoxy and more unsaturated double bonds, so that double bonds and alkoxy are inevitably remained in a prepreg prepared from the resin composition containing the coupling agent; at the moment, the double bonds and the alkoxy groups remained in the prepreg can react with the hydroxyl groups and the double bond groups remained on the surface of the metal foil, so that the combination between the prepreg and the metal foil is realized, and meanwhile, the hyperbranched polysiloxane coupling agent is more stable after being combined with the groups on the surface of the metal foil due to the long molecular chain segment; and the-Si-O-Si-chain segment in the structure of the hyperbranched polysiloxane coupling agent has good flexibility and high tensile strength, so that the stripping strength of the prepared circuit substrate is effectively improved. It is understood that the circuit board of the present invention has excellent dielectric properties, and also has good heat resistance, good appearance properties, and good peel strength.
A printed circuit board is made of the circuit substrate.
Specifically, the printed circuit board is mainly manufactured by the circuit substrate through processes of drilling, hole trimming, microetching, presoaking, activating, accelerating, chemical copper, copper thickening and the like.
Hereinafter, the resin composition, prepreg, circuit substrate and printed circuit board will be further described by the following specific examples.
Example 1
Mixing vinyl triethoxysilane and 1, 3-propylene glycol, wherein the molar ratio of the 1, 3-propylene glycol to the vinyl triethoxysilane is 0.7, reacting for 7h at 100 ℃ under the action of p-toluenesulfonic acid to obtain the hyperbranched polysiloxane coupling agent with the molecular weight of 3800, alkoxy groups accounting for 62% of terminal groups in the hyperbranched polysiloxane coupling agent, and groups A containing unsaturated double bonds accounting for 38% of terminal groups in the hyperbranched polysiloxane coupling agent.
FIG. 1 is a reaction scheme of the hyperbranched polysiloxane coupling agent prepared in example 1. The invention adopts a nuclear magnetic resonance spectrometer to carry out nuclear magnetic resonance hydrogen spectrum test on the hyperbranched polysiloxane coupling agent prepared in the example 1, wherein the nuclear magnetic resonance frequency is 400MHz, and the solvent is CDCl 3 The standard was TMS, and the nuclear magnetic data were as follows: δ 5.45 (m, 1H), δ 5.30 (m, 1H), δ 5.20 (m, 1H), δ 3.77 (m, 4H), δ 1.85 (m, 2H), δ 1.23 (m, 6H). As can be seen from the nuclear magnetic data, δ 5.45ppm is attributed to the end group-Si-CH = 2 The hydrogen proton peak on the middle carbon, delta 5.30-5.20ppm, is attributed to the terminal group-Si-CH = CH 2 The peak of the hydrogen proton on the terminal carbon, delta 3.77ppm, is simultaneously assigned to the terminal Si-O-CH group 2 -CH 3 And a linking group-O-CH 2 -CH 2 -CH 2 The peak of the hydrogen proton on the carbon attached to the oxygen at-O-, delta.1.85 ppm being assigned to the linker-O-CH 2 -CH 2 -CH 2 Hydrogen proton peak on the-O-middle carbon, δ 1.23ppm assigned to the end group-O-CH 2 -CH 3 Hydrogen proton peak on terminal carbon. It can be seen that the terminal groups of the hyperbranched polysiloxane coupling agent prepared in example 1 of the present invention simultaneously contain alkoxy groups and groups a containing unsaturated double bonds.
Adding 100 parts by weight of vinyl benzyl polyphenylene oxide into 150 parts by weight of xylene, and uniformly stirring and dispersing to obtain a vinyl benzyl polyphenylene oxide solution; dissolving 20 parts by weight of the prepared hyperbranched polysiloxane coupling agent in 125 parts by weight of dimethylbenzene, stirring and dispersing for 30min at room temperature, and then slowly adding 320 parts by weight of silicon dioxide while stirring to obtain a silicon dioxide mixture modified by the hyperbranched polysiloxane coupling agent; and then, slowly adding the silicon dioxide mixture modified by the hyperbranched polysiloxane coupling agent into the obtained vinyl benzyl polyphenyl ether solution, and stirring at room temperature for 60min to obtain the resin composition.
