CN104985907A - Manufacturing method for high-TG halogen-free LOW Dk/Df copper-clad plate - Google Patents
Manufacturing method for high-TG halogen-free LOW Dk/Df copper-clad plate Download PDFInfo
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- CN104985907A CN104985907A CN201510317909.4A CN201510317909A CN104985907A CN 104985907 A CN104985907 A CN 104985907A CN 201510317909 A CN201510317909 A CN 201510317909A CN 104985907 A CN104985907 A CN 104985907A
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- halogen
- clad plate
- free copper
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- epoxy resin
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- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 239000003822 epoxy resin Substances 0.000 claims abstract description 24
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 24
- 239000003292 glue Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007731 hot pressing Methods 0.000 claims abstract description 12
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000012779 reinforcing material Substances 0.000 claims abstract description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004744 fabric Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000011256 inorganic filler Substances 0.000 claims abstract description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 238000004026 adhesive bonding Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 229930185605 Bisphenol Natural products 0.000 claims description 6
- 150000002118 epoxides Chemical class 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011889 copper foil Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical group CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract 3
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 abstract 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 238000000748 compression moulding Methods 0.000 abstract 1
- 238000005336 cracking Methods 0.000 abstract 1
- 235000019439 ethyl acetate Nutrition 0.000 abstract 1
- 239000011521 glass Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 class 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 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- 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
- B32B2457/00—Electrical equipment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a manufacturing method for a high-TG halogen-free LOW Dk/Df copper-clad plate. The method comprises the steps that 1, a glue solution is prepared, wherein a modified multifunctional-group phosphate-based epoxy resin/amine curing system is adopted, o-cresol type epoxy resin and bisphenol A type cyanate resin are added, and then a curing agent, a curing accelerant and an inorganic filler are added; a composition of any one or more of acetone, propylene glycol monomethyl ether acetic ester and butanone is used as a solvent for preparing the glue solution; 2, the glue is applied, wherein a low-dielectric-constant NE glass fabric is adopted as a reinforcing material, the reinforcing material is soaked with the obtained glue solution, and stage-B prepregs are obtained through a vertical glue applicator; 3, overlapping and hot pressing are performed, wherein the glued prepregs are overlapped in order, and compression molding is performed through a vacuum hot pressing machine. According to the halogen-free copper-clad plate obtained through the manufacturing method, the TG value is larger than 170 DEG C, the halogen-free copper-clad plate has the special performances of low dielectric constant and few dielectric losses, the Dk value is smaller than 3.8 and the Df value is smaller than 0.07. The halogen-free copper-clad plate can completely meet the requirement for manufacturing high-frequency and high-speed circuit boards, and meanwhile has the excellent performances of perfect heat resistance, good hot cracking decomposition temperature and the like.
Description
Technical field
The present invention relates to copper-clad plate field, particularly relate to a kind of preparation method being applicable to the high TG Halogen LOW Dk/Df copper-clad plate of high-frequency circuit board.
Background technology
After the harmful substance restriction instruction ROHS of European Union and China's Mainland implements successively, comprising the materials such as lead, cadmium, mercury, Cr VI, PBBs and PBDEs must not for the manufacture of electronic product or its assembly; The greening policy that green peace organization promotes (Green Peace) present stage energetically, requires that all manufacturers get rid of bromide fire retardant in its electronic product and polyvinyl chloride completely, has unleaded and halogen-free environment-friendly electronic concurrently to meet.But still have a lot of circuit-board industry to use bromine-containing compound at present, because brominated flame retardant flame retardant effect is excellent, and cost is lower; Halide is when ignition, the hydrogen halide that a large amount of toxicity is large, corrosivity is strong can be discharged, this gas not only contaminated environment, also certain infringement can be caused to health, and hydrocarbon is when existing bromine and chlorine, the extremely toxic substances such as bioxin can be produced in low temperature partial combustion process.
Along with the development of high-density installation SMT technology, and the requirement of PCB pb-free solder, in PCB processing and whole machine installation accessory, the number of occurrence of heat-shock is more than traditional through-hole mounting, so the vitrification point being only improved sheet material just can make reliability ensure to some extent and improve, the PCB reliability failures occurred in the life of product phase seems more and more important concerning client; The halogen-free copper-clad plate of low Tg more easily causes CAF to lose efficacy, and CAF is formed along glass fibre or resin interface shift by copper wire, and can produce internal electrical short-circuits between adjacent conductor, this is very serious problems concerning the design of high density circuit board.
