CN115028998A - Preparation method of non-halogenated low-loss copper-clad plate for high-frequency and high-speed field - Google Patents
Preparation method of non-halogenated low-loss copper-clad plate for high-frequency and high-speed field Download PDFInfo
- Publication number
- CN115028998A CN115028998A CN202210824874.3A CN202210824874A CN115028998A CN 115028998 A CN115028998 A CN 115028998A CN 202210824874 A CN202210824874 A CN 202210824874A CN 115028998 A CN115028998 A CN 115028998A
- Authority
- CN
- China
- Prior art keywords
- parts
- copper
- clad plate
- resin
- preparation
- 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.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- 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 15
- 239000004643 cyanate ester Substances 0.000 claims abstract description 15
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 15
- -1 allyl compound Chemical class 0.000 claims abstract description 9
- 150000001913 cyanates Chemical class 0.000 claims abstract description 9
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 7
- 239000003063 flame retardant Substances 0.000 claims abstract description 7
- 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 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 11
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 7
- 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
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method 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
- 238000002156 mixing Methods 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920001601 polyetherimide Polymers 0.000 claims description 4
- 239000000843 powder Substances 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
- 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 3
- 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 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
- 229920001955 polyphenylene ether Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 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
- 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
- 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
- 239000011342 resin composition Substances 0.000 abstract 3
- 230000000052 comparative effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 239000000463 material 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
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 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
- 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
- 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
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Classifications
-
- 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
-
- 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'
-
- 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
- C08K5/5399—Phosphorus bound to nitrogen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a preparation method of a non-halogenated and low-loss copper-clad plate for the high-frequency and high-speed field, which has the key technology of a resin composition for manufacturing the copper-clad plate and 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, wherein the total halogen content is less than 900ppm, and the halogen-free requirements of European Union and the like are met; the prepared copper-clad plate has the basic performance of the conventional halogen-free copper-clad plate, excellent dielectric property, dielectric constant DK of less than or equal to 3.4, dielectric loss factor Df of less than or equal to 0.0035 and higher glass transition temperature Tg value of 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 non-halogenated low-loss copper-clad plate for the high-frequency and high-speed field.
Background
With the acceleration of 5G communication pace and the development of automobile industry towards intellectualization, electromotion and the like, the market demand for high-frequency/high-speed printed circuit boards (PCB for short) is increasing day by day, and the copper-clad plate is required to have lower dielectric constant and dielectric loss.
Many properties of the copper-clad plate are closely related to the base material, and the selection of the resin with excellent dielectric property is one of important ways for realizing the high-frequency/high-speed copper-clad plate. The prior resin suitable for the high-frequency/high-speed copper-clad plate mainly comprises polyimide, polytetrafluoroethylene, polyphenyl ether and other resins which 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 damp and heat resistance, low moisture absorption rate and low thermal expansion coefficient. However, the BMI melting temperature is relatively high, the difference between the BMI melting temperature and the solidification starting temperature is not large, the processing manufacturability is poor, the crosslinking density is high after solidification, the brittleness is large, the bismaleimide resin needs to be compounded with a toughening agent (such as diallyl bisphenol A, epoxy resin and other resins) in the copper-clad plate application, and the bismaleimide resin base copper-clad plate toughened by the method has high dielectric constant (3.9-4.6, 10GHz) and dielectric loss (0.008-0.013, 10GHz), so that the application of the bismaleimide resin base copper-clad plate in the field of 5G communication (high frequency/high speed) electronic products is limited; the unique triazine ring structure of the cyanate ester condensate endows the cyanate ester condensate with excellent dielectric property, lower moisture absorption rate, better dimensional stability, high temperature resistance and a molding process similar to that of epoxy resin. However, the triazine ring structure with a highly regular structure is formed by curing, the crosslinking density is high, so that the cured product of the triazine ring structure is high in brittleness, and the price of the cyanate ester is high, so that the application of the cyanate ester resin is further limited.
With the increasing market demand for high-frequency and high-speed copper-clad plates, the existing process can not meet the performance requirements of products.
Disclosure of Invention
According to the defects of the prior art, the invention aims to provide the preparation method of the non-halogenated low-loss copper-clad plate for the high-frequency high-speed field.
