CN108146035A - Flame-proof heat-resistant copper-clad plate - Google Patents
Flame-proof heat-resistant copper-clad plate Download PDFInfo
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- CN108146035A CN108146035A CN201711164016.6A CN201711164016A CN108146035A CN 108146035 A CN108146035 A CN 108146035A CN 201711164016 A CN201711164016 A CN 201711164016A CN 108146035 A CN108146035 A CN 108146035A
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- clad plate
- proof heat
- resistant copper
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- 0 CC(C(*)C1)C=CC1=C([C@@]1C=CC=CC1*)c(cc1*)ccc1O Chemical compound CC(C(*)C1)C=CC1=C([C@@]1C=CC=CC1*)c(cc1*)ccc1O 0.000 description 1
Classifications
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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
- 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
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- 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
-
- 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
-
- 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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
-
- 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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Laminated Bodies (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The present invention relates to a kind of flame-proof heat-resistant copper-clad plate, preparation method includes the following steps, filler is obtained as raw material using nanometer titanium dioxide silicon foam, dodecyl benzene sulfonic acid, five water bismuth nitrates and methyl trichlorosilane, Tween-80;Resin prepolymer is obtained for raw material with DOPO and bisphenol A cyanate monomer, phenolic compounds, m-nitrobenzene sulfonic acid pyridiniujm, 2,3 epoxy group cyclopenta ring amyl ethers, dimethylphosphite;Filler is added in o-phthalic acid diglycidyl ester, obtains active filler;Resin prepolymer with benzazolyl compounds is mixed, active filler, isomery undecyl alcohol polyoxyethylene ether phosphate sylvite is then added in, obtains compound system;By compound system, reinforcing material, metal foil hot forming, you can obtain the flame-proof heat-resistant copper-clad plate, with excellent flame retardant property, heat resistance, meet the development and application of flame-proof heat-resistant copper-clad plate.
Description
It is 201510551973.9 the invention belongs to number of patent application, patent application day is September in 2015 2 days, proprietary term
The referred to as divisional application of the preparation method of flame-proof heat-resistant copper-clad plate belongs to product section technical solution.
Technical field
The invention belongs to electronics technical field of composite materials, and in particular to a kind of flame-proof heat-resistant copper-clad plate, obtained product
Available for aerospace, signal transmission, telecommunications field.
Background technology
With the continuous development of science and technology, the application of polymer-based composite is more and more extensive.Meanwhile each application
Field also proposes higher requirement to different materials accordingly.The most advanced branches of science skill particularly as aerospace industry
Art field, it is more harsh to the performance requirement of material, such as they require composite material will have high specific strength, high specific stiffness,
The performances such as high temperature resistant, resistance to ablation.Composite material is by two or more material of different nature, by physically or chemically
Method, material of the composition with new capability on macroscopical (microcosmic).A variety of materials make up for each other's deficiencies and learn from each other in performance, generate association
Same effect makes the comprehensive performance of composite material be better than former composition material and meet a variety of different requirements.
Printed wiring board is formed after circuit makes by copper-clad plate, and copper-clad plate is by glass cloth and is attached to the glass
Resin layer on cloth obtains, therefore the main performance of pcb board with conductor layer hot pressing, as long as particularly signal transmission performance has CCL
It determines, while the performance of CCL and resin matrix relationship are very big.With electronic product to light, thin, small, high density, multifunction send out
Exhibition, element packing density and integrated level are higher and higher, and transmission signal frequency is higher and higher, act the circuit interlayer for transmitting signal function
Away from less and less, line width is more and more narrow, this proposes base electronic material higher requirement, predominantly high-fire resistance, excellent
Dielectric properties, high-insulativity, suitable mechanical performance and processability, particularly dielectric properties.The opposite 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 transmission process keeps certain
When, the frequency for allowing transmission is higher, i.e., in the case where signal frequency is identical, dielectric loss value is smaller, is distorted in signals transmission
Rate is lower.
With fire-retardant attention, it is desirable that product has flame retardant property, fire-retardant to have class requirement, respectively UL94 V-
2nd, UL94 V-1 and UL94 V-0 ranks, wherein UL94 V-0 the ranks international standard whether fire-retardant for existing judgement substance.
Equalization point is found between fire prevention and environmental protection, is the important node of following flame retardant products development.Fire retardant is in modern society
Importance can not be ignored, but as a series of environmental protection policies in Europe are put into effect, development and application is restricted to some extent.Such as
While where support personnel and property are from fire threat, and fire retardant can be made to drop potential hazard existing for human body and environment
It is that the industries such as electrical domestic fire retardant manufacturing enterprise, research institution and downstream electronic, building materials, traffic and furniture are common to minimum
Focus of attention.The introducing of phosphorus-containing compound in the resin matrix of copper-clad plate is prepared, becomes the main skill of copper-clad plate halogen-free flameproof
Art route.At present, reactive phosphorus flame retardant widely used on copper-clad plate field is mainly DOPO class compounds, with phosphorous ring
Based on oxygen resin, phosphorus containing phenolic resin, phosphorus content is between 2-10%, however, being found in practical application, DOPO classes compound tool
There are larger water absorption rate and higher dielectric constant, and the humidity resistance of its manufactured plank is low.Simple resin cannot
Meet the application of copper-clad plate, even if the preferable cyanate ester resin of heat resistance, with 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), simultaneously
Cyanate ester resin also has a low-shrinkage, excellent mechanical property and adhesive property etc., and also because curing is insufficient, brittleness is big etc. lacks
It falls into and fails to widely apply in copper-clad plate field.So using complex technique, the advantages of being not only to integrate organic-inorganic material, also
The organic component that compatibility is different is wanted, is hopeful to prepare the copper-clad plate for meeting commercial Application.
