CN118307854A - Composite material, circuit substrate manufactured by using composite material and manufacturing method of circuit substrate - Google Patents
Composite material, circuit substrate manufactured by using composite material and manufacturing method of circuit substrateInfo
- Publication number
- CN118307854A CN118307854A CN202410570267.8A CN202410570267A CN118307854A CN 118307854 A CN118307854 A CN 118307854A CN 202410570267 A CN202410570267 A CN 202410570267A CN 118307854 A CN118307854 A CN 118307854A
- Authority
- CN
- China
- Prior art keywords
- filler
- powder
- resin
- composite material
- ptfe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000000758 substrate Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000945 filler Substances 0.000 claims abstract description 104
- 229920005989 resin Polymers 0.000 claims abstract description 65
- 239000011347 resin Substances 0.000 claims abstract description 65
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 62
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 62
- 239000004744 fabric Substances 0.000 claims abstract description 59
- 239000000843 powder Substances 0.000 claims abstract description 58
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 31
- 239000011342 resin composition Substances 0.000 claims abstract description 28
- 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 15
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims abstract description 12
- 239000013032 Hydrocarbon resin Substances 0.000 claims abstract description 11
- 229920006270 hydrocarbon resin Polymers 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 239000003292 glue Substances 0.000 claims description 29
- 239000011521 glass Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 239000005062 Polybutadiene Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229920002857 polybutadiene Polymers 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011888 foil Substances 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 238000007731 hot pressing Methods 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002952 polymeric resin Substances 0.000 claims description 8
- 229920003002 synthetic resin Polymers 0.000 claims description 8
- 238000009941 weaving Methods 0.000 claims description 8
- 229910052582 BN Inorganic materials 0.000 claims description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 6
- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 6
- 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 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000006247 magnetic powder Substances 0.000 claims description 6
- 239000010445 mica Substances 0.000 claims description 6
- 229910052618 mica group Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229920006026 co-polymeric resin Polymers 0.000 claims description 5
- 239000002759 woven fabric Substances 0.000 claims description 5
- ZENYUPUKNXGVDY-UHFFFAOYSA-N 1,4-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=C(C(C)=C)C=C1 ZENYUPUKNXGVDY-UHFFFAOYSA-N 0.000 claims description 4
- ZXLAFQNTMMFLSA-UHFFFAOYSA-N 1-ethenyl-4-[2-(4-ethenylphenyl)ethyl]benzene Chemical compound C1=CC(C=C)=CC=C1CCC1=CC=C(C=C)C=C1 ZXLAFQNTMMFLSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910001369 Brass Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 claims description 4
- 239000010951 brass Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 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 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 239000005350 fused silica glass Substances 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000012876 carrier material Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 230000000704 physical effect Effects 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 7
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 239000011115 styrene butadiene Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical group CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Abstract
The invention discloses a composite material, which comprises the following components: (1) a low dielectric thermosetting resin composition; (2) PTFE woven cloth with or without filler; (3) a powder filler; the low-dielectric thermosetting resin composition is one or two or more of cyanate resin, polyphenyl ether resin, vinyl or acrylic acid group end capped polyphenyl ether resin, polyphenyl ether resin with allyl, bismaleimide resin, vinyl end capped siloxane resin and hydrocarbon resin; the composite material or the circuit substrate prepared by adopting the PTFE woven cloth with or without the filler with excellent dielectric property as the carrier material has good dielectric constant and low dielectric loss angle, and the prepreg prepared by adopting the PTFE woven cloth with or without the filler has good process operability and good thickness flatness.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a composite material, a circuit substrate manufactured by using the composite material and a manufacturing method of the circuit substrate.
Background
In recent years, with the development of high performance, high functionality, and networking of information communication apparatuses, in order to transmit and process large-capacity information at high speed, operation signals tend to be high-frequency, and the frequency of use of electronic products continues to be high, and substrate materials are required to be lower in dielectric constant and lower in dielectric loss.