In order to realize the purposes, the adopted technical scheme is as follows:
a preparation method of a non-halogenated low-loss copper-clad plate for the high-frequency and high-speed field comprises the following steps:
(1) uniformly mixing 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 to prepare glue solution;
(2) coating the glue solution obtained in the step (1) on electronic-grade glass cloth, and baking for 5-10min in an oven at the temperature of 130-;
(3) and (3) overlapping a plurality of prepregs prepared in the step (2), covering a copper foil on each of two surfaces of the prepregs, carrying out hot pressing for 240min at the pressure of 1.0-2.8MPa and the temperature of 180-.
Further, the molecular weight of the polyphenylene ether in the step (1) is 800-3000.
Further, the modified cyanate ester resin in the step (1) is a thermoplastic resin modified cyanate ester 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 the step (1) is diallyl bisphenol A or diallyl bisphenol S.
Further, in the step (1), the bismaleimide resin is bismaleimide diphenyl methyl ether or bismaleimide diphenylmethane.
Still further, the curing crosslinking agent in the step (1) comprises the following components in percentage by weight:
10-50% of triallyl cyanurate
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, the filler in the step (1) is at least one of spherical silica micropowder and fused silica micropowder.
Further, in the step (1), the solvent is one or more selected from toluene, benzene, xylene, acetone, butanone, ethyl acetate and butyl acetate.
And further, the glue solution in the step (1) is a resin solution with 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 ester resin and the bismaleimide resin to form a cross-linked network structure, so that high addition amount can be realized, the dielectric properties and toughness of the cyanate ester resin and the bismaleimide resin can be effectively improved, and meanwhile, proper heat resistance can be kept;
(2) the non-halogenated low-loss copper-clad material prepared by the invention has good mechanical property and heat resistance, and simultaneously has good dielectric property: the dielectric constant Dk is less than or equal to 3.4 under 10GHz, the dielectric loss factor Df (10GHz) is less than or equal to 0.0035, the thermal expansion coefficient of the Z axis 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 copper-clad plate can be used for meeting the technical requirement of the copper-clad plate under the 5G communication technical condition, the total halogen content is less than 900ppm, and the non-halogenation requirements of European Union and the like are met;
(3) the copper-clad plate prepared by the invention is halogen-free and environment-friendly, the method has simple process flow, is convenient to produce, has good product performance, and can better meet the market demand.
Detailed Description
The present invention is described below with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
Example 1
A preparation method of a non-halogenated low-loss copper-clad plate for the high-frequency and high-speed field comprises the following steps:
(1) taking 50 parts of polyphenylene oxide with molecular weight of 2000, 60 parts of polyethersulfone cyanate, 20 parts of diallyl bisphenol A, 80 parts of bismaleimide diphenylmethane, 50 parts of curing crosslinking agent (30% of triallyl cyanurate, 30% of triallyl isocyanurate and 40% of trimethylolpropane trimethacrylate), 40 parts of halogen-free flame retardant (40% of DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), 40% of hexaphenoxycyclotriphosphazene and 20% of melamine-isocyanuric acid), 60 parts of filler spherical silicon micro powder, 60 parts of toluene and 30 parts of butanone, and uniformly mixing to prepare a glue solution;
(2) coating the glue solution obtained in the step (1) on electronic-grade glass cloth, and baking for 8min in a baking oven at 150 ℃ to obtain a prepreg;
(3) and (3) overlapping 6 prepregs prepared in the step (2), covering a copper foil on each of two surfaces of the prepregs, carrying out hot pressing for 240min under the conditions that the pressure is 2.8MPa and the temperature is 240 ℃, and cooling to obtain the copper-clad plate.
Example 2
A preparation method of a non-halogenated low-loss copper-clad plate for the high-frequency and high-speed field comprises the following steps:
(1) taking 80 parts of polyphenyl ether with the molecular weight of 3000, 50 parts of polyether ketone cyanate, 30 parts of diallyl bisphenol S, 60 parts of bismaleimide diphenyl methyl ether, 60 parts of a curing crosslinking agent (wherein 20% of triallyl cyanurate, 30% of triallyl isocyanurate and 50% of trimethylolpropane trimethacrylate) by weight, 45 parts of a halogen-free flame retardant (wherein 30% of DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) by weight, 30% of hexaphenoxycyclotriphosphazene and 40% of melamine-isocyanuric acid by weight), 50 parts of filler fused silica micro powder, 50 parts of xylene and 30 parts of acetone by weight, and uniformly mixing to prepare a glue solution;
(2) coating the glue solution obtained in the step (1) on electronic-grade glass cloth, and baking for 10min in an oven at 140 ℃ to obtain a prepreg;
(3) and (3) overlapping 6 prepregs prepared in the step (2), covering a copper foil on each of two surfaces of the prepregs, hot-pressing for 200min under the conditions that the pressure is 2.5MPa and the temperature is 260 ℃, and cooling to obtain the copper-clad plate.
