CN110239164A - Tg copper-clad plate and preparation method thereof in high-fire resistance - Google Patents
Tg copper-clad plate and preparation method thereof in high-fire resistance Download PDFInfo
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- CN110239164A CN110239164A CN201910509041.6A CN201910509041A CN110239164A CN 110239164 A CN110239164 A CN 110239164A CN 201910509041 A CN201910509041 A CN 201910509041A CN 110239164 A CN110239164 A CN 110239164A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
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- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/098—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
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- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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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
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- 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
- 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
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- 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
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- 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
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- 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
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- 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
- B32B2457/08—PCBs, i.e. printed circuit boards
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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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- 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
Abstract
The present invention provides Tg copper-clad plates in a kind of high-fire resistance and preparation method thereof, belong to laminar product field.Tg copper-clad plate in high-fire resistance provided by the invention, including prepreg and copper foil, the prepreg single or double cover copper foil.The preparation method of prepreg be glass fabric is immersed in glue, drying to get.Wherein, the raw material of the glue include 50-300 part filler, 1500-4000 parts of epoxy resin, 200-400 parts of curing agent, 1-10 parts of catalyst and 100-300 parts of solvents by weight.Above-mentioned laminate preparation process are as follows: stack 1-10 layer prepreg, single or double is covered with copper foil, using hot press pressing to get.Tg copper-clad plate has excellent heat resistance, low Z-direction thermal expansion coefficient and superior through-hole ability in high-fire resistance provided by the invention, meets the code requirement of IPC-4101/99.
Description
Technical field
The invention belongs to laminar product field, Tg copper-clad plate and preparation method thereof in especially a kind of high-fire resistance.
Background technique
Copper-clad plate also known as substrate.Supporting material is soaked with resin, one or both sides are coated with copper foil, through made of hot pressing one
Kind board-like material, referred to as copper-clad laminate.It is the basic material for doing printed circuit board, is often substrate.When it is used for multilayer
When plate produces, core plate is also.
Copper-clad plate is the basic material of electronics industry, be mainly used for fabricate printed circuit board, be widely used in television set,
The electronic products such as radio, computer, computer, mobile communication.Substrate is made of high molecular synthetic resin and reinforcing material
Insulating laminated plate；It is covered with that one layer of conductivity be higher, the good pure copper foil of weldability on the surface of the substrate；Copper foil is covered on substrate one
The copper-clad plate in face is known as single-side coated copper plate, and the copper-clad plate that the two sides of substrate covers copper foil claims double face copper；Can copper foil jail
Admittedly overlay on substrate, then completed by adhesive.The thickness of common copper-clad plate has tri- kinds of 1.0mm, 1.5mm and 2.0mm.Cover copper
The type of plate is also more.Paper base plate, glass cloth substrate and pressboard can be divided by insulating materials difference；By binder resin
It is different to be divided into phenolic aldehyde, epoxy, polyester and polytetrafluoroethylene (PTFE) etc. again；Universal and special type can be divided by purposes.
The composition part of copper-clad plate: 1, substrate: the insulating laminated sheet of high molecular synthetic resin and reinforcing material composition can be with
Substrate as copper clad plate.Synthetic resin it is many kinds of, there are commonly phenolic resin, epoxy resin, polytetrafluoroethylene (PTFE) etc..Increase
Strong material generally has papery and two kinds of cloth, they determine the mechanical performance of substrate, such as resistance to dip solderability, bending strength.2,
Copper foil: it is the critical material for manufacturing copper clad plate, it is necessary to have higher conductivity and good weldability.It is required that copper foil surface is not
Must there are scratch, sand holes and gauffer, metal purity is not less than 99.8%, and thickness error is not more than ± 5um.It is advised according to ministry standard
Fixed, the nominal series of copper thickness is 18,25,35,70 and 105um.Currently gradually promote the use of 35um thickness in China
Copper foil.Copper foil is thinner, easier etching and drilling, particularly suitable for manufacturing the highdensity printed board of complex circuit.3, copper is covered
Plate adhesive: adhesive is the key factor that can copper foil be overlayed on securely on substrate.The peel strength of copper clad plate mainly depends on
In the performance of adhesive.
The thermal stress of copper-clad plate is mostly in 10Sec or so in the prior art, and thermal decomposition indexing is at 325 DEG C or so, Bu Nengman
Sufficient increasing demand.
Summary of the invention
Since above-mentioned deficiency exists in the prior art, the present invention provides Tg copper-clad plate and its productions in a kind of high-fire resistance
Technique, raw material and preparation method to glue have carried out major tuneup, have improved epoxy resin, curing agent, filler etc., make
There is the final copper sheet obtained that covers excellent heat resistance, low Z-direction thermal expansion coefficient and superior through-hole ability, perfection to meet IPC-
4101/99 code requirement.
Specifically, the present invention is achieved through the following technical solutions:
Tg copper-clad plate in high-fire resistance, including prepreg and copper foil, the prepreg single or double cover copper foil, institute
The preparation method for stating prepreg includes the following steps:
Glass fabric is immersed in glue, drying to get；
The raw material of the glue include filler, epoxy resin, curing agent, catalysts and solvents；
The raw material of the glue include 50-300 part filler, 1500-4000 parts of epoxy resin, 200- by weight
400 parts of curing agent, 1-10 parts of catalyst and 100-300 parts of solvents；
The epoxy resin is made of epoxy resin A and epoxy resin B, and the epoxy resin A is selected from o-cresol type ring oxygen
Any one in resin, polyfunctional epoxy resin or anacardol base epoxy；
The epoxy resin B is selected from o-cresol type epoxy resin, polyfunctional epoxy resin or anacardol base epoxy
In any one, and epoxy resin A and epoxy resin B type is different.
Preferably, the curing agent is phenolic resin class curing agent；
The phenolic resin is selected from phenol type phenolic resin, adjacent phenol type phenolic resin, multifunctional phenolic resin, Linear Double
In phenol A phenolic resin or bisphenol F phenolic resin any one or it is any a variety of.
Further preferably, the curing agent is multifunctional phenolic resin.
Preferably, the curing agent is phenolic resin class curing agent and/or more amine curing agents to a more step；
Preferably, more amine curing agents are the diamine derivative containing ferrocenyl；
It is highly preferred that the diamine derivative of the ferrocene is N, bis- (two (ferrocenyl) methyl) ethylenediamines of N'-.
Preferably, the preparation method of the anacardol base epoxy includes the following steps:
S1,100-150 part anacardol of meter by weight, 1-3 parts of oxalic acid are mixed under inert gas protection, heating
To 90-100 DEG C, 20-25 parts of 30-40wt% formalins are added, reaction is warming up to 110-120 DEG C after 2-3 hours, be added
450-550 parts of epoxychloropropane and 1-3 parts of alkyl dimethyl ammonium chlorides react 3-5 hours, are cooled to 50-70 DEG C, and 20- is added
30 parts of solid sodium hydroxides, the reaction was continued 1-3 hours, and 50-70 DEG C of water washing twice, merges organic phase to get intermediate A；
S2,65-75 part intermediate A by by weight, 65-75 parts of alkylsiloxanes and 0.001-0.005 parts
The mixing of Karstedt catalyst, is heated to 100-120 DEG C, reacts 5-8 hours, is cooled to 70-80 DEG C, and 2-5 parts of active carbons are added,
Reaction 1-3 hours after, cooled to room temperature, be filtered to remove solid to get.
