CN107722559A - Flame-retardant resin-based copper-clad plate and preparation method thereof - Google Patents

Flame-retardant resin-based copper-clad plate and preparation method thereof Download PDF

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Publication number
CN107722559A
CN107722559A CN201710850704.1A CN201710850704A CN107722559A CN 107722559 A CN107722559 A CN 107722559A CN 201710850704 A CN201710850704 A CN 201710850704A CN 107722559 A CN107722559 A CN 107722559A
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minutes
added
prepreg
stirred
flame
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郑炳洙
徐伟红
夏宇
朴龙星
梁国正
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Suzhou Jufeng New Material Technology Co ltd
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Suzhou Jufeng New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/74—Joining plastics material to non-plastics material
    • B29C66/742—Joining plastics material to non-plastics material to metals or their alloys
    • B29C66/7428—Transition metals or their alloys
    • B29C66/74281—Copper or alloys of 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/002—Panels; Plates; Sheets
    • 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
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • 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
    • 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
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/08—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K9/04—Ingredients treated with organic substances

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  • Crystallography & Structural Chemistry (AREA)
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Abstract

The invention relates to a flame-retardant resin-based copper-clad plate and a preparation method thereof, and the method comprises the following steps of adding a modified silicon dioxide foam system into a bifunctional epoxy system, stirring for 50 minutes at 130 ℃, then adding a monofunctional epoxy system and nano titanium dioxide whiskers at room temperature, and stirring for 30 minutes to obtain glue solution; adjusting the solid content of the glue solution to 55-60% by using PMA, and then impregnating the reinforced material to obtain a prepreg; heating and drying the prepreg to obtain a prepreg; and a prepreg is placed between the two copper foils, and hot press forming is carried out, so that the flame-retardant resin-based copper-clad plate can be obtained, has excellent flame retardant property and heat resistance, and meets the development and application requirements of the flame-retardant resin-based copper-clad plate.

Description

Flame-retarded resin base copper-clad plate and preparation method thereof
Technical field
The invention belongs to electronics technical field of composite materials, and in particular to a kind of flame-retarded resin base copper-clad plate and its preparation side Method, obtained product can be used for Aero-Space, signal transmission, telecommunications field.
Background technology
Printed substrate is to be formed by copper-clad plate after circuit makes, and copper-clad plate is by glass cloth and is attached to the glass Resin bed on cloth obtains with conductor layer hot pressing, therefore the main performance of pcb board, as long as particularly signal transmission performance has CCL Determine, while CCL performance and resin matrix relation are very big.With electronic product to light, thin, small, high density, multifunction send out Exhibition, element packing density and integrated level more and more higher, signal frequency more and more higher is transmitted, act the circuit interlayer for transmitting signal function Away from less and less, line width is more and more narrow, and this proposes higher requirement to base electronic material, predominantly high-fire resistance, excellent Dielectric properties, high-insulativity, suitable mechanical performance and processability, particularly dielectric properties.The relative dielectric system of material Number is smaller, and the transmission speed of signal is faster；Dielectric loss factor is smaller, and loss power of the signal in transmitting procedure keeps certain When, it is allowed to the frequency of transmission is higher, i.e., in the case where signal frequency is identical, dielectric loss value is smaller, distortion in signals transmission Rate is lower.Composite, it is by two or more material of different nature, by method physically or chemically, grand See（It is microcosmic）Upper material of the composition with new capability.Various materials make up for each other's deficiencies and learn from each other in performance, produce cooperative effect, make multiple The combination property of condensation material meets a variety of requirements better than former composition material.
With fire-retardant attention, it is desirable to which product has fire resistance, fire-retardant to have class requirement, respectively UL94 V- 2nd, UL94 V-1 and UL94 V-0 ranks, wherein UL94 V-0 ranks are the whether fire-retardant international standard of existing judgement material. How while support personnel and property are from fire threat, and can makes fire retardant to potential hazard existing for human body and environment Be preferably minimized, be domestic fire retardant manufacturing enterprise, research institution and downstream electronic electrically, building materials, the industry such as traffic and furniture be total to Same focus of attention.The introducing of phosphorus-containing compound in the resin matrix of copper-clad plate is prepared, turns into the main of copper-clad plate halogen-free flameproof Technology path, but found in practical application, DOPO class compounds have larger water absorption rate and higher dielectric constant, and its The humidity resistance of manufactured sheet material is low.Simple resin can not meet the application of copper-clad plate, even if heat resistance is preferable Cyanate ester resin, it has excellent dielectric properties（Dielectric coefficient：2.8~3.2；Dielectric loss factor：0.002~0.003）, High-fire resistance（Glass transition temperature：280~295 DEG C）, while cyanate ester resin also has low-shrinkage, excellent mechanical property Energy and adhesive property etc., also because the defects of solidification is insufficient, fragility is big fails in the extensive application of copper-clad plate field.So use Complex technique, the advantages of being not only to integrate organic-inorganic material, the organic component that compatibility is different is also wanted, be hopeful to prepare and meet The copper-clad plate of commercial Application.