Comparative example 1
Comparative example 1 is different from example 1 in that polyphenylene ether having a molecular weight of 2000 was not added to the raw materials.
Comparative example 2
Comparative example 2 differs from example 1 in that no polyethersulfone cyanate was added to the feed.
Testing of
The copper-clad plates prepared in examples 1-2 and comparative examples 1-2 were subjected to heat resistance, glass transition temperature, dielectric constant and dielectric loss tests, and the test results are shown in table 1.
TABLE 1 comparison of Performance data for copper clad laminates 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 the advantages that the polyphenyl ether can react with the modified cyanate ester resin and the bismaleimide resin to form a cross-linked network structure, so that high addition amount is realized, dielectric properties and toughness of the cyanate ester resin and the bismaleimide resin are effectively improved, and meanwhile, proper heat resistance can be maintained, the dielectric constant Dk (10GHz) of the prepared copper-clad plate is 3.35-3.39, the dielectric loss factor Df (10GHz) is 0.0031-0.0032, the thermal expansion coefficient of the Z axis is 1.8-1.85, and the glass transition temperature Tg can reach more than 210 ℃.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a non-halogenated low-loss copper-clad plate for the high-frequency and high-speed field is characterized by comprising the following steps:
(1) uniformly mixing 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 to prepare glue solution;
(2) coating the glue solution obtained in the step (1) on electronic-grade glass cloth, and baking for 5-10min in an oven at the temperature of 130-;
(3) and (3) overlapping a plurality of prepregs prepared in the step (2), covering a copper foil on each of two surfaces of the prepregs, carrying out hot pressing for 240min at the pressure of 1.0-2.8MPa and the temperature of 180-.
2. The production method as described in claim 1, wherein the polyphenylene ether in the step (1) has a molecular weight of 800-3000.
3. The preparation method according to claim 1, wherein the modified cyanate ester resin in step (1) is a thermoplastic resin modified cyanate ester resin, and the thermoplastic resin is at least one of Polysulfone (PSU), Polyethersulfone (PES), Polyetherimide (PEI), Polycarbonate (PC), Polyetherketone (PEK), and polyphenylene oxide (PPO).
4. The method according to claim 1, wherein the allyl compound in the step (1) is diallyl bisphenol a or diallyl bisphenol S.
5. The method according to claim 1, wherein the bismaleimide resin in the step (1) is bismaleimide diphenyl methyl ether or bismaleimide diphenylmethane.
6. The method according to claim 1, wherein the curing crosslinking agent in step (1) comprises the following components in percentage by weight:
10-50% of triallyl cyanurate
Triallyl isocyanurate 20-60%
10-50% of trimethylolpropane trimethacrylate.
7. The preparation method according to claim 1, wherein the halogen-free flame retardant in step (1) comprises the following components in percentage by weight:
9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) 10-40%
10 to 60 percent of hexaphenoxycyclotriphosphazene
5-50% of melamine-isocyanuric acid.
8. The method according to claim 1, wherein the filler in step (1) is at least one of spherical fine silica powder and molten fine silica powder.
9. The method according to claim 1, wherein the solvent in step (1) is one or more selected from toluene, benzene, xylene, acetone, methyl ethyl ketone, ethyl acetate and butyl acetate.