Information technology develop rapidly now, all kinds of consumer electronics with high speed information processing capacity has been key component indispensable in daily life, the wireless telecommunications of military domain application and wide frequency technology are also rapidly to the transfer of civilian consumer electronics field, and the essential core of electronic information communication will be toward high frequency, high speed future development from now on; In today of high frequency technique sustainable development, 2GHZ, 3GHZ, 6GHZ and high-frequency is developed to from the frequency of traditional below 1GHZ, copper-clad plate is as one of the important component part of electronic product, and its dielectric constant (Dk) and Jie's fissipation factor (Df) just become the most important thing two performance indications being applied in and paying close attention in high frequency field.
The necessary resistance to combustion of circuit board, can not burn at a certain temperature, can only soften.At this moment temperature spot is just called glass transition temperature (TG point), and this value is related to the dimensional stability of pcb board.At present at printed circuit board industry, the TG value of its most halogen-free copper-clad plate is all at about 150 DEG C, dielectric constant (Dk) > 4.5, dielectric loss (Df) > 0.12, this type of sheet material is not suitable for making HF link plate.
Summary of the invention
The object of the present invention is to provide a kind of preparation method being applicable to the high TG Halogen LOW Dk/df copper-clad plate of high-frequency circuit board.
To achieve these goals, the preparation method of high TG Halogen LOW Dk/Df provided by the invention copper-clad plate, the steps include: that configuration glue---gluing---is superimposed, hot pressing;
Glue composition comprises: adopt modification multiple functional radical phosphorus system epoxy resin/amine-type cure system, add orthoresol type epoxy resin, bisphenol A-type cyanate resin, then add curing agent, curing accelerator and inorganic filler; Prepare as solvent with the composition of any or more than one in acetone, 1-Methoxy-2-propyl acetate, butanone;
Gluing: choose dielectric constant be the NE-glass-fiber-fabric of 4.0 ~ 4.5 as reinforcing material, soak with above-mentioned obtained glue, dry obtained B-stage prepreg through vertical gluing machine;
Superimposed, hot pressing: the prepreg of first-class glue is neatly superimposed, two-sided coated with Copper Foil, hot-forming through vacuum hotpressing machine.
In some embodiments, in glue, each Parts by Ingredients is:
In some embodiments, modification multiple functional radical phosphorus system epoxy resin is the multiple functional radical phosphorus system epoxy resin of epoxide equivalent 330 ~ 350; In modification multiple functional radical phosphorus system epoxy resin, phosphorus content is 2.6%.
In some embodiments, orthoresol type epoxy resin is the orthoresol type epoxy resin of epoxide equivalent 200 ~ 220.
In some embodiments, bisphenol A-type cyanate resin to be solid be 75% liquid bisphenol A type cyanate resin.
In some embodiments, curing agent is amine Dicy curing agent.
In some embodiments, curing accelerator is methylimidazole curing accelerator.
In some embodiments, select micron-class superfine aluminium hydroxide and silica as filler, its particle diameter D50 is 1.6-3.2um.
In some embodiments, adopt acetone, 1-Methoxy-2-propyl acetate as solvent.
In some embodiments, in gumming step, the speed of service of vertical gluing machine is 14 ~ 20m/min, and the gel time of prepreg is 106 ~ 126S, and the solids content of obtained prepreg is 42 ~ 53.5%, fluidity 18 ~ 32%; In superimposed, heat-press step, pressing parameter control be: vacuum is 20 → 60torro, and surface pressure is 0.4 ~ 3.6Mpa, and temperature of heat plate is 120 ~ 210 DEG C, and heating rate is 2 ~ 3 DEG C/min; Press time is 120 ~ 160min.
