CN115028998B - Preparation method of halogen-free low-loss copper-clad plate for high-frequency high-speed field - Google Patents
Preparation method of halogen-free low-loss copper-clad plate for high-frequency high-speed field Download PDFInfo
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- CN115028998B CN115028998B CN202210824874.3A CN202210824874A CN115028998B CN 115028998 B CN115028998 B CN 115028998B CN 202210824874 A CN202210824874 A CN 202210824874A CN 115028998 B CN115028998 B CN 115028998B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 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 20
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 20
- 150000001913 cyanates Chemical class 0.000 claims abstract description 10
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims abstract description 10
- -1 allyl compound Chemical class 0.000 claims abstract description 9
- 239000003063 flame retardant Substances 0.000 claims abstract description 8
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000004643 cyanate ester Substances 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000003292 glue Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 4
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 4
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004697 Polyetherimide Substances 0.000 claims description 4
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000011889 copper foil Substances 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920001601 polyetherimide Polymers 0.000 claims description 4
- 229920005992 thermoplastic resin Polymers 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 claims description 2
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 claims description 2
- PVQATPQSBYNMGE-UHFFFAOYSA-N [benzhydryloxy(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)OC(C=1C=CC=CC=1)C1=CC=CC=C1 PVQATPQSBYNMGE-UHFFFAOYSA-N 0.000 claims description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 2
- 239000005350 fused silica glass Substances 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000011342 resin composition Substances 0.000 abstract 3
- 230000000052 comparative effect Effects 0.000 description 7
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000004891 communication Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HSCPDMJPJJSHDA-UHFFFAOYSA-N benzylbenzene;pyrrole-2,5-dione Chemical compound O=C1NC(=O)C=C1.O=C1NC(=O)C=C1.C=1C=CC=CC=1CC1=CC=CC=C1 HSCPDMJPJJSHDA-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229920006258 high performance thermoplastic Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2471/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- 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
- C08K5/00—Use of organic ingredients
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- C08K5/5399—Phosphorus bound to nitrogen
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- 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
Abstract
The invention relates to a preparation method of a halogen-free low-loss copper-clad plate for the high-frequency and high-speed field, which adopts the key technology that a resin composition for manufacturing the copper-clad plate, a bonding sheet and the copper-clad plate manufactured by the resin composition, wherein the resin composition comprises the following components in percentage by weight: 20-100 parts of polyphenyl ether, 10-80 parts of modified cyanate ester resin, 10-30 parts of allyl compound, 50-200 parts of bismaleimide resin, 10-100 parts of curing cross-linking agent, 20-100 parts of halogen-free flame retardant, 10-60 parts of filler and a proper amount of solvent are mixed to form the halogen-free flame retardant, the total halogen content is less than 900ppm, and the halogen-free requirements of European Union and the like are met; besides the basic performance of the conventional halogen-free copper-clad plate, the prepared copper-clad plate has excellent dielectric property, namely a dielectric constant DK is less than or equal to 3.4, a dielectric loss factor Df is less than or equal to 0.0035, and a higher glass transition temperature Tg value is more than or equal to 200 ℃.
Description
Technical Field
The invention belongs to the technical field of copper-clad plate production, and particularly relates to a preparation method of a halogen-free low-loss copper-clad plate for high-frequency and high-speed fields.
Background
With the acceleration of 5G communication pace and the development of the automobile industry to the direction of intellectualization, dynamization, etc., the market demand for high frequency/high speed printed circuit boards (PCBs for short) is increasing, and copper clad laminates are required to have lower dielectric constants and dielectric losses.