Preferably, the alkyl dimethyl ammonium chloride in the preparation method of the anacardol base epoxy is selected from dodecyl
Dimethyl benzyl ammonium chloride, myristyl benzyl dimethyl ammonium chloride, cetalkonium chloride or octadecyl
In dimethyl benzyl ammonium chloride any one or or it is any a variety of.
Preferably, the alkylsiloxane in the preparation method of the anacardol base epoxy is selected from two silicon oxygen of tetramethyl
Alkane, pentamethyl disiloxane, hexaethyldisiloxane, four silicon oxygen of hexam ethylcyclotrisiloxane, heptamethyltrisiloxane or prestox
In alkane any one or or it is any a variety of.
Preferably, the filler is any one or more in silicon powder, Nano carbon balls or graphite foam powder.
Preferably, the filler by by weight 1-3 part Nano carbon balls and the mixing that forms of 1-3 parts of graphite foam powder
Filler.
Preferably, the preparation method of the Nano carbon balls includes the following steps:
S1, the ethanol solution of the ethyl orthosilicate of 3-8 part 0.1-0.3g/mL by weight is added to 5-12 parts of second
It in the solution of alcohol, 0.1-1 part water and 1-3 parts of ammonium hydroxide composition, stirs 1-3 hours, centrifugation takes solid, obtains crude silica；
S2, the crude silica of 1-3 part by weight is dissolved in 60-80 parts of ethyl alcohol, is heated to 60-80 DEG C,
1-3 parts of silane coupling agents are added, stir 24-36 hours, centrifuging and taking solid, it is 4-8 hours dry at 100-120 DEG C, obtain titanium dioxide
Silicon template；
S3,1-3 part silica template by weight is dispersed in 3-8 parts of 0.2-0.8mol/L aqueous sucrose solutions
In, it being transferred in autoclave, is heated to 180-200 DEG C, kept for 2-3 hours, centrifugation takes solid, and it is dry, in inert gas
Under atmosphere 850-900 DEG C carbonization 1-3 hours, obtain carbonization polysaccharide-silica spheres；
S4,1-3 part by weight is carbonized polysaccharide-silica spheres in 2-5 parts of 5-20wt% hydrofluoric acid aqueous solutions
Middle immersion 1-3 hours, centrifuging and taking solid, it is dry to get.
Preferably, the preparation method of the graphite foam powder includes the following steps:
S1, it 0.2-0.8 part PAN base carbon fibre by weight is dissolved in 10-30 parts of DMF is heated to 70-90 DEG C,
2-5 parts of magnesium powders are added, revolving removes liquid, and the ground 100-500 mesh of obtained solid is placed in chemical vapor deposition unit,
In argon gas/hydrogen atmosphere, it is heated to 900-1000 DEG C with the rate of heat addition of 5-10 DEG C/min, and protect at 900-1000 DEG C
It holds 20-60 minutes, is taken out after cooling to room temperature with the furnace, obtain intermediate；
S2,1-3 part intermediate by weight is immersed in 3-5 parts of 1mol/L ferric chloride in aqueous solution 24-72 hours,
Filtering, take solid, be washed with water 1-3 time, dry to get.
Preferably, chemical vapor deposition unit argon flow is 400- in the preparation method S1 of the graphite foam powder
600sccm, hydrogen flowing quantity 100-300sccm.
Preferably, the catalyst is any in 2-methylimidazole, -4 methylimidazole of 2- ethyl or 2- phenylimidazole
It is one or more.
Preferably, the solvent is any one or more in propylene glycol methyl ether acetate, acetone or butanone.
Preferably, the preparation method of the glue includes the following steps:
S1, filler dispersion: epoxy resin A and solvent being added in blender, revolving speed is kept to stir greater than 1000rpm,
Filler is stirred while being added, after the completion of filler addition, the revolving speed for continuing to be remained above 1000rpm is stirred 4-5 hours, obtains intermediate production
Object A；
S2, epoxy resin A and epoxy resin B is added in dosage bunker, intermediate product A is added, stirring obtains intermediate product B；
S3, intermediate product B is added in ingredient large trough, curing agent and catalyst is added, stirring samples after at least 5 hours
Glue curing time is detected, when glue curing time is in 280-320s, stopping stirring is to get glue.
The preparation method of Tg copper-clad plate, includes the following steps: in high-fire resistance
Stack 1-10 layer prepreg, single or double is covered with copper foil, in addition mold, using hot press pressing to get.
Preferably, the preparation method hot press parameter of Tg copper-clad plate is as follows in high-fire resistance:
Initial phase: duration 25-35 minutes, 80-140 DEG C of constant temperature, pressure 50-70psi；
Heating period: 1.2-2.0 DEG C of heating rate/min is warming up to 170-180 DEG C of stopping heating, pressure 50-70psi；
Hot press period: duration was more than or equal to 45 minutes, 170-180 DEG C of constant temperature, pressure 280-370psi；
Cooling stage: cooling rate is cooled to room temperature stopping cooling, pressure 30-50psi less than 2.5 DEG C/min.
Preferably, the mold is steel alloy 4Cr5Mo2V.
The invention has the beneficial effects that: the copper sheet provided by the invention that covers has used novel glue, which has used more
Kind of epoxy resin, also improves filler, also uses a kind of multifunctional phenolic resin as curing agent.Thermosetting property polymerization
Physical stress relaxation in object is limited by being crosslinked, and crosslinking hinders segmentation movement and limits the relaxation of network defective.Together
When, polymerizeing relevant cure shrinkage to thermosetting property leads to the development of the internal residual stress that cannot effectively relax.And it uses more
Solidification internal stress can be effectively reduced as curing agent in function phenolic resin, and this avoids use dicy to solidify.It is covered made from final
Copper sheet has excellent heat resistance, low Z-direction thermal expansion coefficient and superior through-hole ability.
Specific embodiment
Combined with specific embodiments below, the present invention is further elaborated on, following embodiments are only used to explain
The present invention can not be considered as to further limitation of the invention.
Specifically, the raw material sources in following embodiments are as follows:
O-cresol type epoxy resin, model 704K80, epoxide equivalent 215g/eq, South Asia electronic material (Kunshan) are limited
Company's production.
Polyfunctional epoxy resin model 485HA80, epoxide equivalent 400g/eq, South Asia electronic material (Kunshan) are limited
Company's production.
Multifunctional phenolic resin, model 710HK65, epoxide equivalent 107g/eq, South Asia electronic material (Kunshan) limited public affairs
Department's production.
Glass fabric, electron level, model 7628M-127, grammes per square metre 210g/m2, thickness 0.18mm, Mount Taishan glass fibre
The production of Zhou Cheng Co., Ltd.
Copper foil, 1 ounce of thickness, the production of Jin Yuanchao Hui Tong industry Co., Ltd, Lingbao City.
Silicon powder, 1250 mesh of granularity are purchased from Lingshou County Ze Tong mineral products processing factory.
Karstedt catalyst, the production of Ao Kai organosilicon material Co., Ltd, Shenzhen.
Active carbon, Shanghai Songyuan hold 200 mesh cocoanut active charcoals of Environmental Protection Technology Co., Ltd's production.