The preparation method of high TG Halogen LOW Dk/Df provided by the invention copper-clad plate compared with prior art, has the following advantages:
The present invention uses modified multiple functional radical phosphorus system epoxy resin to be the theme resin on formula, add the bisphenol A-type cyanate resin of Tg value is high, heat resistance is good orthoresol type epoxy resin and Heat stability is good, extremely low dielectric constant, then by adopting the NE glass-fiber-fabric of low-k as reinforcing material.Halogen-free copper-clad plate after hot-forming, except the key property such as electric property, insulating properties with conventional halogen-free copper-clad plate, also there is high glass transition temperature, its TG value > 170 DEG C, and also possess low-k, dielectric loss property, Df value < 3.8, Df value < 0.07, can meet the demand making high frequency, high-speed line plate completely, what it made also possesses the premium properties such as splendid heat resistance, hot tearing decomposition temperature substantially simultaneously.
Detailed description of the invention
Explanation that the present invention is described in further detail below by specific embodiment.
The preparation method of high TG Halogen LOW Dk/Df provided by the invention copper-clad plate, the steps include: that configuration glue---gluing---is superimposed, hot pressing.
S1: preparation glue
Described glue composition comprises (weight portion):
According to above-mentioned component preparation glue, gel after uniform stirring, its gel time is 288S;
The modification multiple functional radical phosphorus system epoxy resin of epoxide equivalent 345g/eq, phosphorus content 2.6% be DOPO system epoxy resin by add multiple functional radical resin and the third diphenol phenolic resin modified after epoxy resin.Main feature is: Working window substrate Tg value that is wide, that use it to make is higher, heat resistance and the feature such as flame resistance is good;
Epoxide equivalent is the orthoresol type epoxy resin of 210g/eq; Main Function is: as addition type, improves the TG value of made substrate, heat resistance and chemical resistance etc.
Its chemical constitution and consisting of:
Solid is the liquid bisphenol A type cyanate resin of 75%; This resin has good heat endurance, moisture-proof, the extremely low coefficient of expansion, extremely low dielectric constant and dielectric loss; Mainly play in this invention and reduce the effect such as dielectric constant and dielectric loss.
Its chemical constitution and composition:
Acetone, 1-Methoxy-2-propyl acetate are as solvent, and the prepreg outward appearance made of it is better.
S2: gluing
Dielectric constant be the NE-glass-fiber-fabric of 4.0 ~ 4.5 as reinforcing material, soak with above-mentioned obtained glue, dry the prepreg of obtained B-stage through vertical gluing machine; Gluing speed 19.2m/min, oil temperature 217 DEG C, controling parameters; Gel time 118 ± the 5S of its semi-solid preparation, solids content 44%, fluidity 22.3%.
S3: superimposed, hot pressing
The semi-solid preparation of first-class glue is neatly superimposed, and to make 1.6mm sheet material, its structure is: 8 2116R/C44%; Two-sided coated with Copper Foil again, compressing through vacuum hotpressing machine, concrete pressing parameter is as follows:
Vacuum: 20 ~ 60torro
Surface pressure: 0.6 ~ 3.6Mpa
Temperature of heat plate: 125 ~ 205 DEG C
Heating rate: 2 DEG C/min
Hot pressing time: 155min
When maximum temperature reaches 205 DEG C, corresponding is also maximal pressure 3.6Mpa, now running time 50min.
By above-mentioned steps, the test data of obtained high TG Halogen LOW Dk/Df copper-clad plate is:
| Test event | This example test data |
| Glass transition temperature (Tg, DEG C) | 178 |
| Peel strength (Ib/in) | 12.8 |
| Flame resistance (UL94) | V-0 |
| Water absorption rate | 0.13％ |
| T260(min) | ＞60 |
| Tg(℃) | 410℃ |
| Dk dielectric constant (1GHz) | 3.64 |
| Df dielectric loss (1GHz) | 0.0057 |
In sum, the present invention uses modified multiple functional radical phosphorus system epoxy resin to be the theme resin on formula, add the bisphenol A-type cyanate resin of Tg value is high, heat resistance is good orthoresol type epoxy resin and Heat stability is good, extremely low dielectric constant, then by adopting the NE glass-fiber-fabric of low-k as reinforcing material.Halogen-free copper-clad plate after hot-forming, except the key property such as electric property, insulating properties with conventional halogen-free copper-clad plate, also there is high glass transition temperature, its TG value > 170 DEG C, and also possess low-k, dielectric loss property, Df value < 3.8, Df value < 0.07, can meet the demand making high frequency, high-speed line plate completely, what it made also possesses the premium properties such as splendid heat resistance, hot tearing decomposition temperature substantially simultaneously.