And coating the resin composition on E-type glass cloth, and baking at 145 ℃ for 3min to obtain a prepreg.
And overlapping 6 prepregs, coating copper foil with the thickness of 18 mu m on the two surfaces of the prepregs, and pressing in a vacuum hot press, wherein the pressure is 4MPa, and the pressing time is 3h, so as to obtain the circuit substrate.
Example 2
Mixing vinyl triethoxysilane and 1, 3-propylene glycol, wherein the molar ratio of the 1, 3-propylene glycol to the vinyl triethoxysilane is 0.4, reacting for 5h at 120 ℃ under the action of p-toluenesulfonic acid to obtain the hyperbranched polysiloxane coupling agent with the molecular weight of 4500, alkoxy groups accounting for 69% of terminal groups in the hyperbranched polysiloxane coupling agent, and groups A containing unsaturated double bonds accounting for 31% of terminal groups in the hyperbranched polysiloxane coupling agent.
Adding 100 parts by weight of vinyl benzyl polyphenylene oxide into 150 parts by weight of xylene, and uniformly stirring and dispersing to obtain a vinyl benzyl polyphenylene oxide solution; dissolving 20 parts by weight of the prepared hyperbranched polysiloxane coupling agent in 125 parts by weight of xylene solvent, stirring and dispersing for 60min at room temperature, and then slowly adding 320 parts by weight of silicon dioxide while stirring to obtain a silicon dioxide mixture modified by the hyperbranched polysiloxane coupling agent; and then, slowly adding the silicon dioxide mixture modified by the hyperbranched polysiloxane coupling agent into the obtained vinyl benzyl polyphenyl ether solution, and stirring at room temperature for 70min to obtain the resin composition.
And coating the resin composition on E-type glass cloth, and baking at 145 ℃ for 3min to obtain a prepreg.
And overlapping 6 prepregs, covering copper foil with the thickness of 18 mu m on the two sides of the prepregs, and pressing in a vacuum hot press, wherein the pressure is 4MPa, and the pressing time is 3h, so as to obtain the circuit substrate.
Example 3
Mixing vinyl triethoxysilane and 1, 3-propylene glycol, wherein the molar ratio of the 1, 3-propylene glycol to the vinyl triethoxysilane is 1.4, reacting for 4h at 150 ℃ under the action of p-toluenesulfonic acid to obtain the hyperbranched polysiloxane coupling agent with the molecular weight of 1800, alkoxy groups accounting for 16% of terminal groups in the hyperbranched polysiloxane, and groups A containing unsaturated double bonds accounting for 84% of terminal groups in the hyperbranched polysiloxane.
Adding 100 parts by weight of vinyl benzyl polyphenyl ether into 150 parts by weight of dimethylbenzene, and stirring and dispersing uniformly to obtain a vinyl benzyl polyphenyl ether solution; dissolving 20 parts by weight of the prepared hyperbranched polysiloxane coupling agent in 125 parts by weight of xylene solvent, stirring and dispersing for 30min at room temperature, and then slowly adding 320 parts by weight of silicon dioxide while stirring to obtain a silicon dioxide mixture modified by the hyperbranched polysiloxane coupling agent; and then, slowly adding the silicon dioxide mixture modified by the hyperbranched polysiloxane coupling agent into the obtained vinyl benzyl polyphenyl ether solution, and stirring at room temperature for 60min to obtain the resin composition.
Coating the resin composition on E-type glass cloth, and baking at 145 ℃ for 3min to obtain a prepreg;
and overlapping 6 prepregs, covering copper foils with the thickness of 18 mu m on the two surfaces of the prepregs, and laminating in a vacuum hot press, wherein the pressure is 4MPa, and the laminating time is 3h, so as to obtain the circuit substrate.