The content of the invention
It is an object of the invention to provide a kind of flame-retarded resin base copper-clad plate and preparation method thereof, copper-clad plate tool prepared therefrom There are excellent dielectric properties, excellent heat resistance, anti-flammability, electronic signal transmission materials application can be used as.
To achieve the above object of the invention, the technical solution adopted by the present invention is as follows：
A kind of preparation method of flame-retarded resin base copper-clad plate, comprises the following steps：
（1）By nano silicon foam dispersion in toluene, propionate, the diazoacetic acid tert-butyl ester and nitrous are then added Tert-butyl acrylate；Stirred 15 minutes at 80 DEG C；Then tetramethylethylenediamine is added, the fourth of tin dilaurate two is added after being uniformly dispersed Base zinc, back flow reaction 7 hours, it is eventually adding acetone and obtains the improved silica foam system that solid content is 20~25%；
（2）At 15~25 DEG C, mixing pinacol borine, tetrahydrofuran and 2,3- epoxy radicals cyclopenta ring amyl ether, 35 points are stirred 2- aminoacetophenones are added after clock, continue stirring 20 minutes；Then m-nitrobenzene sulfonic acid pyridiniujm, glycerol monostearate are added Ester, continue stirring 20 minutes, obtain simple function group epoxy systems；
（3）Phthalic acid 2-glycidyl is added after graphene oxide is mixed 30 minutes with isomery undecyl alcohol APEO In ester, 125 DEG C are stirred 20 minutes, then add pungent two mercaptan of 1,8-, are stirred 50 minutes in 130 DEG C, are obtained difunctional epoxy System；
（4）Improved silica foam system is added in difunctional epoxy systems, 130 DEG C are stirred 50 minutes, then in room Under temperature, simple function group epoxy systems, nano titanium oxide whisker are added, stirs 30 minutes, obtains glue；
（5）It is 55~60% with PMA regulation glue solid contents, then lay-up, obtains prepreg；Prepreg is heated It is dried to obtain prepreg；
（6）Prepreg, hot forming are placed between two panels copper foil, you can obtain flame-retarded resin base copper-clad plate.
A kind of flame-retarded resin base copper-clad plate, its preparation method comprise the following steps：
（1）By nano silicon foam dispersion in toluene, propionate, the diazoacetic acid tert-butyl ester and nitrous are then added Tert-butyl acrylate；Stirred 15 minutes at 80 DEG C；Then tetramethylethylenediamine is added, the fourth of tin dilaurate two is added after being uniformly dispersed Base zinc, back flow reaction 7 hours, it is eventually adding acetone and obtains the improved silica foam system that solid content is 20~25%；
（2）At 15~25 DEG C, mixing pinacol borine, tetrahydrofuran and 2,3- epoxy radicals cyclopenta ring amyl ether, 35 points are stirred 2- aminoacetophenones are added after clock, continue stirring 20 minutes；Then m-nitrobenzene sulfonic acid pyridiniujm, glycerol monostearate are added Ester, continue stirring 20 minutes, obtain simple function group epoxy systems；
（3）Phthalic acid 2-glycidyl is added after graphene oxide is mixed 30 minutes with isomery undecyl alcohol APEO In ester, 125 DEG C are stirred 20 minutes, then add pungent two mercaptan of 1,8-, are stirred 50 minutes in 130 DEG C, are obtained difunctional epoxy System；
（4）Improved silica foam system is added in difunctional epoxy systems, 130 DEG C are stirred 50 minutes, then in room Under temperature, simple function group epoxy systems, nano titanium oxide whisker are added, stirs 30 minutes, obtains glue；
（5）It is 55~60% with PMA regulation glue solid contents, then lay-up, obtains prepreg；Prepreg is heated It is dried to obtain prepreg；
（6）Prepreg, hot forming are placed between two panels copper foil, you can obtain flame-retarded resin base copper-clad plate.