Many properties of the copper-clad plate are closely related to the base material, and the selection of resin with excellent dielectric properties is one of important ways for realizing the high-frequency/high-speed copper-clad plate. The existing resin suitable for the high-frequency/high-speed copper-clad plate mainly comprises polyimide, polytetrafluoroethylene, polyphenyl ether and other resins, and the resins have excellent dielectric properties, but have certain defects. For example, polyphenyl ether is a high-performance thermoplastic engineering plastic, is difficult to dissolve in an organic solvent, has insufficient heat resistance and cannot bear the soldering operation of more than 260 ℃ required by the PCB process; the maleimide resin has excellent heat resistance, good moisture and heat resistance, low moisture absorption rate and lower thermal expansion coefficient. However, BMI melting temperature is relatively high, and the difference between BMI melting temperature and curing initial temperature is small, processing manufacturability is poor, and secondly, after curing, crosslinking density is high, brittleness is large, bismaleimide resin is large, and the bismaleimide resin needs to be used in combination with a toughening agent (such as diallyl bisphenol A, epoxy resin and other resins) in the application of a copper-clad plate, and the toughened bismaleimide resin-based copper-clad plate has high dielectric constant (3.9-4.6, 10 GHz) and dielectric loss (0.008-0.013, 10 GHz), so that the application of the bismaleimide resin-based copper-clad plate in the field of 5G communication (high frequency/high speed) electronic products is limited; the unique triazine ring structure of the cured product of the cyanate ester gives the cyanate ester excellent dielectric property, lower moisture absorption rate, better dimensional stability, high temperature resistance and similar molding process as the epoxy resin. However, the cured product of the resin is brittle due to the high crosslinking density of the highly structured triazine ring structure, and the cyanate ester is expensive, which further limits the application of the cyanate ester resin.
Along with the increasing demand of the market for high-frequency high-speed copper-clad plates, the prior art cannot meet the performance requirements of products.
Disclosure of Invention
According to the defects of the prior art, the invention aims to provide a preparation method of a halogen-free and low-loss copper-clad plate for the high-frequency and high-speed field, wherein polyphenyl ether adopted by the invention can react with modified cyanate resin and bismaleimide resin to form a crosslinked network structure, so that high addition amount can be realized, the dielectric properties and toughness of the cyanate resin and the bismaleimide resin can be effectively improved, and meanwhile, the proper heat resistance can be maintained.
In order to achieve the above purpose, the technical scheme adopted is as follows:
a preparation method of a halogen-free low-loss copper-clad plate for the high-frequency and high-speed field comprises the following steps:
(1) Taking 20-100 parts of polyphenyl ether, 10-80 parts of modified cyanate ester resin, 10-30 parts of allyl compound, 50-200 parts of bismaleimide resin, 10-100 parts of curing cross-linking agent, 20-100 parts of halogen-free flame retardant, 10-60 parts of filler and 5-100 parts of solvent, and uniformly mixing to obtain a glue solution;
(2) Coating the glue solution obtained in the step (1) on electronic grade glass cloth, and baking in a baking oven at 130-150 ℃ for 5-10min to obtain a prepreg;
(3) And (3) stacking a plurality of prepregs prepared in the step (2), respectively coating one copper foil on each side of the prepregs, hot-pressing the prepregs for 120-240min under the conditions of the pressure of 1.0-2.8MPa and the temperature of 180-240 ℃, and cooling the prepregs to prepare the copper-clad plate.
Further, the molecular weight of the polyphenylene ether in the step (1) is 800 to 3000.
Further, in the step (1), the modified cyanate resin is a thermoplastic resin modified cyanate resin, and the thermoplastic resin is at least one of Polysulfone (PSU), polyethersulfone (PES), polyetherimide (PEI), polycarbonate (PC), polyetherketone (PEK), and polyphenylene oxide (PPO).
Further, the allyl compound in step (1) is diallyl bisphenol a or diallyl bisphenol S.
Further, the bismaleimide resin in the step (1) is bismaleimide-based diphenyl methyl ether or bismaleimide-based diphenyl methane.
Still further, the curing crosslinker in step (1) comprises the following components in weight percent:
triallyl cyanurate 10-50%
Triallyl isocyanurate 20-60%
10-50% of trimethylolpropane trimethacrylate.
Further, the halogen-free flame retardant in the step (1) comprises the following components in percentage by weight:
further, in the step (1), the filler is at least one of spherical silica micropowder and fused silica micropowder.
Further, the solvent in the step (1) is selected from one or more of toluene, benzene, xylene, acetone, butanone, ethyl acetate and butyl acetate.
Still further, the glue solution in the step (1) is a resin solution with a solid content of 50% -75%.