10. The preparation method according to claim 1, wherein the glue solution in the step (1) is a resin solution with a solid content of 50-75%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210824874.3A CN115028998B (en) | 2022-07-13 | 2022-07-13 | Preparation method of halogen-free low-loss copper-clad plate for high-frequency high-speed field |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210824874.3A CN115028998B (en) | 2022-07-13 | 2022-07-13 | Preparation method of halogen-free low-loss copper-clad plate for high-frequency high-speed field |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115028998A true CN115028998A (en) | 2022-09-09 |
CN115028998B CN115028998B (en) | 2024-02-02 |
Family
ID=83128642
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210824874.3A Active CN115028998B (en) | 2022-07-13 | 2022-07-13 | Preparation method of halogen-free low-loss copper-clad plate for high-frequency high-speed field |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115028998B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117087264A (en) * | 2023-06-15 | 2023-11-21 | 明光瑞智电子科技有限公司 | High-frequency high-speed copper-clad plate and preparation method thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130075138A1 (en) * | 2011-09-22 | 2013-03-28 | Li-Chih Yu | Halogen-free resin composition and copper clad laminate and printed circuit board using same |
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 |
-
2022
- 2022-07-13 CN CN202210824874.3A patent/CN115028998B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130075138A1 (en) * | 2011-09-22 | 2013-03-28 | Li-Chih Yu | Halogen-free resin composition and copper clad laminate and printed circuit board using same |
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 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117087264A (en) * | 2023-06-15 | 2023-11-21 | 明光瑞智电子科技有限公司 | High-frequency high-speed copper-clad plate and preparation method thereof |
CN117087264B (en) * | 2023-06-15 | 2024-02-13 | 明光瑞智电子科技有限公司 | High-frequency high-speed copper-clad plate and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN115028998B (en) | 2024-02-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108485182B (en) | High-frequency resin composition and prepreg and laminated board manufactured by using same | |
CN111378243B (en) | Multifunctional modified resin blended prepreg hydrocarbon composition, application thereof and method for preparing high-frequency high-speed copper-clad plate by using same | |
CN104228216B (en) | A kind of low-loss high-performance copper coated foil plate and preparation method thereof | |
CN111471264A (en) | Filler modified hydrocarbon prepreg, preparation method thereof and method for preparing high-frequency high-speed copper-clad plate by using filler modified hydrocarbon prepreg | |
CN110724261B (en) | High-heat-resistance low-dielectric polyphenylene ether type bismaleimide resin, laminated board and preparation method thereof | |
CN114274618A (en) | Halogen-containing high-Tg high-speed copper-clad plate for communication server and preparation method thereof | |
CN115028998B (en) | Preparation method of halogen-free low-loss copper-clad plate for high-frequency high-speed field | |
CN114605767A (en) | Thermosetting resin composition and application thereof | |
CN108410128B (en) | Resin composition for high-speed high-frequency printed circuit board, prepreg and laminated board | |
CN117533001B (en) | Impact-resistant flame-retardant copper-clad plate and preparation method thereof | |
CN113978061A (en) | Preparation method of copper-clad plate with low dielectric constant, low dielectric loss and low CTE | |
CN114228274A (en) | Halogen-free high-Tg high-speed copper-clad plate for communication server and preparation method thereof | |
CN113844129A (en) | Preparation method of halogen-free copper-clad plate with low dielectric loss and high heat resistance | |
CN115819766B (en) | Modified maleimide prepolymer, resin composition and application of resin composition | |
CN109233724B (en) | High-glass-transition-temperature adhesive and application thereof to covering film | |
CN111825955A (en) | High-frequency prepreg, preparation method thereof, copper-clad plate and preparation method thereof | |
CN111605269A (en) | FR4 copper-clad plate with high relative tracking index and high heat resistance and preparation method thereof | |
CN115181395A (en) | Thermosetting resin composition and application thereof | |
CN111531983B (en) | High-heat-resistance low-dielectric copper-clad plate and preparation method thereof | |
CN113844130A (en) | Preparation method of high-Tg high-frequency copper-clad plate | |
CN116333491B (en) | Halogen-free resin composition suitable for high-speed communication and application thereof | |
CN116552074B (en) | High-heat-dissipation low-dielectric copper-clad plate and preparation method thereof | |
CN117264419B (en) | Halogen-free flame-retardant high-Tg resin composition, resin glue solution, prepreg, copper-clad plate and preparation method thereof, and circuit board | |
CN116970275A (en) | Resin composition, prepreg and preparation method thereof, copper-clad plate and preparation method thereof, and printed circuit board | |
CN116901550B (en) | High-heat-dissipation liquid crystal epoxy resin copper-clad plate and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
CB02 | Change of applicant information |
Address after: 265400 No.268, Guoda Road, Zhaoyuan City, Yantai City, Shandong Province Applicant after: Shandong Jinbao Electronics Co.,Ltd. Address before: 265400 No.268, Guoda Road, Zhaoyuan City, Yantai City, Shandong Province Applicant before: SHANDONG JINBAO ELECTRONICS Co.,Ltd. |
|
CB02 | Change of applicant information | ||
GR01 | Patent grant | ||
GR01 | Patent grant |