A kind of printed circuit board, the preparation method of the printed circuit board comprise the following steps：
（1）By nano silicon foam dispersion in toluene, propionate, the diazoacetic acid tert-butyl ester and nitrous are then added Tert-butyl acrylate；Stirred 15 minutes at 80 DEG C；Then tetramethylethylenediamine is added, the fourth of tin dilaurate two is added after being uniformly dispersed Base zinc, back flow reaction 7 hours, it is eventually adding acetone and obtains the improved silica foam system that solid content is 20~25%；
（2）At 15~25 DEG C, mixing pinacol borine, tetrahydrofuran and 2,3- epoxy radicals cyclopenta ring amyl ether, 35 points are stirred 2- aminoacetophenones are added after clock, continue stirring 20 minutes；Then m-nitrobenzene sulfonic acid pyridiniujm, glycerol monostearate are added Ester, continue stirring 20 minutes, obtain simple function group epoxy systems；
（3）Phthalic acid 2-glycidyl is added after graphene oxide is mixed 30 minutes with isomery undecyl alcohol APEO In ester, 125 DEG C are stirred 20 minutes, then add pungent two mercaptan of 1,8-, are stirred 50 minutes in 130 DEG C, are obtained difunctional epoxy System；
（4）Improved silica foam system is added in difunctional epoxy systems, 130 DEG C are stirred 50 minutes, then in room Under temperature, simple function group epoxy systems, nano titanium oxide whisker are added, stirs 30 minutes, obtains glue；
（5）It is 55~60% with PMA regulation glue solid contents, then lay-up, obtains prepreg；Prepreg is heated It is dried to obtain prepreg；
（6）Prepreg, hot forming are placed between two panels copper foil, you can obtain flame-retarded resin base copper-clad plate；
（7）By the flame-retarded resin base copper-clad plate through overetch, development, printed circuit board is obtained.
A kind of preparation method of printed circuit board, comprises the following steps：
（1）By nano silicon foam dispersion in toluene, propionate, the diazoacetic acid tert-butyl ester and nitrous are then added Tert-butyl acrylate；Stirred 15 minutes at 80 DEG C；Then tetramethylethylenediamine is added, the fourth of tin dilaurate two is added after being uniformly dispersed Base zinc, back flow reaction 7 hours, it is eventually adding acetone and obtains the improved silica foam system that solid content is 20~25%；
（2）At 15~25 DEG C, mixing pinacol borine, tetrahydrofuran and 2,3- epoxy radicals cyclopenta ring amyl ether, 35 points are stirred 2- aminoacetophenones are added after clock, continue stirring 20 minutes；Then m-nitrobenzene sulfonic acid pyridiniujm, glycerol monostearate are added Ester, continue stirring 20 minutes, obtain simple function group epoxy systems；
（3）Phthalic acid 2-glycidyl is added after graphene oxide is mixed 30 minutes with isomery undecyl alcohol APEO In ester, 125 DEG C are stirred 20 minutes, then add pungent two mercaptan of 1,8-, are stirred 50 minutes in 130 DEG C, are obtained difunctional epoxy System；
（4）Improved silica foam system is added in difunctional epoxy systems, 130 DEG C are stirred 50 minutes, then in room Under temperature, simple function group epoxy systems, nano titanium oxide whisker are added, stirs 30 minutes, obtains glue；
（5）It is 55~60% with PMA regulation glue solid contents, then lay-up, obtains prepreg；Prepreg is heated It is dried to obtain prepreg；
（6）Prepreg, hot forming are placed between two panels copper foil, you can obtain flame-retarded resin base copper-clad plate；
（7）By the flame-retarded resin base copper-clad plate through overetch, development, printed circuit board is obtained.
In the present invention, step（1）In, the nanometer titanium dioxide silicon foam, propionate, the diazoacetic acid tert-butyl ester, Asia The nitric acid tert-butyl ester, tetramethylethylenediamine, the mass ratio of di lauric dibutyl zinc are 1: 3: 1: 1.5: 1.5: 0.005.The present invention The creative di lauric dibutyl zinc that first passes through is catalyst, and it is organic to form reactivity in the particle surface of silicon dioxide foam Thing, it is different from existing coupling agent surface treatment, obtained nanometer titanium dioxide silicon foam is reacted per se with stronger reactive group, The solidification process that resin compounded system is beneficial to participate in resin is directly used in, the table of filler is on the one hand adjusted by several organic molecular species Surface properties, preventing inorganic particulate, it produces the too fast influence of partial polymerization to resin, it can in addition contain adjust crosslinked polymer net Network so that cured product crosslinking is reasonable, is unlikely to that fragility is excessive, and the application of especially several compounds improves the heat-resisting of system With dielectric properties.
In the present invention, step（2）In, pinacol borine, tetrahydrofuran, 2,3- epoxy radicals cyclopenta rings amyl ether, 2- ammonia Benzoylformaldoxime, m-nitrobenzene sulfonic acid pyridiniujm, the mass ratio of glycerin monostearate are 0.025: 0.5: 1: 0.08: 0.01: 0.1.The present invention first by pinacol borine be used for copper-clad plate preparation, its is expensive, and dosage is few, applied to the present invention it is fire-retardant simultaneously Heat-resisting and dielectric properties will not be reduced, can also improve the mating reaction of moisture-proof, especially m-nitrobenzene sulfonic acid pyridiniujm, can be with Its advantage is given full play to, obtained product is fabulous without fire retardant, fire resistance.