Example 4
Mixing vinyl triethoxysilane and 1, 3-propylene glycol, wherein the molar ratio of the 1, 3-propylene glycol to the vinyl triethoxysilane is 0.7, reacting for 5h at 120 ℃ under the action of p-toluenesulfonic acid to obtain the hyperbranched polysiloxane coupling agent with the molecular weight of 3800, alkoxy groups accounting for 62% of terminal groups in the hyperbranched polysiloxane coupling agent, and groups A containing unsaturated double bonds accounting for 38% of terminal groups in the hyperbranched polysiloxane coupling agent.
Adding 100 parts by weight of vinyl benzyl polyphenyl ether into 150 parts by weight of dimethylbenzene, and stirring and dispersing uniformly to obtain a vinyl benzyl polyphenyl ether solution; dissolving 5 parts by weight of the prepared hyperbranched polysiloxane coupling agent in 35 parts by weight of xylene solvent, stirring and dispersing for 60min at room temperature, and then slowly adding 150 parts by weight of silicon dioxide while stirring to obtain a silicon dioxide mixture modified by the hyperbranched polysiloxane coupling agent; then, the silica mixture modified by the hyperbranched polysiloxane coupling agent was slowly added to the obtained vinylbenzylpolyphenylene ether solution, and stirred at room temperature for 70min to obtain a resin composition.
And coating the resin composition on E-type glass cloth, and baking at 145 ℃ for 3min to obtain a prepreg.
And overlapping 6 prepregs, covering copper foils with the thickness of 18 mu m on the two surfaces of the prepregs, and laminating in a vacuum hot press, wherein the pressure is 4MPa, and the laminating time is 3h, so as to obtain the circuit substrate.
Example 5
Mixing vinyl triethoxysilane and 1, 3-propylene glycol, wherein the molar ratio of the 1, 3-propylene glycol to the vinyl triethoxysilane is 0.7, reacting for 5h at 120 ℃ under the action of p-toluenesulfonic acid to obtain the hyperbranched polysiloxane coupling agent with the molecular weight of 3800, alkoxy groups accounting for 62% of terminal groups in the hyperbranched polysiloxane coupling agent, and groups A containing unsaturated double bonds accounting for 38% of terminal groups in the hyperbranched polysiloxane coupling agent.
Adding 100 parts by weight of vinyl benzyl polyphenyl ether into 150 parts by weight of dimethylbenzene, and stirring and dispersing uniformly to obtain a vinyl benzyl polyphenyl ether solution; dissolving 12 parts by weight of the prepared hyperbranched polysiloxane coupling agent in 95 parts by weight of xylene solvent, stirring and dispersing for 60min at room temperature, and then slowly adding 250 parts by weight of silicon dioxide while stirring to obtain a silicon dioxide mixture modified by the hyperbranched polysiloxane coupling agent; then, the silica mixture modified by the hyperbranched polysiloxane coupling agent was slowly added to the obtained vinylbenzylpolyphenylene ether solution, and stirred at room temperature for 70min to obtain a resin composition.
And coating the resin composition on E-type glass cloth, and baking at 145 ℃ for 3min to obtain a prepreg.
And overlapping 6 prepregs, covering copper foils with the thickness of 18 mu m on the two surfaces of the prepregs, and laminating in a vacuum hot press, wherein the pressure is 4MPa, and the laminating time is 3h, so as to obtain the circuit substrate.
Example 6
Mixing vinyl triethoxysilane and 1, 12-dodecanediol, wherein the molar ratio of the 1, 12-dodecanediol to the vinyl triethoxysilane is 0.7, reacting for 5h at 120 ℃ under the action of p-toluenesulfonic acid to obtain the hyperbranched polysiloxane coupling agent with the molecular weight of 4400, wherein alkoxy groups account for 62% of terminal groups in the hyperbranched polysiloxane coupling agent, and groups A containing unsaturated double bonds account for 38% of terminal groups in the hyperbranched polysiloxane coupling agent.