Currently, high frequency circuit substrates use low dielectric constant resins, including polyphenylene ether, cyanate ester, hydrocarbon resins, PTFE, and the like, to achieve good high frequency performance. The circuit substrate generally uses E-glass fiber as a reinforcing material. However, the dielectric constant of the woven glass cloth is relatively large (dielectric constant of E-glass 6.6, dielectric loss tangent of 0.006, dielectric constant of Q-glass 3.8, dielectric loss tangent of 0.0002), and the dielectric constant and dielectric loss tangent of the circuit board made of other resins other than PTFE are hardly lowered due to the large dielectric constant and dielectric loss tangent of the woven glass cloth.
In addition, although a Q glass cloth having a low dielectric loss tangent is used for a circuit board to obtain a low dielectric loss, the Q glass cloth is brittle in glass component and is easily broken, and a defect is easily generated in a composite material or a circuit board to be manufactured.
Disclosure of Invention
The invention aims to provide a composite material, a circuit substrate manufactured by using the composite material and a manufacturing method thereof, so as to solve the problems in the background art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a composite material, the composition comprising:
A low dielectric thermosetting resin composition;
PTFE woven cloth with or without filler;
A powder filler;
The low-dielectric thermosetting resin composition is one or two or more of cyanate resin, polyphenyl ether resin, vinyl or acrylic acid group end capped polyphenyl ether resin, polyphenyl ether resin with allyl, bismaleimide resin, vinyl end capped siloxane resin and hydrocarbon resin;
The PTFE woven fabric with or without the filler is formed by slitting a PTFE sintered film with or without the filler into filaments, and weaving the filaments of PTFE into a PTFE plain woven fabric with or without the filler by adopting a plain weaving method;
The powder filler is selected from one or more of crystalline silica, fused silica, spherical silica, alumina, titanium dioxide, strontium titanate, barium strontium titanate, boron nitride, aluminum nitride, silicon carbide, glass chopped fibers, glass powder, talcum powder, mica powder, carbon black, carbon nano tube, metal powder, magnetic powder and polyphenylene sulfide powder; the powder filler content is 0-50% by volume of the total amount of the low dielectric thermosetting resin composition and the powder filler, the powder filler has a particle size median of 0-15 μm and a maximum particle size of not more than 100 μm.
As a further scheme of the invention: the low dielectric thermosetting resin composition also comprises a curing initiator, wherein the dosage of the curing initiator is 1-10% of that of the low dielectric thermosetting resin composition.
As still further aspects of the invention: the low dielectric thermosetting resin composition also comprises a flame retardant.
As still further aspects of the invention: the hydrocarbon resin comprises one or any combination of vinyl polybutadiene resin, copolymer resin of polybutadiene and styrene, 1, 2-bis (4-vinyl phenyl) ethane polymer resin, 1, 4-diisopropenyl benzene polymer resin, benzocyclobutene polymer and divinylbenzene oligomer resin, wherein the weight of the vinyl polybutadiene resin is more than 60 percent.
The vinyl polybutadiene resin may be a copolymer resin of polybutadiene and styrene.
As still further aspects of the invention: the filler added in the PTFE woven cloth with or without the filler is one or more of self-crystallized silicon dioxide, fused silicon dioxide, spherical silicon dioxide, aluminum oxide, titanium dioxide, strontium titanate, barium strontium titanate, boron nitride, aluminum nitride, silicon carbide, glass chopped fiber, glass powder, talcum powder, mica powder, carbon black, carbon nano tube, metal powder, magnetic powder and polyphenylene sulfide powder.
As still further aspects of the invention: the diameter of the monofilament in the PTFE woven cloth with or without the filler is 1-9 mu m, and the thickness of the PTFE woven cloth with or without the filler is 0.03-0.2 mm.
As still further aspects of the invention: the surface of the powder filler is treated with a coupling agent.
A circuit substrate made of a composite material, comprising: the prepreg is made of the composite material, and the metal foils are copper, brass, aluminum, nickel or alloys of the metals or composite metal foils.