In the present invention, step（3）In, graphene oxide, isomery undecyl alcohol APEO, phthalic acid two shrink sweet The mass ratio of pungent two mercaptan of grease, 1,8- is 0.001: 0.02: 1: 0.2.This is very crucial, graphene from being not used in copper-clad plate, Because its conductive energy, with copper-clad plate dielectric layer insulating properties on the contrary, still it has good performance, the invention Selective oxidation graphene, and first mixed with isomery undecyl alcohol APEO, add in epoxy, graphite can be greatly improved The reactivity and decentralization of alkene so that graphene avoids gathering while playing catalytic performance.
In the present invention, step（4）In, improved silica foam system, difunctional epoxy systems, simple function group epoxy System, the mass ratio of nano titanium oxide whisker are 0.3: 0.4: 1: 0.008.The present invention uses simple function group epoxy and difunctionality Group, it is still heat-resisting good not using conventional four-functional group epoxy, processability is also improved, on the one hand due to improved silica The effect of foam, the catalysis of graphene is also critically important in addition, while glycerin monostearate and pungent two mercaptan of 1,8- can all strengthen Solidification effect.
In the present invention, step（5）In, in the prepreg, the mass fraction of reinforcing material is 30~35%；The increasing Strong material is electronic-grade glass fiber cloth；The heat drying is 150 DEG C/20s+175 DEG C/50s+190 DEG C/15s, and this is for this Invent critically important, especially ensure stability of the graphene in hot-press solidifying, avoid local conductivity issues, while ladder liter The effect of the compatilizer of temperature and small molecule, turn avoid the presence of bubble, pin hole, while brilliant using very small amount nano titanium oxide Certain diluting effect must be provided, avoid topical gel transition, good basis is laid for hot-press solidifying；Step（6）In, the gold Category paper tinsel is rolled copper foil；The pressure condition during hot pressing is 15~40kg/cm2, pressing-in temp is 190~230 DEG C, during pressing Between be 190~210min；1~10 prepreg is placed between the two panels copper foil.The present invention by overall compatibility and technological design, Obtained epoxy radicals copper-clad plate is heat-resisting very well, dielectric is fine, it is fire-retardant very well, hydroscopicity it is low, other performances all meet IPC marks.
The rolled copper foil that the present invention uses belongs to flaky crystal institutional framework, has excellent pliability；Its consistency is high, Surface has homogeneous flatness, and surface roughness is low, as signal transmitting layer, can overcome under high frequency condition electric current by leading " skin effect " caused during electric layer, impedance caused by reduction, be advantageous to the quick transmission of signal.
The present invention is by overall compatibility and technological design, and obtained epoxy radicals copper-clad plate is heat-resisting very well, dielectric is fine, fire-retardant Very well, hydroscopicity is low, and other performances all meet IPC marks.First with propionate, the diazoacetic acid tert-butyl ester, nitrite tert-butyl, Tetramethylethylenediamine monomer improves filler organic to the processing of nanometer titanium dioxide silicon foam while reducing filler reactivity Dispersiveness in thing, particularly high polymer, the active filler after processing do not interfere with polymer solidification when adding resin prepolymer Process, improve the density of cross-linked network on the contrary, increase flexible points, it is important to propionate, the diazoacetic acid tert-butyl ester, nitrous acid The tert-butyl ester, the dosage of tetramethylethylenediamine cause it not react completely, and some small molecule monomers can be with improved silica Foam system mixes with epoxy, is played a role when hot-press solidifying.The modified filler of material of the present invention simultaneously, avoid often There is adverse effect of the dangling bonds to dielectric properties in rule filler, have good low-k, can be used as high-frequency electronic material. The present invention is acted on, in combination with polymerization without fire retardant is used by modified filler and pungent two mercaptan of pinacol borine, 1,8- Thing reaction effect, material can form finer and close protective layer in heated and burning, reach excellent hot oxygen screen effect, from And assign adhesive joint between solid material excellent heat resistance and anti-flammability, while mechanical property, adhesive property are good；Overcome existing skill Mechanical properties decrease, the problem of heat-resisting decline that the bonding that art filler fire retardant is brought declines and reactive flame retardant is brought.