Compared with the prior art, the invention has the beneficial effects that:
(1) The polyphenyl ether adopted by the invention can react with the modified cyanate resin and the bismaleimide resin to form a crosslinked network structure, so that high addition amount can be realized, the dielectric property and toughness of the cyanate resin and the bismaleimide resin can be effectively improved, and meanwhile, the proper heat resistance can be maintained;
(2) The invention has the advantages of no halogenation, low loss, good mechanical property and heat resistance, and good dielectric property in the high-frequency and high-speed field: the dielectric constant Dk is less than or equal to 3.4 at 10GHz, the dielectric loss factor Df (10 GHz) is less than or equal to 0.0035, the Z-axis thermal expansion coefficient is less than or equal to 1.85%, the glass transition temperature Tg can reach more than 210 ℃, the peel strength is 1.51-1.85N/mm, the halogen-free copper clad laminate can be used for meeting the technical requirements of copper clad laminates under the 5G communication technical condition, the total halogen content is less than 900ppm, and the halogen-free requirements of European Union and the like are met;
(3) The copper-clad plate prepared by the method is halogen-free and environment-friendly, has simple process flow, is convenient to produce, has good product performance, and can better meet market demands.
Detailed Description
The invention is described below in connection with examples which are given solely for the purpose of illustration and are not intended to limit the scope of the invention.
Example 1
A preparation method of a halogen-free low-loss copper-clad plate for the high-frequency and high-speed field comprises the following steps:
(1) Taking 50 parts of polyphenyl ether with a molecular weight of 2000, 60 parts of polyether sulfone cyanate, 20 parts of diallyl bisphenol A, 80 parts of bismaleimide diphenylmethane, 50 parts of curing cross-linking agent (30% triallyl cyanurate, 30% triallyl isocyanurate and 40% trimethylolpropane trimethacrylate by weight), 40 parts of halogen-free flame retardant (40% DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) by weight, 40% hexaphenoxy cyclotriphosphazene, 20% melamine-isocyanuric acid by weight), 60 parts of filler spherical silicon micropowder, 60 parts of toluene and 30 parts of butanone by weight, and uniformly mixing to obtain a glue solution;
(2) Coating the glue solution obtained in the step (1) on electronic grade glass cloth, and baking in a baking oven at 150 ℃ for 8min to obtain a prepreg;
(3) And (3) stacking 6 prepregs prepared in the step (2), respectively coating one copper foil on each side of the prepregs, hot-pressing the prepregs for 240min under the conditions of 2.8MPa and 240 ℃ and cooling the prepregs to prepare the copper-clad plate.
Example 2
A preparation method of a halogen-free low-loss copper-clad plate for the high-frequency and high-speed field comprises the following steps:
(1) 80 parts of polyphenyl ether with a molecular weight of 3000, 50 parts of polyether ketone cyanate, 30 parts of diallyl bisphenol S, 60 parts of bismaleimide-based diphenyl ether, 60 parts of curing cross-linking agent (wherein 20% of triallyl cyanurate, 30% of triallyl isocyanurate and 50% of trimethylolpropane trimethacrylate by weight), 45 halogen-free flame retardant (wherein 30% of DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) by weight, 30% of hexaphenoxy cyclotriphosphazene and 40% of melamine-isocyanuric acid by weight), 50 parts of filler molten silicon micropowder, 50 parts of xylene and 30 parts of acetone are uniformly mixed to prepare glue solution;
(2) Coating the glue solution obtained in the step (1) on electronic grade glass cloth, and baking for 10min in a baking oven at 140 ℃ to obtain a prepreg;
(3) And (3) stacking 6 prepregs prepared in the step (2), respectively coating one copper foil on each side of the prepregs, hot-pressing the prepregs for 200min under the conditions of 2.5MPa and 260 ℃, and cooling the prepregs to prepare the copper-clad plate.
Comparative example 1
Comparative example 1 differs from example 1 in that no polyphenylene ether having a molecular weight of 2000 was added to the raw material.
Comparative example 2
Comparative example 2 differs from example 1 in that polyethersulfone cyanate was not added to the raw material.
Testing
The copper clad laminates prepared in examples 1-2 and comparative examples 1-2 were subjected to heat resistance, glass transition temperature, dielectric constant and dielectric loss test, and the test results are shown in table 1.