A manufacturing method of a circuit substrate manufactured by composite materials comprises the following steps:
Step 1, weighing a composition of the composite material: (1) a low dielectric thermosetting resin composition; (2) a PTFE woven cloth added with filler; (3) a powder filler;
step 2, dissolving and diluting the low-dielectric thermosetting resin composition to proper viscosity by using a solvent, then adding the powder filler and the auxiliary agent, stirring and mixing the mixture to uniformly disperse the powder filler therein, and preparing a glue solution;
Step 3, dipping PTFE woven cloth with or without filler into the glue solution, and then baking at 80-200 ℃ to remove the solvent to form prepreg;
And 4, laminating a plurality of prepregs, respectively pressing one metal foil up and down, and putting the prepregs into a press for hot pressing to obtain the circuit substrate, wherein the hot pressing temperature is 80-250 ℃, and the hot pressing pressure is 25-70 Kg/cm 2.
As still further aspects of the invention: the solid content of the glue solution in the step 2 is 30-80%; the glue solution forms a resin layer on the surface of PTFE woven cloth without filler or with filler, and the thickness of the resin layer is controlled to be 100 mu m.
Compared with the prior art, the invention has the beneficial effects that:
the composite material or the circuit substrate prepared by adopting the PTFE woven cloth with or without the filler with excellent dielectric property as the carrier material has good dielectric constant and low dielectric loss angle, and the prepreg prepared by adopting the PTFE woven cloth with or without the filler has good process operability and good thickness flatness.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In an embodiment of the present invention, a composite material, the composition of which comprises:
(1) A low dielectric thermosetting resin composition;
(2) PTFE woven cloth with or without filler;
(3) A powder filler;
The low-dielectric thermosetting resin composition is one or two or more of cyanate resin, polyphenyl ether resin, vinyl or acrylic acid group end capped polyphenyl ether resin, polyphenyl ether resin with allyl groups, bismaleimide resin, vinyl end capped siloxane resin, hydrocarbon resin and the like, wherein the hydrocarbon resin is polybutadiene resin containing more than 60 percent of vinyl or copolymer resin of polybutadiene and styrene, 1, 2-bis (4-vinyl phenyl) ethane polymer resin, 1, 4-diisopropenylbenzene polymer resin, benzocyclobutene polymer, divinylbenzene oligomer resin and the like;
the PTFE woven cloth with or without the filler is prepared by cutting a PTFE sintering film with or without the filler into filaments, manufacturing the PTFE sintering film by an extrusion, rolling and expansion stretching method, weaving the filaments of PTFE into a PTFE plain woven cloth with or without the filler by adopting a plain weaving method, and performing surface treatment, preferably sodium naphthalene treatment, on the fiber surface of the PTFE woven cloth with the filler;
The powder filler is selected from one or more of crystalline silica, fused silica, spherical silica, alumina, titanium dioxide, strontium titanate, barium strontium titanate, boron nitride, aluminum nitride, silicon carbide, glass chopped fibers, glass powder, talcum powder, mica powder, carbon black, carbon nano tube, metal powder, magnetic powder and polyphenylene sulfide powder; the powder filler content is 0-50% by volume of the total amount of the low dielectric thermosetting resin composition and the powder filler, the powder filler has a particle size median of 0-15 μm and a maximum particle size of not more than 100 μm.
The low dielectric thermosetting resin composition also comprises a curing initiator, wherein the dosage of the curing initiator is 1-10% of that of the low dielectric thermosetting resin composition.
The low dielectric thermosetting resin composition also comprises a flame retardant.
The low dielectric thermosetting resin composition comprises hydrocarbon resin; the hydrocarbon resin is one or any combination of polybutadiene resin containing more than 60 percent of vinyl, 1, 2-bis (4-vinyl phenyl) ethane polymer resin, 1, 4-diisopropenylbenzene polymer resin, benzocyclobutene polymer and divinylbenzene oligomer resin.
The vinyl polybutadiene resin may be a copolymer resin of polybutadiene and styrene.