Adding 100 parts by weight of vinyl benzyl polyphenylene oxide into 150 parts by weight of xylene, and uniformly stirring and dispersing to obtain a vinyl benzyl polyphenylene oxide solution; dissolving 20 parts by weight of the prepared hyperbranched polysiloxane coupling agent in 125 parts by weight of xylene solvent, stirring and dispersing for 60min at room temperature, and then slowly adding 320 parts by weight of silicon dioxide while stirring to obtain a silicon dioxide mixture modified by the hyperbranched polysiloxane coupling agent; then, the silica mixture modified by the hyperbranched polysiloxane coupling agent was slowly added to the obtained vinylbenzylpolyphenylene ether solution, and stirred at room temperature for 70min to obtain a resin composition.
And coating the resin composition on E-type glass cloth, and baking at 145 ℃ for 3min to obtain a prepreg.
And overlapping 6 prepregs, covering copper foils with the thickness of 18 mu m on the two surfaces of the prepregs, and laminating in a vacuum hot press, wherein the pressure is 4MPa, and the laminating time is 3h, so as to obtain the circuit substrate.
Example 7
Mixing vinyl triethoxysilane and neopentyl glycol, wherein the molar ratio of the neopentyl glycol to the vinyl triethoxysilane is 0.7, reacting for 5 hours at 120 ℃ under the action of p-toluenesulfonic acid to obtain the hyperbranched polysiloxane coupling agent with the molecular weight of 4000, wherein an alkoxy group accounts for 62% of a terminal group in the hyperbranched polysiloxane coupling agent, and a group A containing an unsaturated double bond accounts for 38% of the terminal group in the hyperbranched polysiloxane coupling agent.
Adding 100 parts by weight of vinyl benzyl polyphenyl ether into 150 parts by weight of dimethylbenzene, and stirring and dispersing uniformly to obtain a vinyl benzyl polyphenyl ether solution; dissolving 20 parts by weight of the prepared hyperbranched polysiloxane coupling agent in 125 parts by weight of xylene solvent, stirring and dispersing for 60min at room temperature, and then slowly adding 320 parts by weight of silicon dioxide while stirring to obtain a silicon dioxide mixture modified by the hyperbranched polysiloxane coupling agent; and then, slowly adding the silicon dioxide mixture modified by the hyperbranched polysiloxane coupling agent into the obtained vinyl benzyl polyphenyl ether solution, and stirring at room temperature for 70min to obtain the resin composition.
And coating the resin composition on E-type glass cloth, and baking at 145 ℃ for 3min to obtain a prepreg.
And overlapping 6 prepregs, covering copper foils with the thickness of 18 mu m on the two surfaces of the prepregs, and laminating in a vacuum hot press, wherein the pressure is 4MPa, and the laminating time is 3h, so as to obtain the circuit substrate.
Example 8
The only difference compared with example 1 is that 60 parts by weight of trienyl isocyanurate compound was further added to xylene to prepare a resin composition, a prepreg and a circuit substrate.
Example 9
The only difference compared to example 1 is that talc was used instead of silica to prepare the resin composition, prepreg, and circuit substrate.
Example 10
Compared with example 1, the difference is that the molar ratio of 1, 3-propylene glycol to vinyltriethoxysilane is 1.6, a hyperbranched polysiloxane coupling agent having a molecular weight of 3300, alkoxy groups accounting for 8% of the terminal groups in the hyperbranched polysiloxane coupling agent, and groups a containing unsaturated double bonds accounting for 55% of the terminal groups in the hyperbranched polysiloxane coupling agent is prepared, and a resin composition, a prepreg, and a circuit board are prepared using the same.