PAN base carbon fibre, the 1.5D PAN base carbon fibre of Accessories during Binzhou Qi Dong carbon materials Co., Ltd production.
Magnesium powder, partial size are 3 μm, and Hebi Glan is produced up to Mei Ye Co., Ltd.
Silane coupling agent KH560, entitled γ-(2,3- the third oxygen of the epoxy) propyl trimethoxy silicane of chemistry, Hubei Chu Shengwei
Chemical Co., Ltd.'s production.
Mold materials are steel alloy 4Cr5Mo2V, and middle mountain Fahrenheit die steel Co., Ltd provides.
All fillers cross 1250 meshes using preceding.
Embodiment 1
Tg copper-clad plate in high-fire resistance, is made of prepreg and copper foil, the prepreg two-sided copper foil covered, and described half
Steps are as follows for the preparation method of cured plate:
Glass fabric is immersed in glue, by electronic-grade glass fiber cloth frame on cloth holder containing dipping machine, by glass fibers
Wei Bu by being saturated with the impregnating groove of glue, be impregnated with glue glass fabric be put into 170 DEG C of baking 1min of baking oven to get；
The raw material of the glue include 140 parts of fillers by weight, 2500 parts of epoxy resin, 300 parts of curing agent,
4 parts of catalyst and 250 parts of solvents；
The epoxy resin up to 1250 parts of epoxy resin A and 1250 parts of epoxy resin B by forming by weight, the ring
Oxygen Resin A is o-cresol type epoxy resin；The epoxy resin B is polyfunctional epoxy resin；
The filler is silicon powder；
The curing agent is multifunctional phenolic resin；
The catalyst is 2-methylimidazole；
The solvent is propylene glycol methyl ether acetate.
Steps are as follows for the preparation method of the glue:
S1, filler dispersion: by 1000 parts of o-cresol type epoxy resin and 250 parts of propylene glycol monomethyl ether acetic acid by weight
Ester is added in blender, keeps revolving speed 1200rpm stirring, is stirring while being added 140 parts of silicon powders by weight, addition
After the completion, continue to keep the revolving speed of 1200rpm to stir 4 hours, obtain intermediate product A；
S2, by by weight 250 parts of o-cresol type epoxy resin and the addition of 1250 parts of polyfunctional epoxy resins match
In hopper, intermediate product A is added, stirring obtains intermediate product B；
S3, intermediate product B is added in ingredient large trough, 300 parts of multifunctional phenolic resin and 4 by weight is added
Part 2-methylimidazole, sample detection glue curing time after 500rpm is stirred 5 hours, when glue curing time is in 280-320s
When, stop stirring to get glue.
The preparation method of Tg copper-clad plate in high-fire resistance, steps are as follows:
7 layers of prepreg are stacked, it is two-sided to be covered with copper foil, in addition mold, is pressed using hot press, cut as needed, i.e.,
?；
Hot press parameter is as follows:
Initial phase: duration 30 minutes, 100 DEG C of constant temperature, pressure 60psi；
Heating period: 1.5 DEG C/min of heating rate is warming up to 180 DEG C of stopping heatings, pressure 60psi；
Hot press period: duration 45 minutes, 180 DEG C of constant temperature, pressure 320psi；
Cooling stage: cooling rate is 2 DEG C/min, is cooled to room temperature stopping cooling, pressure 40psi.
Embodiment 2
Tg copper-clad plate in high-fire resistance, is made of prepreg and copper foil, the prepreg two-sided copper foil covered, and described half
Steps are as follows for the preparation method of cured plate:
Glass fabric is immersed in glue, by electronic-grade glass fiber cloth frame on cloth holder containing dipping machine, by glass fibers
The glass fabric that Wei Bu by being saturated with the impregnating groove of glue, can be impregnated with glue be put into 170 DEG C of baking 1min of baking oven to get；
The raw material of the glue include 140 parts of fillers by weight, 2500 parts of epoxy resin, 300 parts of curing agent,
4 parts of catalyst and 250 parts of solvents；
The epoxy resin up to 1250 parts of epoxy resin A and 1250 parts of epoxy resin B by forming by weight, the ring
Oxygen Resin A is o-cresol type epoxy resin；The epoxy resin B is anacardol base epoxy；
The filler is silicon powder；
The curing agent is multifunctional phenolic resin；
The catalyst is 2-methylimidazole；
The solvent is propylene glycol methyl ether acetate.
Steps are as follows for the preparation method of the anacardol base epoxy:
S1,120 parts of anacardols of meter by weight, 2 parts of oxalic acid are mixed under nitrogen protection, is heated to 90 DEG C, adds
Enter 22 parts of 35wt% formalins, reaction is warming up to 115 DEG C after 2 hours, 480 parts of epoxychloropropane and 2 parts of tetradecanes are added
Base dimethyl benzyl ammonium chloride reacts 4 hours, is cooled to 70 DEG C, 23 parts of solid sodium hydroxides are added, the reaction was continued 2 hours, makes
Twice with 60 DEG C of water washings, 60 DEG C of each dosages of water be with it is isometric to cleaning solution, merge organic phase to get intermediate A；
S2,70 parts of intermediate As by by weight, 70 parts of hexam ethylcyclotrisiloxanes and 0.0013 part of Karstedt catalysis
Agent mixing, is heated to 115 DEG C, reacts 6 hours, is cooled to 75 DEG C, and 3 parts of active carbons are added and naturally cool to after reaction 1 hour
Room temperature sieves with 100 mesh sieve, remove solid to get.
Steps are as follows for the preparation method of the glue:
S1, filler dispersion: by 1000 parts of o-cresol type epoxy resin and 250 parts of propylene glycol monomethyl ether acetic acid by weight
Ester is added in blender, keeps revolving speed 1200rpm stirring, is stirring while being added 140 parts of silicon powders by weight, addition
After the completion, continue to keep the revolving speed of 1200rpm to stir 4 hours, obtain intermediate product A；
S2, by by weight 250 parts of o-cresol type epoxy resin and the addition of 1250 parts of anacardol base epoxies match
In hopper, intermediate product A is added, stirring obtains intermediate product B；
S3, intermediate product B is added in ingredient large trough, 300 parts of multifunctional phenolic resin and 4 by weight is added
Part 2-methylimidazole, sample detection glue curing time after 500rpm is stirred 5 hours, when glue curing time is in 280-320s
When, stop stirring to get glue.
The preparation method of Tg copper-clad plate in high-fire resistance, steps are as follows:
7 layers of prepreg are stacked, it is two-sided to be covered with copper foil, in addition mold, is pressed using hot press, cut as needed, i.e.,
?；
Hot press parameter is as follows:
Initial phase: duration 30 minutes, 100 DEG C of constant temperature, pressure 60psi；
Heating period: 1.5 DEG C/min of heating rate is warming up to 180 DEG C of stopping heatings, pressure 60psi；
Hot press period: duration 45 minutes, 180 DEG C of constant temperature, pressure 320psi；
Cooling stage: cooling rate is 2 DEG C/min, is cooled to room temperature stopping cooling, pressure 40psi.