The filler added in the PTFE woven cloth with or without the filler is one or more of self-crystallized silicon dioxide, fused silicon dioxide, spherical silicon dioxide, aluminum oxide, titanium dioxide, strontium titanate, barium strontium titanate, boron nitride, aluminum nitride, silicon carbide, glass chopped fiber, glass powder, talcum powder, mica powder, carbon black, carbon nano tube, metal powder, magnetic powder, polyphenylene sulfide powder and the like, wherein the filler content of the fiber in the PTFE woven cloth with the filler accounts for 0-70 volume percent of the total amount of the fluorine-containing polymer and the filler, the filler content accounts for less than 5 volume percent of the total amount of the fluorine-containing polymer and the filler, and the aim of improving the dimensional stability cannot be achieved well; the filler content is higher than 30% by volume of the total amount of the fluorine-containing polymer and the filler, the strength of the produced fiber is not high, the formability is poor, and the filler content is preferably 5-30% by volume of the total amount of the fluorine-containing polymer and the filler.
The monofilament diameter of the PTFE woven cloth with or without the filler is 1-9 mu m, the thickness of the PTFE woven cloth with or without the filler is 0.03-0.2 mm, the thickness of the PTFE woven cloth with or without the filler is 0.03-0.05 mm, the thickness of the PTFE woven cloth with or without the filler is 0.06-0.1 mm, and the thickness of the PTFE woven cloth with or without the filler is 0.2 mm.
The surface of the powder filler is treated with a coupling agent for better performance.
A circuit substrate made of a composite material, comprising: the prepreg is made of the composite material, and the metal foils are copper, brass, aluminum, nickel or alloys of the metals or composite metal foils.
A manufacturing method of a circuit substrate manufactured by composite materials comprises the following steps:
Step 1, weighing a composition of the composite material: (1) a low dielectric thermosetting resin composition; (2) a PTFE woven cloth added with filler; (3) a powder filler;
step 2, dissolving and diluting the low-dielectric thermosetting resin composition to proper viscosity by using a solvent, then adding the powder filler and the auxiliary agent, stirring and mixing the mixture to uniformly disperse the powder filler therein, and preparing a glue solution;
Step 3, dipping PTFE woven cloth with or without filler into the glue solution, controlling the thickness to be proper, and then baking at 80-200 ℃ to remove the solvent to form prepreg;
In order to obtain prepregs with different thicknesses, PTFE woven fabrics with fillers with different thicknesses can be adopted; the PTFE woven cloth added with the filler is obtained by cutting a PTFE sintered film (manufactured by extrusion, rolling and expansion stretching) added with the filler into filaments, and weaving the filaments into the PTFE woven cloth added with the filler by adopting a plain weaving method; the monofilament diameter of the woven cloth is from 1 μm to 9 μm, alternatively 1 μm,3 μm,5 μm, 7 μm and 9 μm, the thickness of the PTFE woven cloth added with filler is from 0.03 mm to 0.2 mm, alternatively 0.03 mm, 0.05 mm, 0.06 mm, 0.1 mm and 0.2 mm, and the glue solution forms a resin layer on the surface of the PTFE woven cloth added with filler, and the thickness is controlled below 100 μm, preferably below 50 μm and more preferably below 20 μm;
the dipping operation can be carried out by adopting a general gluing machine for manufacturing a copper-clad plate, the temperature of a baking oven of the gluing machine can be set in a sectional manner, and the temperature range adopted by the baking oven is 80-200 ℃ so as to remove solvents and the like;
The solid content of the glue solution is 30-80%; the glue solution forms a resin layer on the surface of PTFE woven cloth without filler or with filler, and the thickness of the resin layer is controlled below 100 micrometers;
And 4, laminating a plurality of prepregs, respectively pressing one metal foil up and down, putting the prepregs into a press for hot pressing to obtain the circuit substrate, wherein the hot pressing temperature is 80-250 ℃, the hot pressing pressure is 25-70 Kg/cm 2, and the metal foil is copper, brass, aluminum, nickel or alloy or composite metal foil of the metals.
The solid content of the glue solution in the step 2 is 30-80%; the glue solution forms a resin layer on the surface of PTFE woven cloth without filler or with filler, and the thickness of the resin layer is controlled to be 100 mu m.