In the present invention, organic-compound system is the primary bond composition of resin matrix composite system, and rigid Nano filling can be It is dispersed in evenly in resin, improves the intensity and thermal level of its solidfied material；Particularly present invention, avoiding between compound interface There is hole, the formation of polymer interpenetration network will not be hindered, ensure the intensity of solidfied material.To organic-inorganic dielectric material Speech, organic matter is the short slab of heat resistance, several small molecules in material of the invention be present and coordinates under curing agent effect, structure is very It is stable, and there is extra high heat resistance.The inorganic material purity that includes of system of the present invention is high, ultra-fine, good fluidity, particle diameter Narrowly distributing, particularly the invention carry out propionate, the diazoacetic acid tert-butyl ester, Asia on silicon dioxide foam surface The nitric acid tert-butyl ester, tetramethylethylenediamine catalytic reaction, inorganic material external connection active reactive group can improve inorganic particulate Compatibility between polymer, organic group are connected to the very strong inorganic molecule of heat resistance so that polymer of the invention exists Remain to keep original state constant thus sufficiently stable under the high temperature conditions under the degradation temperature of general polymerization thing；Oxygen index (OI) surpasses 38,320 degree of wickings are crossed more than 30 minutes, this using multi-functional epoxy systems for never not appearing in the newspapers.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art:
Preparation method mesocomplex system composition provided by the invention is reasonable, then prepares technique, in obtained copper-clad plate base material Inorganic nanoparticles have uniform decentralization in system, and preparation process belongs to chemical process, the inorganic matter and resin of formation Between surface adhesion be much stronger than the surface adhesion of traditional physical mechanical blending.The material system composition that the present invention utilizes Rationally, compatibility is good between each component, and modified epoxy base copper-clad plate has thus been prepared, and has good mechanics Property, heat resistance, meet the development and application of modified epoxy base copper-clad plate；Comprehensive polymer, the component of inorganic particulate two it is excellent Point, improve two components the shortcomings that, so as to improve to obtain the combination property of material；Solidification effect is good, and cross-linked structure is uniform, small molecule On the one hand compound as the compatilizer of macromolecule organic, can increase the compatibility of system each component, on the other hand avoid The defects of crosslinking is uneven is formed during hot-press solidifying, ensures that resin system forms stable structure, particularly improves Conventional epoxy Heat-resisting, the dielectricity of resin, and fire retardant is free of, by reasonable reaction, it successfully avoid existing reactive phosphor-containing flame-proof point The defects of son is hygroscopic, achieves unexpected effect.
Embodiment
With reference to embodiment, the invention will be further described：
Embodiment one
（1）By nano silicon foam dispersion in toluene, propionate, the diazoacetic acid tert-butyl ester and nitrous are then added Tert-butyl acrylate；Stirred 15 minutes at 80 DEG C；Then tetramethylethylenediamine is added, the fourth of tin dilaurate two is added after being uniformly dispersed Base zinc, back flow reaction 7 hours, it is eventually adding acetone and obtains the improved silica foam system that solid content is 25%；
（2）At 25 DEG C, mixing pinacol borine, tetrahydrofuran and 2,3- epoxy radicals cyclopenta ring amyl ether, after stirring 35 minutes 2- aminoacetophenones are added, continue stirring 20 minutes；Then m-nitrobenzene sulfonic acid pyridiniujm, glycerin monostearate are added, after Continuous stirring 20 minutes, obtains simple function group epoxy systems；
（3）Add graphene oxide into o-phthalic acid diglycidyl ester, 125 DEG C are stirred 20 minutes, then add 1,8- Pungent two mercaptan, stirred 50 minutes in 130 DEG C, obtain difunctional epoxy systems；
（4）Improved silica foam system is added in difunctional epoxy systems, 130 DEG C are stirred 50 minutes, then room temperature Under, simple function group epoxy systems, nano titanium oxide whisker are added, stirs 30 minutes, obtains glue；
（5）It is 60% with PMA regulation glue solid contents, then the glass cloth of lay-up 1080, obtains prepreg；Prepreg Prepreg is obtained through 150 DEG C/20s+175 DEG C/50s+190 DEG C/15s heat dryings, it contains the mass fraction of glass cloth and is 35%；
（6）6 prepregs, hot forming, you can obtain the flame-retarded resin are placed between two panels half ounce copper foil Base copper-clad plate；The hot pressing condition is 15kg/cm2/190℃/20min+25kg/cm2/200℃/40min+35kg/cm2/230 DEG C/140min+ Temperature falls.