Comparative example 1
Compared with the embodiment 1, the difference is that the molar ratio of the 1, 3-propylene glycol to the vinyl triethoxysilane is 2.5, the hyperbranched polysiloxane coupling agent with the alkoxy groups accounting for 0% of the terminal groups in the hyperbranched polysiloxane coupling agent and the unsaturated double bond-containing groups A accounting for 50% of the terminal groups in the hyperbranched polysiloxane coupling agent is prepared, and the resin composition, the prepreg and the circuit substrate are prepared by using the hyperbranched polysiloxane coupling agent.
Comparative example 2
Compared with example 1, the difference is only that methyl triethoxysilane is used for replacing vinyl triethoxysilane, the corresponding hyperbranched polysiloxane coupling agent is prepared, and the resin composition, the prepreg and the circuit substrate are prepared by using the hyperbranched polysiloxane coupling agent.
Comparative example 3
Compared with the embodiment 1, the difference is only that the ordinary silane coupling agent 3- (methacryloyloxy) propyl trimethoxy silane is used for replacing the hyperbranched polysiloxane coupling agent to carry out surface treatment on the silica filler, and a resin composition, a prepreg and a circuit substrate are prepared.
Comparative example 4
Compared with example 1, the difference is only that phenolic hydroxyl polyphenylene ether is used to replace vinyl benzyl polyphenylene ether, and resin compositions, prepregs and circuit substrates are prepared.
Comparative example 5
Compared with example 1, the difference is that hyperbranched coupling agent with the structural formula shown in fig. 4 is used to replace hyperbranched polysiloxane coupling agent to perform surface treatment on silica filler to prepare resin composition, prepreg and circuit substrate.
Analysis of various Properties
In the present invention, 20mL of the resin compositions prepared in examples 1 to 6 and comparative examples 1 to 3 were placed in respective 250mL measuring cylinders, sealed and left to stand for 72 hours, and the presence or absence of the bleeding of the filler from the bottom thereof and the height of the bleeding of the filler were observed, and the test results are shown in Table 1.
TABLE 1
| Height of filler precipitation (mL) | |
| Example 1 | 1.65 |
| Example 2 | 1.63 |
| Example 3 | 2.1 |
| Example 4 | 2.2 |
| Example 5 | 1.75 |
| Example 6 | 3.5 |
| Example 7 | 1.65 |
| Example 8 | 1.6 |
| Example 9 | 3 |
| Example 10 | 3.7 |
| Comparative example 1 | 25 |
| Comparative example 2 | 15 |
| Comparative example 3 | 7 |
| Comparative example 4 | 16 |
| Comparative example 5 | 4 |
As can be seen from Table 1, the resin composition prepared by the present invention has the filler uniformly dispersed therein and has good stability. Meanwhile, by combining the data of example 1 and example 10, it can be seen that the ratio of alkoxy groups to unsaturated double bond-containing groups a in the hyperbranched polysiloxane coupling agent can be controlled by controlling the ratio of the amount of 1, 3-propanediol to vinyltriethoxysilane, thereby controlling the dispersion effect of the filler in the resin. If the amount is outside the range defined in the present invention, the dispersibility of the filler in the resin is lowered. In addition, combining the data of example 1 and comparative examples 1 and 2, it can be seen that the alkoxy group and the unsaturated double bond-containing group a in the structure of the hyperbranched polysiloxane coupling agent of the present invention have a synergistic effect on the surface treatment of the filler, so that the dispersibility of the filler in the resin is better.
The circuit substrates in example 1 and comparative example 3 were respectively taken and tested under an electron microscope under the same testing conditions, and the corresponding electron microscope images are shown in fig. 2 and fig. 3. As can be seen from fig. 2 and 3, the fillers in the circuit substrate of example 1 of the present invention are uniformly dispersed, and there is no filler aggregation, while the fillers in the circuit substrate of comparative example 3 have aggregation, and the light-colored region in the framed region of fig. 3 is the filler aggregation, and the maximum aggregate particle size of the fillers is 18 μm. Therefore, in the circuit substrate prepared by the resin composition, the filler has better dispersity, so that the appearance of the circuit substrate is improved conveniently.