Invention content
The object of the present invention is to provide a kind of preparation method of flame-proof heat-resistant copper-clad plate, the flame-proof heat-resistant copper-clad plate of preparation has
There are excellent dielectric properties, excellent heat resistance, anti-flammability can be used as electronic signal transmission material application.
To achieve the above object of the invention, the technical solution adopted by the present invention is:A kind of preparation side of flame-proof heat-resistant copper-clad plate
Method includes the following steps:
(1) by nano silicon dioxide foam dispersion in deionized water, dodecyl benzene sulfonic acid, five water nitric acid are then added in
Bismuth and methyl trichlorosilane;Then hydro-thermal reaction 2 hours at 150 DEG C;Then filtering reacting liquid, filter cake are added in ethyl alcohol, point
Tween-80 is added after dissipating uniformly, is stirred in 60 DEG C 2 hours, finally drying obtains filler;
(2) mixing DOPO and bisphenol A cyanate monomer, 95 DEG C of stirrings add in phenolic compounds after 25 minutes, continue stirring 30
Minute;Then m-nitrobenzene sulfonic acid pyridiniujm, 2,3- epoxy group cyclopenta ring amyl ethers are added in, continues stirring 20 minutes;It adds in
Dimethylphosphite stirs 30 minutes in 100 DEG C;Obtain resin prepolymer;
(3) filler is added in o-phthalic acid diglycidyl ester, 125 DEG C are stirred 1 hour, obtain active filler;It will
Resin prepolymer is mixed with benzazolyl compounds, is stirred 30 minutes in 120 DEG C;Then active filler is added in, 30 points are stirred in 130 DEG C
Clock;Then isomery undecyl alcohol polyoxyethylene ether phosphate sylvite is added in, compound system is obtained within 50 minutes in 140 DEG C of stirrings;
(4) glue is made in the dissolving of above-mentioned compound system solvent, then reinforcing material is immersed in above-mentioned glue;Leaching
After the heated drying of reinforcing material after stain, prepreg is obtained;Prepreg is cut out into burr removing;Take the preimpregnation of 2~5 sanction burr removings
Bed of material poststack is two-sided to be covered with metal foil, hot forming, you can obtains the flame-proof heat-resistant copper-clad plate;In the prepreg, enhancing
The mass fraction of material is 20~22%;
The chemical structural formula of the phenolic compounds is:
The chemical structural formula of the benzazolyl compounds is:
Wherein R1For hydrogen or methyl, R2For methyl or methyl formate base, R3For amino or cyanogen
Base.
In the present invention, in step (1), the nanometer titanium dioxide silicon foam, dodecyl benzene sulfonic acid, five water bismuth nitrates and first
Base trichlorosilane, Tween-80 mass ratio be 1: 0.2: 0.2: 0.35: 0.05;The grain of the filler
Diameter is 560~880nm.The invention first passes through dodecyl benzene sulfonic acid as medium, is prepared for silicon bismuth complex, then
It is handled using Tween-80, it is different from existing coupling agent surface treatment, what hydro-thermal reaction obtained
Filter cake is directly used in that resin compounded system is improper per se with stronger reactive group, can influence the solidification process of resin, lead to
On the one hand surface nature that Tween-80 adjusts filler is crossed, prevents it from generating partial polymerization mistake to resin
Fast influence, in addition it can adjust crosslinked polymer network so that cured product crosslinking is reasonable, and it is excessive to be unlikely to brittleness.
In the present invention, in step (2), DOPO, bisphenol A cyanate monomer, phenolic compounds, m-nitrobenzene sulfonic acid pyridiniujm,
2,3- epoxy group cyclopenta ring amyl ethers, dimethylphosphite mass ratio be 0.05: 1: 0.2~0.3: 0.08~0.085:
0.58~0.63: 0.09~0.12.Flame retardant property, most important or and resin system can be provided using organic phosphorus compound
(cyanate, phenolic compounds and 2,3- epoxy group cyclopenta ring amyl ether) has preferable reactivity, can be by phosphorus-containing groups
Polymer segment is substituted into, the flame retardant effect that otherwise more phosphorus has also been unable to reach again;System is anti-when preparing resin prepolymer simultaneously
Answering property is relatively low, ensures that organic matter does not form big strand before curing, is conducive to the infiltration of follow-up reinforcing material and glues
It connects, and some micromolecular compounds start to react with macromolecular chain, reduces cyanate ester monomer, phenolic compounds, epoxy monomer
Density, be conducive to uniformity during polymer polymerizing.Small molecule either prepolymer is changed by chemical reaction by chemistry
The macromolecular that key is bonded together will necessarily cause volume contraction, simultaneously because the fuel factor of solidification process can also cause resinite
Volume contraction, can bring resin material bodies itself huge internal stress, crackle or interfacial adhesion can be caused and destroyed;Present invention choosing
With the organic composite of shrinking percentage complementation, technique is prepared, material volume shrinking percentage is effectively reduced, down to 0.32%.