The compositions of the composite materials selected in the examples and comparative examples of the present invention are shown in Table 1 below:
TABLE 1
| Manufacturer(s) | Product name or brand | Material content |
| Sartomer | Ricon100 | Styrene-butadiene resin |
| Japanese Cadda | PB3000 | Polybutadiene resin |
| Kraton | R2010 | Diisopropenyl polymer |
| Sha Bike A | SA9000 | Polyphenylene ether |
| Shandong holy spring | Divinylbenzene oligomer resin | |
| Sibelco | 525 | Silica micropowder |
| Shanghai Gao Qiao | DCP | Dicumyl peroxide |
| Henan Guangdong | 1080 Glass woven cloth | Thickness 0.05mm, basis weight 48g/m2 |
| Homemade | PTFE plain weave cloth containing filler or not containing filler |
Example 1
Weighing 80 parts by weight of liquid styrene-butadiene resin Ricon100, 20 parts by weight of R2010, 45 parts by weight of silicon dioxide (525), and mixing a proper amount of decabromodiphenyl ethane and 2.5 parts by weight of an initiator DCP;
Regulating the viscosity to a proper level by using toluene as a solvent, and uniformly stirring and mixing the mixture to uniformly disperse the powder filler in the resin to prepare a glue solution;
dipping the PTFE woven cloth without filler (the surface of the woven cloth is treated by sodium naphthalene) in the glue solution, and then drying to remove the solvent to obtain a prepreg, so as to form the prepreg;
Eight prepregs of the resulting prepreg were laminated, and copper foil having a thickness of 1oz (ounce) was laminated on both sides thereof, and cured in a press for 2 hours at a curing pressure of 50Kg/cm 2 and a curing temperature of 230℃and physical properties shown in Table 2.
Example 2
Weighing 60 parts by weight of liquid styrene-butadiene resin Ricon100, 40 parts by weight of divinylbenzene oligomer resin, 35 parts by weight of silicon dioxide (525), a proper amount of decabromodiphenylethane and 2.5 parts by weight of initiator DCP, and mixing;
Regulating the viscosity to a proper level by using toluene as a solvent, and uniformly stirring and mixing the mixture to uniformly disperse the powder filler in the resin to prepare a glue solution;
impregnating the glue solution with PTFE woven cloth containing filler (the surface of the woven cloth is treated by sodium naphthalene), drying and removing the solvent to obtain a prepreg, and forming the prepreg;
Eight prepregs of the resulting prepreg were laminated, and copper foil having a thickness of 1oz (ounce) was laminated on both sides thereof, and cured in a press for 2 hours at a curing pressure of 50Kg/cm 2 and a curing temperature of 230℃and physical properties shown in Table 2.
Example 3
50 Parts by weight of liquid PB3000, 50 parts by weight of divinylbenzene oligomer resin, 65 parts by weight of silica (525), a proper amount of decabromodiphenylethane and 2.5 parts by weight of initiator DCP are weighed and mixed;
Regulating the viscosity to a proper level by using toluene as a solvent, and uniformly stirring and mixing the mixture to uniformly disperse the powder filler in the resin to prepare a glue solution;
impregnating the glue solution with PTFE woven cloth containing filler (the surface of the woven cloth is treated by sodium naphthalene), drying and removing the solvent to obtain a prepreg, and forming the prepreg;
Eight prepregs of the resulting prepreg were laminated, and copper foil having a thickness of 1oz (ounce) was laminated on both sides thereof, and cured in a press for 2 hours at a curing pressure of 50Kg/cm 2 and a curing temperature of 240℃and physical properties shown in Table 2.
Example 4
80 Parts by weight of liquid R2010, 20 parts by weight of divinylbenzene oligomer resin, 45 parts by weight of silica (525), an appropriate amount of decabromodiphenylethane and 1.5 parts by weight of initiator DCP are weighed and mixed;
Regulating the viscosity to a proper level by using toluene as a solvent, and uniformly stirring and mixing the mixture to uniformly disperse the powder filler in the resin to prepare a glue solution;
impregnating the glue solution with PTFE woven cloth containing filler (the surface of the woven cloth is treated by sodium naphthalene), drying and removing the solvent to obtain a prepreg, and forming the prepreg;
Eight prepregs of the resulting prepreg were laminated, and copper foil having a thickness of 1oz (ounce) was laminated on both sides thereof, and cured in a press for 2 hours at a curing pressure of 50Kg/cm 2 and a curing temperature of 190℃and physical properties as shown in Table 2.