The dielectric properties, heat resistance, dielectric stability, CTE (coefficient of thermal expansion) properties, water resistance and appearance properties of the circuit substrates prepared in examples 1 to 9 and comparative examples 1 to 5 were measured under the same conditions, and the results are shown in table 2.
The measurement method is as follows:
dielectric properties: normal state dielectric loss Df 1 : measured according to the method specified in IEC 61189-721-2015; namely, the Df of each circuit substrate at the frequency of 10GHz is obtained through the test of the SPDR method of the separated dielectric column resonant cavity 1 The value is obtained.
Dielectric stability: dielectric loss Df in thermal state 2 : removing copper foil on the surface of each circuit substrate, treating at 125 ℃ for 72h, and measuring according to the method specified in IEC61189-721-2015 to obtain the copper foil; namely, the Df of each circuit substrate with the removed copper foil at the frequency of 10GHz is obtained through the SPDR method test of the separation medium column resonant cavity 2 ；ΔDf＝Df 2 -Df 1 The smaller the Δ Df value, the better the dielectric stability of the material.
Heat resistance: glass transition temperature (Tg) test: the measurement was carried out by the TMA method defined by IPC-TM-650.4.24.
The agglomerated particle size of the filler is as follows: and detecting each circuit substrate by adopting an electron microscope, observing the dispersion condition of the filler in the circuit substrate under the electron microscope, and measuring the agglomerated particle size of the filler.
CTE (coefficient of thermal expansion): the coefficient of thermal expansion of each circuit board was measured by the CTE test method specified in IPC-TM-650.4.24 using a TMA instrument, and the coefficient of thermal expansion was a Z-axis value of 50 to 260 ℃.
Hydrophobic angle: and (3) measuring the contact angle of the distilled water and each circuit substrate in the air by using a water contact angle measuring instrument, and measuring for many times and averaging to obtain the hydrophobic angle.
The appearance is as follows: each 0.9 m-size circuit board was evaluated by observing the appearance of each circuit board with the copper foil removed by the human eye 2 The number of dried flowers of the circuit substrate in the inner.
TABLE 2
As can be seen from table 2, the hyperbranched polysiloxane coupling agent with a specific structure is adopted in the resin composition of the present invention, compared with the common silane coupling agent and the hyperbranched coupling agent with a structural formula shown in fig. 4, the alkoxy group and the group a containing an unsaturated double bond in the structure of the hyperbranched polysiloxane coupling agent have a synergistic effect, such that the dispersibility of the filler in the polyphenylene ether resin is better, the thermal expansion coefficients of the resin composition and the circuit substrate are greatly reduced, the circuit substrate can have excellent dielectric properties, and at the same time, the heat resistance is improved, the water resistance and peel strength are improved, and the apparent properties are good.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (12)
1. The resin composition is characterized by comprising the following components in parts by weight: 100 parts of polyphenyl ether with unsaturated double bond end capping, 0.1-35 parts of hyperbranched polysiloxane coupling agent, 150-350 parts of filler and solvent;
the hyperbranched polysiloxane coupling agent has a structural general formula shown in formula (I):
wherein R is 1 Selected from hydrocarbyl groups; r 2 、R 3 And R 4 Each independently selected from alkoxy or unsaturated double bond containing group A, and R 2 、R 3 And R 4 At least one of them is selected from alkoxy; r 5 Selected from groups A containing unsaturated double bonds.
2. The resin composition of claim 1, wherein R is 1 Selected from straight chain alkyl with 2-10 carbon atoms;
and/or, R 2 、R 3 And R 4 Each independently selected from alkoxy with 2-9 carbon atoms or unsaturated double bond-containing group A with 2-6 carbon atoms, and R 2 、R 3 And R 4 At least one of them is selected from alkoxy;
and/or, R 5 Selected from unsaturated double bond-containing groups A with 2-6 carbon atoms.