A series of detailed description listed is above only illustrating for feasibility embodiment of the present invention; they are also not used to limit the scope of the invention, all do not depart from the skill of the present invention equivalent implementations done of spirit or change all should be included within protection scope of the present invention.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit of the present invention or essential characteristic, the present invention can be realized in other specific forms.Therefore, no matter from which point, all should embodiment be regarded as exemplary, and be nonrestrictive, scope of the present invention is limited by claims instead of above-mentioned explanation, and all changes be therefore intended in the implication of the equivalency by dropping on claim and scope are included in the present invention.
In addition, be to be understood that, although this description is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of description is only for clarity sake, those skilled in the art should by description integrally, and the technical scheme in each embodiment also through appropriately combined, can form other embodiments that it will be appreciated by those skilled in the art that.
Claims (10)
1. the preparation method of halogen-free copper-clad plate, the steps include: that configuration glue---gluing---is superimposed, hot pressing;
It is characterized in that, described glue composition comprises: adopt modification multiple functional radical phosphorus system epoxy resin/amine-type cure system, add orthoresol type epoxy resin, bisphenol A-type cyanate resin, then add curing agent, curing accelerator and inorganic filler; Prepare as solvent with the composition of any or more than one in acetone, 1-Methoxy-2-propyl acetate, butanone;
Gluing: choose dielectric constant be the NE-glass-fiber-fabric of 4.0 ~ 4.5 as reinforcing material, soak with above-mentioned obtained glue, dry obtained B-stage prepreg through vertical gluing machine;
Superimposed, hot pressing: the prepreg of first-class glue is neatly superimposed, two-sided coated with Copper Foil, hot-forming through vacuum hotpressing machine.
2. the preparation method of halogen-free copper-clad plate according to claim 1, is characterized in that, in described glue, each Parts by Ingredients is:
3. the preparation method of halogen-free copper-clad plate according to claim 2, is characterized in that, described modification multiple functional radical phosphorus system epoxy resin is the multiple functional radical phosphorus system epoxy resin of epoxide equivalent 330 ~ 350; In described modification multiple functional radical phosphorus system epoxy resin, phosphorus content is 2.6%.
4. the preparation method of halogen-free copper-clad plate according to claim 2, is characterized in that, described orthoresol type epoxy resin is the orthoresol type epoxy resin of epoxide equivalent 200 ~ 220.
5. the preparation method of halogen-free copper-clad plate according to claim 2, is characterized in that, described bisphenol A-type cyanate resin to be solid be 75% liquid bisphenol A type cyanate resin.
6. the preparation method of halogen-free copper-clad plate according to claim 2, is characterized in that, described curing agent is amine Dicy curing agent.
7. the preparation method of halogen-free copper-clad plate according to claim 2, is characterized in that, described curing accelerator is methylimidazole curing accelerator.
8. the preparation method of halogen-free copper-clad plate according to claim 2, is characterized in that, selects micron-class superfine aluminium hydroxide and silica as filler, and its particle diameter D50 is 1.6-3.2um.
9. the preparation method of halogen-free copper-clad plate according to claim 2, is characterized in that, adopts acetone, 1-Methoxy-2-propyl acetate as solvent.
10. the preparation method of halogen-free copper-clad plate according to claim 1, is characterized in that,
In gumming step, the speed of service of described vertical gluing machine is 14 ~ 20m/min, and the gel time of described prepreg is 106 ~ 126S, and the solids content of obtained described prepreg is 42 ~ 53.5%, fluidity 18 ~ 32%;
In superimposed, heat-press step, pressing parameter control be: vacuum is 20 → 60torro, and surface pressure is 0.4 ~ 3.6Mpa, and temperature of heat plate is 120 ~ 210 DEG C, and heating rate is 2 ~ 3 DEG C/min; Press time is 120 ~ 160min.
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Cited By (1)
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| CN106240132A (en) * | 2016-07-27 | 2016-12-21 | 重庆德凯实业股份有限公司 | A kind of manufacture method of halogen-free flameproof High Tg CCL |
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