Embodiment 3
Tg copper-clad plate in high-fire resistance, is made of prepreg and copper foil, the prepreg two-sided copper foil covered, and described half
Steps are as follows for the preparation method of cured plate:
Glass fabric is immersed in glue, by electronic-grade glass fiber cloth frame on cloth holder containing dipping machine, by glass fibers
The glass fabric that Wei Bu by being saturated with the impregnating groove of glue, can be impregnated with glue be put into 170 DEG C of baking 1min of baking oven to get；
The raw material of the glue include 140 parts of fillers by weight, 2500 parts of epoxy resin, 300 parts of curing agent,
4 parts of catalyst and 250 parts of solvents；
The epoxy resin up to 1250 parts of epoxy resin A and 1250 parts of epoxy resin B by forming by weight, the ring
Oxygen Resin A is polyfunctional epoxy resin；The epoxy resin B is anacardol base epoxy；
The filler is silicon powder；
The curing agent is multifunctional phenolic resin；
The catalyst is 2-methylimidazole；
The solvent is propylene glycol methyl ether acetate.
Steps are as follows for the preparation method of the anacardol base epoxy:
S1,120 parts of anacardols of meter by weight, 2 parts of oxalic acid are mixed under nitrogen protection, is heated to 90 DEG C, adds
Enter 22 parts of 35wt% formalins, reaction is warming up to 115 DEG C after 2 hours, 480 parts of epoxychloropropane and 2 parts of tetradecanes are added
Base dimethyl benzyl ammonium chloride reacts 4 hours, is cooled to 70 DEG C, 23 parts of solid sodium hydroxides are added, the reaction was continued 2 hours, makes
Twice with 60 DEG C of water washings, 60 DEG C of each dosages of water be with it is isometric to cleaning solution, merge organic phase to get intermediate A；
S2,70 parts of intermediate As by by weight, 70 parts of hexam ethylcyclotrisiloxanes and 0.0013 part of Karstedt catalysis
Agent mixing, is heated to 115 DEG C, reacts 6 hours, is cooled to 75 DEG C, and 3 parts of active carbons are added and naturally cool to after reaction 1 hour
Room temperature sieves with 100 mesh sieve, remove solid to get.
Steps are as follows for the preparation method of the glue:
S1, filler dispersion: by 1000 parts of polyfunctional epoxy resins and 250 parts of propylene glycol monomethyl ether acetic acid by weight
Ester is added in blender, keeps revolving speed 1200rpm stirring, is stirring while being added 140 parts of silicon powders by weight, addition
After the completion, continue to keep the revolving speed of 1200rpm to stir 4 hours, obtain intermediate product A；
S2, by by weight 250 parts of polyfunctional epoxy resins and the addition of 1250 parts of anacardol base epoxies match
In hopper, intermediate product A is added, stirring obtains intermediate product B；
S3, intermediate product B is added in ingredient large trough, 300 parts of multifunctional phenolic resin and 4 by weight is added
Part 2-methylimidazole, sample detection glue curing time after 500rpm is stirred 5 hours, when glue curing time is in 280-320s
When, stop stirring to get glue.
The preparation method of Tg copper-clad plate in high-fire resistance, steps are as follows:
7 layers of prepreg are stacked, it is two-sided to be covered with copper foil, in addition mold, is pressed using hot press, cut as needed, i.e.,
?；
Hot press parameter is as follows:
Initial phase: duration 30 minutes, 100 DEG C of constant temperature, pressure 60psi；
Heating period: 1.5 DEG C/min of heating rate is warming up to 180 DEG C of stopping heatings, pressure 60psi；
Hot press period: duration 45 minutes, 180 DEG C of constant temperature, pressure 320psi；
Cooling stage: cooling rate is 2 DEG C/min, is cooled to room temperature stopping cooling, pressure 40psi.
Embodiment 4
Tg copper-clad plate in high-fire resistance, is made of prepreg and copper foil, the prepreg two-sided copper foil covered, and described half
Steps are as follows for the preparation method of cured plate:
Glass fabric is immersed in glue, by electronic-grade glass fiber cloth frame on cloth holder containing dipping machine, by glass fibers
The glass fabric that Wei Bu by being saturated with the impregnating groove of glue, can be impregnated with glue be put into 170 DEG C of baking 1min of baking oven to get；
The raw material of the glue include 140 parts of fillers by weight, 2500 parts of epoxy resin, 300 parts of curing agent,
4 parts of catalyst and 250 parts of solvents；
The epoxy resin up to 1250 parts of epoxy resin A and 1250 parts of epoxy resin B by forming by weight, the ring
Oxygen Resin A is o-cresol type epoxy resin；The epoxy resin B is anacardol base epoxy；
The filler is silicon powder；
The curing agent has 270 parts of multifunctional phenolic resin and bis- (two (ferrocenyls) of 30 parts of N, N'- by weight
Methyl) ethylenediamine composition；
The catalyst is 2-methylimidazole；
The solvent is propylene glycol methyl ether acetate.
Steps are as follows for the preparation method of the anacardol base epoxy:
S1,120 parts of anacardols of meter by weight, 2 parts of oxalic acid are mixed under nitrogen protection, is heated to 90 DEG C, adds
Enter 22 parts of 35wt% formalins, reaction is warming up to 115 DEG C after 2 hours, 480 parts of epoxychloropropane and 2 parts of tetradecanes are added
Base dimethyl benzyl ammonium chloride reacts 4 hours, is cooled to 70 DEG C, 23 parts of solid sodium hydroxides are added, the reaction was continued 2 hours, makes
Twice with 60 DEG C of water washings, 60 DEG C of each dosages of water be with it is isometric to cleaning solution, merge organic phase to get intermediate A；
S2,70 parts of intermediate As by by weight, 70 parts of hexam ethylcyclotrisiloxanes and 0.0013 part of Karstedt catalysis
Agent mixing, is heated to 115 DEG C, reacts 6 hours, is cooled to 75 DEG C, and 3 parts of active carbons are added and naturally cool to after reaction 1 hour
Room temperature sieves with 100 mesh sieve, remove solid to get.
Steps are as follows for the preparation method of the glue:
S1, filler dispersion: by 1000 parts of o-cresol type epoxy resin and 250 parts of propylene glycol monomethyl ether acetic acid by weight
Ester is added in blender, keeps revolving speed 1200rpm stirring, is stirring while being added 140 parts of silicon powders by weight, addition
After the completion, continue to keep the revolving speed of 1200rpm to stir 4 hours, obtain intermediate product A；
S2, by by weight 250 parts of o-cresol type epoxy resin and the addition of 1250 parts of anacardol base epoxies match
In hopper, intermediate product A is added, stirring obtains intermediate product B；
S3, intermediate product B is added in ingredient large trough, 270 parts of multifunctional phenolic resin, 30 by weight is added
Part N, bis- (two (ferrocenyl) methyl) ethylenediamines of N'- and 4 parts of 2-methylimidazoles, sample detection glue after 500rpm is stirred 5 hours
Liquid curing time, when glue curing time is in 280-320s, stopping stirring is to get glue.