In the present embodiment, step（1）In, the nanometer titanium dioxide silicon foam, propionate, the diazoacetic acid tert-butyl ester, Nitrite tert-butyl, tetramethylethylenediamine, the mass ratio of di lauric dibutyl zinc are 1: 3: 1: 1.5: 1.5: 0.005；Step （2）In, pinacol borine, tetrahydrofuran, 2,3- epoxy radicals cyclopenta rings amyl ether, 2- aminoacetophenones, m-nitrobenzene sulfonic acid Pyridiniujm, the mass ratio of glycerin monostearate are 0.025: 0.5: 1: 0.08: 0.01: 0.1；Step（3）In, graphite oxide Alkene, isomery undecyl alcohol APEO, o-phthalic acid diglycidyl ester, the mass ratio of pungent two mercaptan of 1,8- are 0.001: 0.02∶1∶0.2；Step（4）In, improved silica foam system, difunctional epoxy systems, simple function group epoxy systems, The mass ratio of nano titanium oxide whisker is 0.3: 0.4: 1: 0.008.
Comparative example one
As embodiment one, wherein step（1）Nanometer titanium dioxide silicon foam is handled only with 1%KH550.
Comparative example two
As embodiment one, wherein step（2）M-nitrobenzene sulfonic acid pyridiniujm and pinacol boron are replaced with zinc borate flame retardant Alkane.
Comparative example three
As embodiment one, wherein step（3）It is added without graphene oxide.
Comparative example four
As embodiment one, wherein step（3）It is added without isomery undecyl alcohol APEO.
Comparative example five
As embodiment one, wherein step（4）It is added without nano titanium oxide whisker.
According to mechanical performance of the IPC standard methods to the sheet material in the embodiment and comparative example of above-mentioned preparation, dielectricity Energy and hot property, adhesive property are determined, as a result referring to table 1.
The performance of the flame-retarded resin base copper-clad plate of table 1
By the flame-retarded resin base copper-clad plate through overetch, development, the printed circuit board based on modified epoxy is obtained, this category In existing conventional printed circuit boards technology of preparing.
To sum up, flame-retarded resin base copper-clad plate composition disclosed by the invention is reasonable, and compatibility is good between each component, thus makes It is standby to have obtained flame-retarded resin base copper-clad plate, there is good fire resistance, excellent heat resistance, especially with low moisture absorption Rate；Meet the development and application of flame-retarded resin base copper-clad plate.

Claims (10)

1. a kind of preparation method of flame-retarded resin base copper-clad plate, comprises the following steps：
（1）By nano silicon foam dispersion in toluene, propionate, the diazoacetic acid tert-butyl ester and nitrous are then added Tert-butyl acrylate；Stirred 15 minutes at 80 DEG C；Then tetramethylethylenediamine is added, the fourth of tin dilaurate two is added after being uniformly dispersed Base zinc, back flow reaction 7 hours, it is eventually adding acetone and obtains the improved silica foam system that solid content is 20~25%；
（2）At 15~25 DEG C, mixing pinacol borine, tetrahydrofuran and 2,3- epoxy radicals cyclopenta ring amyl ether, 35 points are stirred 2- aminoacetophenones are added after clock, continue stirring 20 minutes；Then m-nitrobenzene sulfonic acid pyridiniujm, glycerol monostearate are added Ester, continue stirring 20 minutes, obtain simple function group epoxy systems；
（3）Phthalic acid 2-glycidyl is added after graphene oxide is mixed 30 minutes with isomery undecyl alcohol APEO In ester, 125 DEG C are stirred 20 minutes, then add pungent two mercaptan of 1,8-, are stirred 50 minutes in 130 DEG C, are obtained difunctional epoxy System；
（4）Improved silica foam system is added in difunctional epoxy systems, 130 DEG C are stirred 50 minutes, then in room Under temperature, simple function group epoxy systems, nano titanium oxide whisker are added, stirs 30 minutes, obtains glue；
（5）It is 55~60% with PMA regulation glue solid contents, then lay-up, obtains prepreg；Prepreg is heated It is dried to obtain prepreg；
（6）Prepreg, hot forming are placed between two panels copper foil, you can obtain the flame-retarded resin base copper-clad plate.
2. the preparation method of flame-retarded resin base copper-clad plate according to claim 1, it is characterised in that：Step（1）In, it is described to receive Rice silicon dioxide foam, propionate, the diazoacetic acid tert-butyl ester, nitrite tert-butyl, tetramethylethylenediamine, tin dilaurate two The mass ratio of butyl zinc is 1: 3: 1: 1.5: 1.5: 0.005.
3. the preparation method of flame-retarded resin base copper-clad plate according to claim 1, it is characterised in that：Step（2）In, pinacol Borine, tetrahydrofuran, 2,3- epoxy radicals cyclopenta rings amyl ether, 2- aminoacetophenones, m-nitrobenzene sulfonic acid pyridiniujm, single tristearin The mass ratio of acid glyceride is 0.025: 0.5: 1: 0.08: 0.01: 0.1.