TABLE 1 comparison of the Performance data for the copper-clad plates of examples 1-2 and comparative examples 1-2
As can be seen from Table 1, compared with comparative examples 1-2, the copper-clad plate prepared in examples 1-2 has a dielectric constant Dk (10 GHz) of 3.35-3.39, a dielectric loss factor Df (10 GHz) of 0.0031-0.0032, a Z-axis thermal expansion coefficient of 1.8-1.85%, and a glass transition temperature Tg of 210 ℃ or above, because the polyphenylene oxide can react with the modified cyanate resin and the bismaleimide resin to form a crosslinked network structure, thereby realizing high addition, effectively improving the dielectric properties and toughness of the cyanate resin and the bismaleimide resin, and simultaneously maintaining proper heat resistance.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (1)
1. The preparation method of the halogen-free low-loss copper-clad plate for the high-frequency and high-speed field is characterized by comprising the following steps of:
(1) Taking 20-100 parts of polyphenyl ether, 10-80 parts of modified cyanate ester resin, 10-30 parts of allyl compound, 50-200 parts of bismaleimide resin, 10-100 parts of curing cross-linking agent, 20-100 parts of halogen-free flame retardant, 10-60 parts of filler and 5-100 parts of solvent, and uniformly mixing to obtain a glue solution;
(2) Coating the glue solution obtained in the step (1) on electronic grade glass cloth, and baking in a baking oven at 130-150 ℃ for 5-10min to obtain a prepreg;
(3) Stacking a plurality of prepregs prepared in the step (2), respectively coating one copper foil on each side of the prepregs, hot-pressing the prepregs for 120-240min under the conditions of the pressure of 1.0-2.8MPa and the temperature of 180-240 ℃, and cooling the prepregs to prepare the copper-clad plate;
the molecular weight of the polyphenyl ether in the step (1) is 800-3000;
the modified cyanate resin in the step (1) is thermoplastic resin modified cyanate resin, and the thermoplastic resin is at least one of Polysulfone (PSU), polyethersulfone (PES), polyetherimide (PEI), polycarbonate (PC), polyetherketone (PEK) and polyphenylene oxide (PPO);
the allyl compound in the step (1) is diallyl bisphenol A or diallyl bisphenol S;
the bismaleimide resin in the step (1) is bismaleimide-based diphenyl methyl ether or bismaleimide-based diphenyl methane;
the curing cross-linking agent in the step (1) comprises the following components in percentage by weight:
triallyl cyanurate 10-50%
Triallyl isocyanurate 20-60%
10-50% of trimethylolpropane trimethacrylate;
the halogen-free flame retardant in the step (1) comprises the following components in percentage by weight:
10-40% of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)
Hexaphenoxy cyclotriphosphazene 10-60%
Melamine-isocyanuric acid 5-50%;
the filler in the step (1) is at least one of spherical silica micropowder and fused silica micropowder;
the solvent in the step (1) is selected from one or more of toluene, benzene, xylene, acetone, butanone, ethyl acetate and butyl acetate;
the glue solution in the step (1) is a resin solution with the solid content of 50-75 percent.
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| CN103013110A (en) * | 2011-09-27 | 2013-04-03 | 台光电子材料股份有限公司 | Halogen-free resin composition as well as copper foil substrate and printed circuit board applying same |
| CN104177809A (en) * | 2013-05-21 | 2014-12-03 | 台光电子材料股份有限公司 | Low-dielectric halogen-free resin composition and application thereof |
| CN110776739A (en) * | 2019-09-05 | 2020-02-11 | 艾蒙特成都新材料科技有限公司 | Thermosetting resin composition for high-speed substrate, copper-clad plate and preparation method of copper-clad plate |
| CN112079868A (en) * | 2020-08-18 | 2020-12-15 | 艾蒙特成都新材料科技有限公司 | Halogen-free flame-retardant cyclotriphosphazene maleimide resin, laminated board and preparation method thereof |
| CN114181652A (en) * | 2021-12-28 | 2022-03-15 | 深圳市纽菲斯新材料科技有限公司 | Low-dielectric-loss insulating adhesive film and preparation method and application thereof |
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| US9422412B2 (en) * | 2011-09-22 | 2016-08-23 | Elite Material Co., Ltd. | Halogen-free resin composition and copper clad laminate and printed circuit board using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103013110A (en) * | 2011-09-27 | 2013-04-03 | 台光电子材料股份有限公司 | Halogen-free resin composition as well as copper foil substrate and printed circuit board applying same |
| CN104177809A (en) * | 2013-05-21 | 2014-12-03 | 台光电子材料股份有限公司 | Low-dielectric halogen-free resin composition and application thereof |
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| CN112079868A (en) * | 2020-08-18 | 2020-12-15 | 艾蒙特成都新材料科技有限公司 | Halogen-free flame-retardant cyclotriphosphazene maleimide resin, laminated board and preparation method thereof |
| CN114181652A (en) * | 2021-12-28 | 2022-03-15 | 深圳市纽菲斯新材料科技有限公司 | Low-dielectric-loss insulating adhesive film and preparation method and application thereof |
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