The preparation method of Tg copper-clad plate in high-fire resistance, steps are as follows:
7 layers of prepreg are stacked, it is two-sided to be covered with copper foil, in addition mold, is pressed using hot press, cut as needed, i.e.,
?；
Hot press parameter is as follows:
Initial phase: duration 30 minutes, 100 DEG C of constant temperature, pressure 60psi；
Heating period: 1.5 DEG C/min of heating rate is warming up to 180 DEG C of stopping heatings, pressure 60psi；
Hot press period: duration 45 minutes, 180 DEG C of constant temperature, pressure 320psi；
Cooling stage: cooling rate is 2 DEG C/min, is cooled to room temperature stopping cooling, pressure 40psi.
Embodiment 5
Tg copper-clad plate in high-fire resistance, is made of prepreg and copper foil, the prepreg two-sided copper foil covered, and described half
Steps are as follows for the preparation method of cured plate:
Glass fabric is immersed in glue, by electronic-grade glass fiber cloth frame on cloth holder containing dipping machine, by glass fibers
The glass fabric that Wei Bu by being saturated with the impregnating groove of glue, can be impregnated with glue be put into 170 DEG C of baking 1min of baking oven to get；
The raw material of the glue include 140 parts of fillers by weight, 2500 parts of epoxy resin, 300 parts of curing agent,
4 parts of catalyst and 250 parts of solvents；
The epoxy resin up to 1250 parts of epoxy resin A and 1250 parts of epoxy resin B by forming by weight, the ring
Oxygen Resin A is o-cresol type epoxy resin；The epoxy resin B is anacardol base epoxy；
The filler is graphite foam powder；
The curing agent has 270 parts of multifunctional phenolic resin and bis- (two (ferrocenyls) of 30 parts of N, N'- by weight
Methyl) ethylenediamine composition；
The catalyst is 2-methylimidazole；
The solvent is propylene glycol methyl ether acetate.
Steps are as follows for the preparation method of the anacardol base epoxy:
S1,120 parts of anacardols of meter by weight, 2 parts of oxalic acid are mixed under nitrogen protection, is heated to 90 DEG C, adds
Enter 22 parts of 35wt% formalins, reaction is warming up to 115 DEG C after 2 hours, 480 parts of epoxychloropropane and 2 parts of tetradecanes are added
Base dimethyl benzyl ammonium chloride reacts 4 hours, is cooled to 70 DEG C, 23 parts of solid sodium hydroxides are added, the reaction was continued 2 hours, makes
Twice with 60 DEG C of water washings, 60 DEG C of each dosages of water be with it is isometric to cleaning solution, merge organic phase to get intermediate A；
S2,70 parts of intermediate As by by weight, 70 parts of hexam ethylcyclotrisiloxanes and 0.0013 part of Karstedt catalysis
Agent mixing, is heated to 115 DEG C, reacts 6 hours, is cooled to 75 DEG C, and 3 parts of active carbons are added and naturally cool to after reaction 1 hour
Room temperature sieves with 100 mesh sieve, remove solid to get.
Steps are as follows for the preparation method of the graphite foam powder:
S1, it 0.4 part of PAN base carbon fibre by weight is dissolved in 15 parts of DMF is heated to 80 DEG C, 3 parts of magnesium are added
Powder, revolving remove liquid, and obtained solid grinding, which sieves with 100 mesh sieve, to be placed in chemical vapor deposition unit, in argon gas/hydrogen gas
In atmosphere, wherein argon flow 500sccm, hydrogen flowing quantity 200sccm are heated to 1000 with the rate of heat addition of 10 DEG C/min
DEG C, and kept for 30 minutes at 1000 DEG C, it is taken out after cooling to room temperature with the furnace, obtains intermediate；
S2,2 parts of intermediates by weight are immersed in 5 parts of 1mol/L ferric chloride in aqueous solution 36 hours, cross 500 mesh
Sieve, takes solid, is washed with water 3 times, the dosage of each washing water be 2 times, 60 DEG C of solid masses at dry 8 hours to get.
Steps are as follows for the preparation method of the glue:
S1, filler dispersion: by 1000 parts of o-cresol type epoxy resin and 250 parts of propylene glycol monomethyl ether acetic acid by weight
Ester is added in blender, keeps revolving speed 1200rpm stirring, is stirring while being added 140 parts of graphite foam powder by weight,
After the completion of addition, continues to keep the revolving speed of 1200rpm to stir 4 hours, obtain intermediate product A；
S2, by by weight 250 parts of o-cresol type epoxy resin and the addition of 1250 parts of anacardol base epoxies match
In hopper, intermediate product A is added, stirring obtains intermediate product B；
S3, intermediate product B is added in ingredient large trough, 270 parts of multifunctional phenolic resin, 30 by weight is added
Part N, bis- (two (ferrocenyl) methyl) ethylenediamines of N'- and 4 parts of 2-methylimidazoles, sample detection glue after 500rpm is stirred 5 hours
Liquid curing time, when glue curing time is in 280-320s, stopping stirring is to get glue.
The preparation method of Tg copper-clad plate in high-fire resistance, steps are as follows:
7 layers of prepreg are stacked, it is two-sided to be covered with copper foil, in addition mold, is pressed using hot press, cut as needed, i.e.,
?；
Hot press parameter is as follows:
Initial phase: duration 30 minutes, 100 DEG C of constant temperature, pressure 60psi；
Heating period: 1.5 DEG C/min of heating rate is warming up to 180 DEG C of stopping heatings, pressure 60psi；
Hot press period: duration 45 minutes, 180 DEG C of constant temperature, pressure 320psi；
Cooling stage: cooling rate is 2 DEG C/min, is cooled to room temperature stopping cooling, pressure 40psi.
Embodiment 6
Tg copper-clad plate in high-fire resistance, is made of prepreg and copper foil, the prepreg two-sided copper foil covered, and described half
Steps are as follows for the preparation method of cured plate:
Glass fabric is immersed in glue, by electronic-grade glass fiber cloth frame on cloth holder containing dipping machine, by glass fibers
The glass fabric that Wei Bu by being saturated with the impregnating groove of glue, can be impregnated with glue be put into 170 DEG C of baking 1min of baking oven to get；
The raw material of the glue include 140 parts of fillers by weight, 2500 parts of epoxy resin, 300 parts of curing agent,
4 parts of catalyst and 250 parts of solvents；
The epoxy resin up to 1250 parts of epoxy resin A and 1250 parts of epoxy resin B by forming by weight, the ring
Oxygen Resin A is o-cresol type epoxy resin；The epoxy resin B is anacardol base epoxy；
The filler is Nano carbon balls；
The curing agent has 270 parts of multifunctional phenolic resin by weight
The catalyst is 2-methylimidazole；
The solvent is propylene glycol methyl ether acetate.
Steps are as follows for the preparation method of the anacardol base epoxy:
S1,120 parts of anacardols of meter by weight, 2 parts of oxalic acid are mixed under nitrogen protection, is heated to 90 DEG C, adds
Enter 22 parts of 35wt% formalins, reaction is warming up to 115 DEG C after 2 hours, 480 parts of epoxychloropropane and 2 parts of tetradecanes are added
Base dimethyl benzyl ammonium chloride reacts 4 hours, is cooled to 70 DEG C, 23 parts of solid sodium hydroxides are added, the reaction was continued 2 hours, makes
Twice with 60 DEG C of water washings, 60 DEG C of each dosages of water be with it is isometric to cleaning solution, merge organic phase to get intermediate A；
S2,70 parts of intermediate As by by weight, 70 parts of hexam ethylcyclotrisiloxanes and 0.0013 part of Karstedt catalysis
Agent mixing, is heated to 115 DEG C, reacts 6 hours, is cooled to 75 DEG C, and 3 parts of active carbons are added and naturally cool to after reaction 1 hour
Room temperature sieves with 100 mesh sieve, remove solid to get.