4. the preparation method of flame-retarded resin base copper-clad plate according to claim 1, it is characterised in that：Step（3）In, aoxidize stone Black alkene, isomery undecyl alcohol APEO, o-phthalic acid diglycidyl ester, the mass ratio of pungent two mercaptan of 1,8- are 0.001: 0.02∶1∶0.2。
5. the preparation method of flame-retarded resin base copper-clad plate according to claim 1, it is characterised in that：Step（4）In, modified two Silica foam system, difunctional epoxy systems, simple function group epoxy systems, the mass ratio of titanium dioxide crystal whisker are 0.3: 0.4∶1∶0.008。
6. the preparation method of flame-retarded resin base copper-clad plate according to claim 1, it is characterised in that：Step（5）In, described half In cured sheets, the mass fraction of reinforcing material is 30~35%；The reinforcing material is electronic-grade glass fiber cloth；The heating Drying is 150 DEG C/20s+175 DEG C/50s+190 DEG C/15s；Step（6）In, the metal foil is rolled copper foil；During the hot pressing Pressure condition be 15~40kg/cm2, pressing-in temp is 190~230 DEG C, and pressing time is 190~210min；The two panels 1~10 prepreg is placed between copper foil.
A kind of 7. flame-retarded resin base copper-clad plate, it is characterised in that：The preparation method of the flame-retarded resin base copper-clad plate includes following Step：
（1）By nano silicon foam dispersion in toluene, propionate, the diazoacetic acid tert-butyl ester and nitrous are then added Tert-butyl acrylate；Stirred 15 minutes at 80 DEG C；Then tetramethylethylenediamine is added, the fourth of tin dilaurate two is added after being uniformly dispersed Base zinc, back flow reaction 7 hours, it is eventually adding acetone and obtains the improved silica foam system that solid content is 20~25%；
（2）At 15~25 DEG C, mixing pinacol borine, tetrahydrofuran and 2,3- epoxy radicals cyclopenta ring amyl ether, 35 points are stirred 2- aminoacetophenones are added after clock, continue stirring 20 minutes；Then m-nitrobenzene sulfonic acid pyridiniujm, glycerol monostearate are added Ester, continue stirring 20 minutes, obtain simple function group epoxy systems；
（3）Phthalic acid 2-glycidyl is added after graphene oxide is mixed 30 minutes with isomery undecyl alcohol APEO In ester, 125 DEG C are stirred 20 minutes, then add pungent two mercaptan of 1,8-, are stirred 50 minutes in 130 DEG C, are obtained difunctional epoxy System；
（4）Improved silica foam system is added in difunctional epoxy systems, 130 DEG C are stirred 50 minutes, then in room Under temperature, simple function group epoxy systems, nano titanium oxide whisker are added, stirs 30 minutes, obtains glue；
（5）It is 55~60% with PMA regulation glue solid contents, then lay-up, obtains prepreg；Prepreg is heated It is dried to obtain prepreg；
（6）Prepreg, hot forming are placed between two panels copper foil, you can obtain the flame-retarded resin base copper-clad plate.
8. flame-retarded resin base copper-clad plate according to claim 7, it is characterised in that：Step（1）In, the nano silicon Foam, propionate, the diazoacetic acid tert-butyl ester, nitrite tert-butyl, tetramethylethylenediamine, the matter of di lauric dibutyl zinc Amount is than being 1: 3: 1: 1.5: 1.5: 0.005；Step（2）In, pinacol borine, tetrahydrofuran, 2,3- epoxy radicals cyclopenta ring penta Base ether, 2- aminoacetophenones, m-nitrobenzene sulfonic acid pyridiniujm, the mass ratio of glycerin monostearate are 0.025: 0.5: 1: 0.08 ∶0.01∶0.1；Step（3）In, graphene oxide, isomery undecyl alcohol APEO, o-phthalic acid diglycidyl ester, 1, The mass ratio of pungent two mercaptan of 8- is 0.001: 0.02: 1: 0.2；Step（4）In, improved silica foam system, difunctional Epoxy systems, simple function group epoxy systems, the mass ratio of titanium dioxide crystal whisker are 0.3: 0.4: 1: 0.008；Step（5）In, institute State in prepreg, the mass fraction of reinforcing material is 30~35%；The reinforcing material is electronic-grade glass fiber cloth；It is described Heat drying is 150 DEG C/20s+175 DEG C/50s+190 DEG C/15s；Step（6）In, the metal foil is rolled copper foil；The heat Pressure condition during pressure is 15~40kg/cm2, pressing-in temp is 190~230 DEG C, and pressing time is 190~210min；It is described 1~10 prepreg is placed between two panels copper foil.