Example 5
Weighing 5 parts by weight of liquid SA9000, 95 parts by weight of divinylbenzene oligomer resin, 45 parts by weight of silicon dioxide (525), a proper amount of decabromodiphenylethane and 2.5 parts by weight of initiator DCP, and mixing;
Regulating the viscosity to a proper level by using toluene as a solvent, and uniformly stirring and mixing the mixture to uniformly disperse the powder filler in the resin to prepare a glue solution;
impregnating the glue solution with PTFE woven cloth containing filler (the surface of the woven cloth is treated by sodium naphthalene), drying and removing the solvent to obtain a prepreg, and forming the prepreg;
Eight prepregs of the resulting prepreg were laminated, and copper foil having a thickness of 1oz (ounce) was laminated on both sides thereof, and cured in a press for 2 hours at a curing pressure of 50Kg/cm 2 and a curing temperature of 200℃and physical properties shown in Table 2.
Comparative example 1
50 Parts by weight of liquid PB3000, 50 parts by weight of divinylbenzene oligomer resin, 65 parts by weight of silica (525), an appropriate amount of decabromodiphenylethane, 2.5 parts by weight of initiator DCP;
Regulating the viscosity to a proper level by using toluene as a solvent, and uniformly stirring and mixing the mixture to uniformly disperse the powder filler in the resin to prepare a glue solution;
Dipping 1080 glass woven cloth into the glue solution, drying to remove solvent to obtain prepreg, and forming prepreg;
Eight prepregs of the resulting prepreg were laminated, and copper foil having a thickness of 1oz (ounce) was laminated on both sides thereof, and cured in a press for 2 hours at a curing pressure of 50Kg/cm 2 and a curing temperature of 240℃and physical properties shown in Table 2.
Comparative example 2
Bisphenol A epoxy resin and brominated epoxy resin are dissolved in dimethylformamide, and dicyandiamide with an amine equivalent of 0.7 mol ratio relative to the epoxy resin is added as a curing agent and a proper amount of 2-MI (2-methylimidazole) is used as an accelerator. Then mixing at room temperature to obtain a glue solution.
The PTFE woven cloth added with the filler and having a thickness of 50 μm was impregnated with the above glue solution, and then baked in an oven at 155℃to remove the solvent dimethylformamide, thereby producing a prepreg having a thickness of 67. Mu.m.
And 5 pieces of the prepared prepreg are overlapped, one piece of copper foil is respectively covered on the upper part and the lower part, the circuit substrate is prepared by placing the circuit substrate in a press for hot pressing, the curing temperature is 177 ℃, the curing pressure is 45Kg/cm 2, and the curing time is 90 minutes. The physical properties are shown in Table 2.
Table 2 physical property data of examples and comparative examples
The above examples and comparative examples all refer to IPC4101 standard for testing circuit substrates, and the dielectric properties were tested by SPDR (splite post dielectric resonator) method under the conditions of a-state, 10GHz.
As can be seen from examples 1,2, 3,4, and 5 above, the circuit board obtained by using a thermosetting resin having a low dielectric loss tangent in combination with a PTFE braid has a low dielectric constant and a low dielectric loss tangent and is excellent in high-frequency performance; as can be seen from comparative examples 1 and 2, since a thermosetting resin or a glass woven cloth having a large dielectric loss tangent is used in combination, the dielectric constant and dielectric loss tangent of the circuit board produced are much larger; therefore, the use of a thermosetting resin excellent in dielectric properties in combination with a PTFE woven cloth excellent in dielectric properties and a fluororesin polymer can provide a composite material excellent in dielectric properties and a circuit board, and the use of the composite material in a high-frequency circuit can provide a better signal transmission effect.
Although the present invention has been described with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements and changes may be made without departing from the spirit and principles of the present invention.