Steps are as follows for the preparation method of the Nano carbon balls:
S1, the ethanol solution of the ethyl orthosilicate of 4 parts of 0.2g/mL by weight is added to 7 parts of ethyl alcohol, 0.5 part
In the solution of water and 2 parts of 25wt% ammonium hydroxide composition, 500rpm is stirred 2 hours, and 7000rpm is centrifuged 10 minutes, is taken solid, is obtained crude
Silica；
S2,1 part of crude silica by weight is dissolved in 70 parts of ethyl alcohol, is heated to 70 DEG C, 2 parts of silicon is added
Alkane coupling agent KH560,100rpm stirring 24 hours, 7000rpm, which is centrifuged, took solid for 10 minutes, 6 hours dry at 110 DEG C, obtained two
Silica template；
S3,2 parts of silica templates by weight are dispersed in 6 parts of 0.5mol/L aqueous sucrose solutions, are transferred to
In autoclave, 190 DEG C are heated to, is kept for 2 hours, 5000rpm is centrifuged 10 minutes, solid is taken, drying 12 hours at 50 DEG C,
It is carbonized 2 hours at 900 DEG C in a nitrogen atmosphere, obtains carbonization polysaccharide-silica spheres；
S4,1 part of carbonization polysaccharide-silica spheres by weight are impregnated 3 in 3 parts of 12wt% hydrofluoric acid aqueous solutions
Hour, 5000rpm is centrifuged 10 minutes, take solid, 70 DEG C of dryings 6 hours to get.
Steps are as follows for the preparation method of the glue:
S1, filler dispersion: by 1000 parts of o-cresol type epoxy resin and 250 parts of propylene glycol monomethyl ether acetic acid by weight
Ester is added in blender, keeps revolving speed 1200rpm stirring, is stirring while being added 140 parts of Nano carbon balls by weight, adding
After the completion of adding, continues to keep the revolving speed of 1200rpm to stir 4 hours, obtain intermediate product A；
S2, by by weight 250 parts of o-cresol type epoxy resin and the addition of 1250 parts of anacardol base epoxies match
In hopper, intermediate product A is added, stirring obtains intermediate product B；
S3, intermediate product B is added in ingredient large trough, 270 parts of multifunctional phenolic resin and 4 by weight is added
Part 2-methylimidazole, sample detection glue curing time after 500rpm is stirred 5 hours, when glue curing time is in 280-320s
When, stop stirring to get glue.
The preparation method of Tg copper-clad plate in high-fire resistance, steps are as follows:
7 layers of prepreg are stacked, it is two-sided to be covered with copper foil, in addition mold, is pressed using hot press, cut as needed, i.e.,
?；
Hot press parameter is as follows:
Initial phase: duration 30 minutes, 100 DEG C of constant temperature, pressure 60psi；
Heating period: 1.5 DEG C/min of heating rate is warming up to 180 DEG C of stopping heatings, pressure 60psi；
Hot press period: duration 45 minutes, 180 DEG C of constant temperature, pressure 320psi；
Cooling stage: cooling rate is 2 DEG C/min, is cooled to room temperature stopping cooling, pressure 40psi.
Embodiment 7
Tg copper-clad plate in high-fire resistance, is made of prepreg and copper foil, the prepreg two-sided copper foil covered, and described half
Steps are as follows for the preparation method of cured plate:
Glass fabric is immersed in glue, by electronic-grade glass fiber cloth frame on cloth holder containing dipping machine, by glass fibers
The glass fabric that Wei Bu by being saturated with the impregnating groove of glue, can be impregnated with glue be put into 170 DEG C of baking 1min of baking oven to get；
The raw material of the glue include 140 parts of fillers by weight, 2500 parts of epoxy resin, 300 parts of curing agent,
4 parts of catalyst and 250 parts of solvents；
The epoxy resin up to 1250 parts of epoxy resin A and 1250 parts of epoxy resin B by forming by weight, the ring
Oxygen Resin A is o-cresol type epoxy resin；The epoxy resin B is anacardol base epoxy；
The filler by by weight 100 parts of graphite foam powder and 40 parts of Nano carbon balls form；
The curing agent has 270 parts of multifunctional phenolic resin by weight
The catalyst is 2-methylimidazole；
The solvent is propylene glycol methyl ether acetate.
Steps are as follows for the preparation method of the anacardol base epoxy:
S1,120 parts of anacardols of meter by weight, 2 parts of oxalic acid are mixed under nitrogen protection, is heated to 90 DEG C, adds
Enter 22 parts of 35wt% formalins, reaction is warming up to 115 DEG C after 2 hours, 480 parts of epoxychloropropane and 2 parts of tetradecanes are added
Base dimethyl benzyl ammonium chloride reacts 4 hours, is cooled to 70 DEG C, 23 parts of solid sodium hydroxides are added, the reaction was continued 2 hours, makes
Twice with 60 DEG C of water washings, 60 DEG C of each dosages of water be with it is isometric to cleaning solution, merge organic phase to get intermediate A；
S2,70 parts of intermediate As by by weight, 70 parts of hexam ethylcyclotrisiloxanes and 0.0013 part of Karstedt catalysis
Agent mixing, is heated to 115 DEG C, reacts 6 hours, is cooled to 75 DEG C, and 3 parts of active carbons are added and naturally cool to after reaction 1 hour
Room temperature sieves with 100 mesh sieve, remove solid to get.
Steps are as follows for the preparation method of the graphite foam powder:
S1, it 0.4 part of PAN base carbon fibre by weight is dissolved in 15 parts of DMF is heated to 80 DEG C, 3 parts of magnesium are added
Powder, revolving remove liquid, and obtained solid grinding, which sieves with 100 mesh sieve, to be placed in chemical vapor deposition unit, in argon gas/hydrogen gas
In atmosphere, wherein argon flow 500sccm, hydrogen flowing quantity 200sccm are heated to 1000 with the rate of heat addition of 10 DEG C/min
DEG C, and kept for 30 minutes at 1000 DEG C, it is taken out after cooling to room temperature with the furnace, obtains intermediate；
S2,2 parts of intermediates by weight are immersed in 5 parts of 1mol/L ferric chloride in aqueous solution 36 hours, cross 500 mesh
Sieve, takes solid, is washed with water 3 times, the dosage of each washing water be 2 times, 60 DEG C of solid masses at dry 8 hours to get.