9. a kind of printed circuit board, it is characterised in that the preparation method of the printed circuit board comprises the following steps：
（1）By nano silicon foam dispersion in toluene, propionate, the diazoacetic acid tert-butyl ester and nitrous are then added Tert-butyl acrylate；Stirred 15 minutes at 80 DEG C；Then tetramethylethylenediamine is added, the fourth of tin dilaurate two is added after being uniformly dispersed Base zinc, back flow reaction 7 hours, it is eventually adding acetone and obtains the improved silica foam system that solid content is 20~25%；
（2）At 15~25 DEG C, mixing pinacol borine, tetrahydrofuran and 2,3- epoxy radicals cyclopenta ring amyl ether, 35 points are stirred 2- aminoacetophenones are added after clock, continue stirring 20 minutes；Then m-nitrobenzene sulfonic acid pyridiniujm, glycerol monostearate are added Ester, continue stirring 20 minutes, obtain simple function group epoxy systems；
（3）Phthalic acid 2-glycidyl is added after graphene oxide is mixed 30 minutes with isomery undecyl alcohol APEO In ester, 125 DEG C are stirred 20 minutes, then add pungent two mercaptan of 1,8-, are stirred 50 minutes in 130 DEG C, are obtained difunctional epoxy System；
（4）Improved silica foam system is added in difunctional epoxy systems, 130 DEG C are stirred 50 minutes, then in room Under temperature, simple function group epoxy systems, nano titanium oxide whisker are added, stirs 30 minutes, obtains glue；
（5）It is 55~60% with PMA regulation glue solid contents, then lay-up, obtains prepreg；Prepreg is heated It is dried to obtain prepreg；
（6）Prepreg, hot forming are placed between two panels copper foil, you can obtain flame-retarded resin base copper-clad plate；
（7）By the flame-retarded resin base copper-clad plate through overetch, development, printed circuit board is obtained.
10. a kind of preparation method of printed circuit board, it is characterised in that comprise the following steps：
（1）By nano silicon foam dispersion in toluene, propionate, the diazoacetic acid tert-butyl ester and nitrous are then added Tert-butyl acrylate；Stirred 15 minutes at 80 DEG C；Then tetramethylethylenediamine is added, the fourth of tin dilaurate two is added after being uniformly dispersed Base zinc, back flow reaction 7 hours, it is eventually adding acetone and obtains the improved silica foam system that solid content is 20~25%；
（2）At 15~25 DEG C, mixing pinacol borine, tetrahydrofuran and 2,3- epoxy radicals cyclopenta ring amyl ether, 35 points are stirred 2- aminoacetophenones are added after clock, continue stirring 20 minutes；Then m-nitrobenzene sulfonic acid pyridiniujm, glycerol monostearate are added Ester, continue stirring 20 minutes, obtain simple function group epoxy systems；
（3）Phthalic acid 2-glycidyl is added after graphene oxide is mixed 30 minutes with isomery undecyl alcohol APEO In ester, 125 DEG C are stirred 20 minutes, then add pungent two mercaptan of 1,8-, are stirred 50 minutes in 130 DEG C, are obtained difunctional epoxy System；
（4）Improved silica foam system is added in difunctional epoxy systems, 130 DEG C are stirred 50 minutes, then in room Under temperature, simple function group epoxy systems, nano titanium oxide whisker are added, stirs 30 minutes, obtains glue；
（5）It is 55~60% with PMA regulation glue solid contents, then lay-up, obtains prepreg；Prepreg is heated It is dried to obtain prepreg；
（6）Prepreg, hot forming are placed between two panels copper foil, you can obtain flame-retarded resin base copper-clad plate；
（7）By the flame-retarded resin base copper-clad plate through overetch, development, printed circuit board is obtained.
CN201710850704.1A 2017-09-20 2017-09-20 Flame-retardant resin-based copper-clad plate and preparation method thereof Pending CN107722559A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101550264A (en) * 2009-04-30 2009-10-07 苏州生益科技有限公司 Resin matching fluid used for metal foil laminated board
CN102936396A (en) * 2012-11-29 2013-02-20 彭代信 Toughening epoxy resin composition
CN105172297A (en) * 2015-09-02 2015-12-23 苏州益可泰电子材料有限公司 Flame-resistant and heat-resistant copper clad laminate preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101550264A (en) * 2009-04-30 2009-10-07 苏州生益科技有限公司 Resin matching fluid used for metal foil laminated board
CN102936396A (en) * 2012-11-29 2013-02-20 彭代信 Toughening epoxy resin composition
CN105172297A (en) * 2015-09-02 2015-12-23 苏州益可泰电子材料有限公司 Flame-resistant and heat-resistant copper clad laminate preparation method

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