Claims (10)
1. A composite material, characterized in that the composition comprises:
A low dielectric thermosetting resin composition;
PTFE woven cloth with or without filler;
A powder filler;
The low-dielectric thermosetting resin composition is one or two or more of cyanate resin, polyphenyl ether resin, vinyl or acrylic acid group end capped polyphenyl ether resin, polyphenyl ether resin with allyl, bismaleimide resin, vinyl end capped siloxane resin and hydrocarbon resin;
The PTFE woven fabric with or without the filler is formed by slitting a PTFE sintered film with or without the filler into filaments, and weaving the filaments of PTFE into a PTFE plain woven fabric with or without the filler by adopting a plain weaving method;
The powder filler is selected from one or more of crystalline silica, fused silica, spherical silica, alumina, titanium dioxide, strontium titanate, barium strontium titanate, boron nitride, aluminum nitride, silicon carbide, glass chopped fibers, glass powder, talcum powder, mica powder, carbon black, carbon nano tube, metal powder, magnetic powder and polyphenylene sulfide powder; the powder filler content is 0-50% by volume of the total amount of the low dielectric thermosetting resin composition and the powder filler, the powder filler has a particle size median of 0-15 μm and a maximum particle size of not more than 100 μm.
2. A composite material according to claim 1, wherein: the low dielectric thermosetting resin composition also comprises a curing initiator, wherein the dosage of the curing initiator is 1-10% of that of the low dielectric thermosetting resin composition.
3. A composite material according to claim 1, wherein: the low dielectric thermosetting resin composition also comprises a flame retardant.
4. A composite material according to claim 1, wherein: the low dielectric thermosetting resin composition comprises hydrocarbon resin; the hydrocarbon resin comprises one or any combination of polybutadiene resin containing more than 60 percent of vinyl, copolymer resin of polybutadiene and styrene, 1, 2-bis (4-vinyl phenyl) ethane polymer resin, 1, 4-diisopropenylbenzene polymer resin, benzocyclobutene polymer and divinylbenzene oligomer resin.
5. A composite material according to claim 1, wherein: the filler added in the PTFE woven cloth with or without the filler is one or more of self-crystallized silicon dioxide, fused silicon dioxide, spherical silicon dioxide, aluminum oxide, titanium dioxide, strontium titanate, barium strontium titanate, boron nitride, aluminum nitride, silicon carbide, glass chopped fiber, glass powder, talcum powder, mica powder, carbon black, carbon nano tube, metal powder, magnetic powder and polyphenylene sulfide powder.
6. A composite material according to claim 1, wherein: the diameter of the monofilament in the PTFE woven cloth with or without the filler is 1-9 mu m, and the thickness of the PTFE woven cloth with or without the filler is 0.03-0.2 mm.
7. A composite material according to claim 1, wherein: the surface of the powder filler is treated with a coupling agent.
8. The circuit substrate made of the composite material according to claim 1, comprising: a plurality of mutually overlapped prepregs and metal foils respectively pressed on two sides of the prepregs, which is characterized in that: the prepreg is made of the composite material, and the metal foil is copper, brass, aluminum, nickel or an alloy of the metals or a composite metal foil.
9. The method for manufacturing a circuit substrate made of a composite material according to claim 8, wherein: comprising the following steps:
step 1, weighing a composition of the composite material: a low dielectric thermosetting resin composition; PTFE woven cloth added with filler; a powder filler;
step 2, dissolving and diluting the low-dielectric thermosetting resin composition to proper viscosity by using a solvent, then adding the powder filler and the auxiliary agent, stirring and mixing the mixture to uniformly disperse the powder filler therein, and preparing a glue solution;
Step 3, dipping PTFE woven cloth with or without filler into the glue solution, and then baking at 80-200 ℃ to remove the solvent to form prepreg;
And 4, laminating a plurality of prepregs, respectively pressing one metal foil up and down, and putting the prepregs into a press for hot pressing to obtain the circuit substrate, wherein the hot pressing temperature is 80-250 ℃, and the hot pressing pressure is 25-70 Kg/cm 2.
10. The method for manufacturing a circuit substrate made of a composite material according to claim 9, wherein: the solid content of the glue solution in the step 2 is 30-80%; the glue solution forms a resin layer on the surface of PTFE woven cloth without filler or with filler, and the thickness of the resin layer is controlled to be 100 mu m.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118307854A true CN118307854A (en) | 2024-07-09 |
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