Steps are as follows for the preparation method of the Nano carbon balls:
S1, the ethanol solution of the ethyl orthosilicate of 4 parts of 0.2g/mL by weight is added to 7 parts of ethyl alcohol, 0.5 part
In the solution of water and 2 parts of 25wt% ammonium hydroxide composition, 500rpm is stirred 2 hours, and 7000rpm is centrifuged 10 minutes, is taken solid, is obtained crude
Silica；
S2,1 part of crude silica by weight is added in 70 parts of ethyl alcohol, is heated to 70 DEG C, 2 parts of silane is added
Coupling agent KH560,100rpm stirring 24 hours, 7000rpm, which is centrifuged, took solid for 10 minutes, 6 hours dry at 110 DEG C, obtained dioxy
SiClx template；
S3,2 parts of silica templates by weight are dispersed in 6 parts of 0.5mol/L aqueous sucrose solutions, are transferred to
In autoclave, 190 DEG C are heated to, is kept for 2 hours, 5000rpm is centrifuged 10 minutes, solid is taken, drying 12 hours at 50 DEG C,
It is carbonized 2 hours at 900 DEG C in a nitrogen atmosphere, obtains carbonization polysaccharide-silica spheres；
S4,1 part of carbonization polysaccharide-silica spheres by weight are impregnated 3 in 3 parts of 12wt% hydrofluoric acid aqueous solutions
Hour, 5000rpm is centrifuged 10 minutes, take solid, 70 DEG C of dryings 6 hours to get.
Steps are as follows for the preparation method of the glue:
S1, filler dispersion: by 1000 parts of o-cresol type epoxy resin and 250 parts of propylene glycol monomethyl ether acetic acid by weight
Ester is added in blender, keeps revolving speed 1200rpm stirring, is stirring while 100 parts of graphite foam powder by weight are added
It is formed with 40 parts of Nano carbon balls, after the completion of addition, continues to keep the revolving speed of 1200rpm to stir 4 hours, obtain intermediate product A；
S2, by by weight 250 parts of o-cresol type epoxy resin and the addition of 1250 parts of anacardol base epoxies match
In hopper, intermediate product A is added, stirring obtains intermediate product B；
S3, intermediate product B is added in ingredient large trough, 270 parts of multifunctional phenolic resin, 30 by weight is added
Part N, bis- (two (ferrocenyl) methyl) ethylenediamines of N'- and 4 parts of 2-methylimidazoles, sample detection glue after 500rpm is stirred 5 hours
Liquid curing time, when glue curing time is in 280-320s, stopping stirring is to get glue.
The preparation method of Tg copper-clad plate in high-fire resistance, steps are as follows:
7 layers of prepreg are stacked, it is two-sided to be covered with copper foil, in addition mold, is pressed using hot press, cut as needed, i.e.,
?；
Hot press parameter is as follows:
Initial phase: duration 30 minutes, 100 DEG C of constant temperature, pressure 60psi；
Heating period: 1.5 DEG C/min of heating rate is warming up to 180 DEG C of stopping heatings, pressure 60psi；
Hot press period: duration 45 minutes, 180 DEG C of constant temperature, pressure 320psi；
Cooling stage: cooling rate is 2 DEG C/min, is cooled to room temperature stopping cooling, pressure 40psi.
Test case 1
Tg copper-clad plate in high-fire resistance made from embodiment 1 carries out its main performance by the requirement of IPC-4101/99
Test, test result are as shown in table 1.
1 embodiment of table, 1 performance
Test case 2
Glass transition temperature
Use the glass transition temperature of Tg copper-clad plate in high-fire resistance made from differential scanning calorimetry (DSC) testing example 1-7.
Test result is as shown in table 2.
2 glass transition temperature of table (Tg)
| Glass transition temperature/DEG C | |
| Embodiment 1 | 155 |
| Embodiment 2 | 155 |
| Embodiment 3 | 156 |
| Embodiment 4 | 156 |
| Embodiment 5 | 157 |
| Embodiment 6 | 156 |
| Embodiment 7 | 157 |
As seen from the above table, the present invention provides Tg copper-clad plate glass transition temperature in high-fire resistance and is all larger than 150 DEG C, meets IPC-
4101 standards.
Test case 3
Z-direction thermal expansion coefficient
Z-direction thermal expansion coefficient is carried out to Tg copper-clad plate in high-fire resistance made from embodiment 1-7 using thermal expansion test instrument
Test.
Test result is as shown in table 3.
3 Z-direction thermal expansion coefficient of table (Z-axis CTE)
As seen from the above table, Tg copper-clad plate has excellent Z-direction thermal expansion coefficient in high-fire resistance provided by the invention, especially
It has a certain impact after filler changes to the Z-direction coefficient of expansion of copper-clad plate.
Test case 4
Thermal decomposition temperature
Use the thermal decomposition temperature of Tg copper-clad plate in high-fire resistance made from differential scanning calorimetry (DSC) testing example 1-7.
Test condition is 10 DEG C/min of heating rate, nitrogen atmosphere, 5% mass loss.
Test result is as shown in table 4.
4 thermal decomposition temperature of table
As seen from the above table, the thermal decomposition temperature of Tg copper-clad plate is in higher level in high-fire resistance provided by the invention,
Beyond 325 DEG C as defined in standard, also remote super copper-clad plates other in the prior art.
Test case 5
Thermal stress
The heat of Tg copper-clad plate is answered in the not etched high-fire resistance referring to made from IPC-4101 standard testing embodiment 1-7
Power.Test condition is float288 DEG C/10Sec.
Test result is as shown in table 5.
5 thermal stress of table
| Thermal stress/Sec | |
| Embodiment 1 | 120 |
| Embodiment 2 | 144 |
| Embodiment 3 | 125 |
| Embodiment 4 | 208 |
| Embodiment 5 | 211 |
| Embodiment 6 | 220 |
| Embodiment 7 | 277 |
As seen from the above table, the thermal stress of Tg copper-clad plate is in higher level in high-fire resistance provided by the invention, remote super
Standard value Sec, reaches as high as 277Sec.
Claims (10)
1. Tg copper-clad plate in high-fire resistance, including prepreg and copper foil, the prepreg single or double covers copper foil, special
Sign is that the preparation method of the prepreg includes the following steps:
Glass fabric is immersed in glue, drying to get；
The raw material of the glue include 50-300 part filler, 1500-4000 parts of epoxy resin, 200-400 by weight
Part curing agent, 1-10 parts of catalyst and 100-300 parts of solvents；
The epoxy resin is made of epoxy resin A and epoxy resin B, the epoxy resin A be selected from o-cresol type epoxy resin,
Any one in polyfunctional epoxy resin or anacardol base epoxy；
The epoxy resin B is in o-cresol type epoxy resin, polyfunctional epoxy resin or anacardol base epoxy
Any one, and epoxy resin A and epoxy resin B type is different.
2. Tg copper-clad plate in high-fire resistance according to claim 1, which is characterized in that the curing agent is phenolic resin class
Curing agent；
The phenolic resin is selected from phenol type phenolic resin, adjacent phenol type phenolic resin, multifunctional phenolic resin, linear bisphenol-A
In phenolic resin or bisphenol F phenolic resin any one or it is any a variety of.
3. Tg copper-clad plate in high-fire resistance according to claim 2, which is characterized in that the curing agent is multifunctional phenolic aldehyde
Resin.