3. The resin composition according to claim 1, wherein the unsaturated double bond-containing group a comprises one of an acrylate group, a methacrylate group, and a vinyl group.
4. The resin composition according to any one of claims 1 to 3, wherein the alkoxy group accounts for 10 to 70% of the terminal group in the hyperbranched polysiloxane coupling, and the unsaturated double bond-containing group A accounts for 30 to 90% of the terminal group in the hyperbranched polysiloxane coupling agent.
5. Resin composition according to any one of claims 1-3, characterized in that the hyperbranched polysiloxane coupling agent has a number average molecular weight of 1500-4500.
6. The resin composition as claimed in any one of claims 1 to 3, wherein the unsaturated double bond-containing capped polyphenylene ether has a number average molecular weight of 1000 to 3000;
and/or the polyphenylene ether containing the unsaturated double bond end-capping comprises one or more of vinyl polyphenylene ether, vinyl benzyl polyphenylene ether, acrylate-based polyphenylene ether, methacrylate-based polyphenylene ether and allyl polyphenylene ether.
7. The resin composition according to any one of claims 1 to 3, wherein the number of the unsaturated double bond-containing groups B in the terminal group of the unsaturated double bond-containing capped polyphenylene ether is 1 to 3.
8. The resin composition according to any one of claims 1 to 3, further comprising one or more of a crosslinking curing agent, an initiator, and a flame retardant.
9. A resin composition according to any of claims 1-3, characterized in that the filler comprises one or more of silica, talc, mica or metal hydroxide.
10. A prepreg obtained by coating a reinforcing material with the resin composition according to any one of claims 1 to 9 and drying the coating.
11. A circuit substrate, comprising a dielectric layer and a metal foil provided on at least one surface of the dielectric layer; wherein the dielectric layer comprises at least one prepreg according to claim 10.
12. A printed circuit board produced from the circuit substrate according to claim 11.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285340A (en) * | 2023-04-06 | 2023-06-23 | 陕西科技大学 | Cable core wrapping tape for high-temperature-resistant muscovite-based flexible cable and preparation method thereof |
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| US20180215971A1 (en) * | 2015-10-21 | 2018-08-02 | Shengyi Technology Co., Ltd. | Polyphenyl ether resin composition and use thereof in high-frequency circuit substrate |
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| CN110229338A (en) * | 2019-04-28 | 2019-09-13 | 武汉理工大学 | A kind of hyperbranched polyorganosiloxane and its preparation method and application |
| CN113801462A (en) * | 2021-09-28 | 2021-12-17 | 浙江华正新材料股份有限公司 | Resin composition, prepreg, circuit board and printed circuit board |
| CN114085525A (en) * | 2021-12-13 | 2022-02-25 | 南亚新材料科技股份有限公司 | Low-thermal expansion coefficient resin composition and application thereof |
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| US20180215971A1 (en) * | 2015-10-21 | 2018-08-02 | Shengyi Technology Co., Ltd. | Polyphenyl ether resin composition and use thereof in high-frequency circuit substrate |
| CN108752592A (en) * | 2018-06-06 | 2018-11-06 | 中国航发北京航空材料研究院 | The synthetic method of dissaving polymer and the application in modified heat convertible resin |
| CN110229338A (en) * | 2019-04-28 | 2019-09-13 | 武汉理工大学 | A kind of hyperbranched polyorganosiloxane and its preparation method and application |
| CN113801462A (en) * | 2021-09-28 | 2021-12-17 | 浙江华正新材料股份有限公司 | Resin composition, prepreg, circuit board and printed circuit board |
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| CN116285340A (en) * | 2023-04-06 | 2023-06-23 | 陕西科技大学 | Cable core wrapping tape for high-temperature-resistant muscovite-based flexible cable and preparation method thereof |
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