4. Tg copper-clad plate in high-fire resistance according to claim 1, which is characterized in that the anacardol base epoxy
Preparation method includes the following steps:
S1,100-150 part anacardol of meter by weight, 1-3 parts of oxalic acid are mixed under inert gas protection, is heated to
90-100 DEG C, 20-25 parts of 30-40wt% formalins are added, reaction is warming up to 110-120 DEG C after 2-3 hours, 450- is added
550 parts of epoxychloropropane and 1-3 parts of alkyl dimethyl ammonium chlorides react 3-5 hours, are cooled to 50-70 DEG C, are added 20-30 parts
Solid sodium hydroxide, the reaction was continued 1-3 hours, and 50-70 DEG C of water washing twice, merges organic phase to get intermediate A；
S2, by 65-75 part intermediate A, 65-75 parts of alkylsiloxanes and 0.001-0.005 parts of Karstedt by weight
Catalyst mixing, is heated to 100-120 DEG C, reacts 5-8 hours, is cooled to 70-80 DEG C, and 2-5 parts of active carbons are added, and reacts 1-3
Hour after, cooled to room temperature, be filtered to remove solid to get.
5. Tg copper-clad plate in high-fire resistance according to claim 1, which is characterized in that the filler is silicon powder, carbon is received
Rice ball or graphite foam powder in any one or more.
6. Tg copper-clad plate in high-fire resistance according to claim 5, which is characterized in that the preparation method of the Nano carbon balls
Include the following steps:
S1, the ethanol solution of the ethyl orthosilicate of 3-8 part 0.1-0.3g/mL by weight is added to 5-12 parts of ethyl alcohol,
It in the solution of 0.1-1 parts of water and 1-3 parts of ammonium hydroxide composition, stirs 1-3 hours, centrifugation takes solid, obtains crude silica；
S2, the crude silica of 1-3 part by weight is dissolved in 60-80 parts of ethyl alcohol, is heated to 60-80 DEG C, be added
1-3 parts of silane coupling agents stir 24-36 hours, centrifuging and taking solid, 4-8 hours dry at 100-120 DEG C, obtain silica mould
Plate；
S3,1-3 part silica template by weight is dispersed in 3-8 parts of 0.2-0.8mol/L aqueous sucrose solutions, is turned
It moving in autoclave, is heated to 180-200 DEG C, kept for 2-3 hours, centrifugation takes solid, and it is dry, in inert gas atmosphere
Under 850-900 DEG C carbonization 1-3 hours, obtain carbonization polysaccharide-silica spheres；
S4,1-3 part carbonization polysaccharide-silica spheres by weight are soaked in 2-5 parts of 5-20wt% hydrofluoric acid aqueous solutions
Bubble 1-3 hour, centrifuging and taking solid, dry to get.
7. Tg copper-clad plate in high-fire resistance according to claim 5, which is characterized in that the preparation side of the graphite foam powder
Method includes the following steps:
S1, it 0.2-0.8 part PAN base carbon fibre by weight is dissolved in 10-30 parts of DMF is heated to 70-90 DEG C, be added
2-5 parts of magnesium powders, revolving remove liquid, and the ground 100-500 mesh of obtained solid is placed in chemical vapor deposition unit, in argon
In gas/hydrogen atmosphere, it is heated to 900-1000 DEG C with the rate of heat addition of 5-10 DEG C/min, and keep at 900-1000 DEG C
It 20-60 minutes, is taken out after cooling to room temperature with the furnace, obtains intermediate；
S2,1-3 part intermediate by weight is immersed in 3-5 parts of 1mol/L ferric chloride in aqueous solution 24-72 hours, mistake
Filter, take solid, be washed with water 1-3 time, dry to get.
8. Tg copper-clad plate in high-fire resistance according to claim 1, which is characterized in that the catalyst is selected from 2- methyl miaow
Any one or more in azoles, -4 methylimidazole of 2- ethyl or 2- phenylimidazole.
9. Tg copper-clad plate in high-fire resistance according to claim 1, which is characterized in that the preparation method of the glue includes
Following step:
S1, filler dispersion: epoxy resin A and solvent are added in blender, keeps revolving speed to stir greater than 1000rpm, is stirring
Filler is added simultaneously, after the completion of filler addition, the revolving speed for continuing to be remained above 1000rpm is stirred 4-5 hours, obtains intermediate product A；
S2, epoxy resin A and epoxy resin B is added in dosage bunker, intermediate product A is added, stirring obtains intermediate product B；
S3, intermediate product B is added in ingredient large trough, curing agent and catalyst, sample detection after stirring at least 5 hours is added
Glue curing time, when glue curing time is in 280-320s, stopping stirring is to get glue.
10. the preparation method of Tg copper-clad plate in high-fire resistance described in any one of claim 1-9, which is characterized in that including
Following step:
Stack 1-10 layer prepreg, single or double is covered with copper foil, in addition mold, using hot press pressing to get.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112430380A (en) * | 2020-11-23 | 2021-03-02 | 江苏诺德新材料股份有限公司 | Epoxy resin and glass fiber composite material composition and high-frequency copper-clad plate manufactured by same |
| TWI791249B (en) * | 2021-07-27 | 2023-02-01 | 財團法人工業技術研究院 | Impregnation liquid and activated carbon cloth and method of forming the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723356A (en) * | 2009-12-14 | 2010-06-09 | 同济大学 | Method for graphitizing amorphous carbon material at low temperature |
| CN101864146A (en) * | 2010-06-13 | 2010-10-20 | 宏昌电子材料股份有限公司 | Epoxy resin composition for printed circuit copper-clad plate |
| CN102102000A (en) * | 2010-12-30 | 2011-06-22 | 上海南亚覆铜箔板有限公司 | Adhesive of medium glass transition temperature epoxy glass cloth-based copper-clad laminate suitable for lead-free process |
| CN102166854A (en) * | 2010-12-30 | 2011-08-31 | 上海南亚覆铜箔板有限公司 | Intermediate-Tg lead-free compatible copper foil-covered board and preparation method thereof |
| CN103012743A (en) * | 2012-12-14 | 2013-04-03 | 中国林业科学研究院林产化学工业研究所 | Cashew novolac epoxy resin and preparation method thereof |
-
2019
- 2019-06-13 CN CN201910509041.6A patent/CN110239164B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723356A (en) * | 2009-12-14 | 2010-06-09 | 同济大学 | Method for graphitizing amorphous carbon material at low temperature |
| CN101864146A (en) * | 2010-06-13 | 2010-10-20 | 宏昌电子材料股份有限公司 | Epoxy resin composition for printed circuit copper-clad plate |
| CN102102000A (en) * | 2010-12-30 | 2011-06-22 | 上海南亚覆铜箔板有限公司 | Adhesive of medium glass transition temperature epoxy glass cloth-based copper-clad laminate suitable for lead-free process |
| CN102166854A (en) * | 2010-12-30 | 2011-08-31 | 上海南亚覆铜箔板有限公司 | Intermediate-Tg lead-free compatible copper foil-covered board and preparation method thereof |
| CN103012743A (en) * | 2012-12-14 | 2013-04-03 | 中国林业科学研究院林产化学工业研究所 | Cashew novolac epoxy resin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 上海科学院、上海产业技术研究院: "《多孔材料—奇妙的微结构》", 31 January 2018, 上海科学普及出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112430380A (en) * | 2020-11-23 | 2021-03-02 | 江苏诺德新材料股份有限公司 | Epoxy resin and glass fiber composite material composition and high-frequency copper-clad plate manufactured by same |
| TWI791249B (en) * | 2021-07-27 | 2023-02-01 | 財團法人工業技術研究院 | Impregnation liquid and activated carbon cloth and method of forming the same |
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