In the present invention, in step (3), filler, o-phthalic acid diglycidyl ester, resin prepolymer, benzazolyl compounds,
The mass ratio of isomery undecyl alcohol polyoxyethylene ether phosphate sylvite is 0.32~0.45: 0.12~0.15: 1: 0.08~0.09:
0.01~0.015.Cyanate ester monomer is easily influenced when polymerizeing by other functional groups, this is that advantage also has bad place, if anti-with it
The compound answered can retain the defects of its polymerization density can also improve its brittleness, reaction is too fast, then favorably, if instead and its
Its extent of reaction of the material damage of reaction, then it is unfavorable;The present invention reduces filler reactivity first with epoxy monomer to filler processing
While improve dispersibility of the filler in organic matter, particularly high polymer, active filler that treated adds in resin prepolymer
Polymer curing process is not interfered with during object, improves the density of cross-linked network instead, increases flexible points.Resin solidification includes solidifying
Glue-curing-last handling process, in the curing process heat release have close with the Physical and mechanical properties of curing degree and product
Relationship.High exothermic temperature is conducive to resin solidification, but excessively high exothermic temperature is then harmful, resin volume can be caused to receive
The increase of contracting and the appearance of micro-crack, thus lead to the decline of material mechanical performance, particularly for there is the product of micro-crack meaning
Taste the leakage of medium, and corrosion resistance is caused to decline;The addition of phenolic compounds, Tween-80 of the present invention
Resin solidification highest exothermic peak can be effectively reduced, and gel time is not influenced simultaneously.Pass through adding for small organic molecule
Enter and the epoxidation of filler is handled, cyanate ester resin, phenolic compounds and epoxy resin cure technique tend in the present invention
Unanimously, so as to obtain the excellent resin combination of heat resistance, mechanical performance, chemical resistance.Material structure of the present invention contains
Even nanoscale hole avoids adverse effect of the conventional fillers there are dangling bonds to dielectric properties, has good low dielectric
Constant can be used as high-frequency electronic material.Material can form finer and close protective layer in heated and burning, reach excellent heat
Oxygen screen effect, so as to assign adhesive joint between solid material excellent heat resistance and anti-flammability, while mechanical property, adhesive property are good
It is good;Overcome the bonding that prior art filler fire retardant brings declines and reactive flame retardant is brought mechanical properties decrease,
The problem of heat-resisting decline.
In the present invention, in step (4), solvent is butanone, the mixture of ethylene glycol monomethyl ether;The reinforcing material is electron level
Glass fabric;The metal foil is prepared after etching by the rolled copper foil that thickness is 18~35 μm.Pressure during hot pressing
Condition is 15~35kg/cm2, pressing-in temp is 180~230 DEG C, and pressing time is 170~200min;The piece of the prepreg
Number is determined according to the thickness of copper-clad plate of actual requirement.The rolled copper foil that the present invention uses belongs to flaky crystal institutional framework,
With excellent flexibility;Its consistency is high, and surface has uniform flatness, and surface roughness is low, as signal transmitting layer,
Electric current under high frequency condition can be overcome to pass through " skin effect " generated during conductive layer, the impedance of generation is reduced, be conducive to letter
Number quick transmission.
In the present invention, organic-compound system is the primary bond ingredient of resin matrix composite system, and rigid Nano filling can be
It is dispersed in resin evenly, improves the intensity and thermal level of its solidfied material;Particularly the invention avoids between compound interface
There is hole, the formation of polymer interpenetration network will not be interfered, ensure the intensity of solidfied material.To organic-inorganic dielectric material
Speech, organic matter are the short slabs of heat resistance, are become very surely there are special big pi-conjugated electronics bond structure in material of the invention
It is fixed, and with extra high heat resistance.The inorganic material purity that includes of system of the present invention is high, ultra-fine, good fluidity, grain size divide
Cloth is narrow, and particularly the invention adds dodecyl benzene sulfonic acid and polyoxyethylene when preparing compounded mix
Alcohol acid anhydride monoleate, and it is pre-processed using epoxy monomer before resin prepolymer is added in, reunite in resin matrix
Phenomenon is few;Inorganic material external connection active reactive group can improve the compatibility between inorganic particulate and polymer, organic
Group is connected to the very strong inorganic molecule of heat resistance so that polymer of the invention remains under the degradation temperature of general polymerization object
Keep original state constant thus sufficiently stable under the high temperature conditions;Initial pyrolyzation temperature is more than 400 DEG C, glass transition
Temperature is more than 240 DEG C.
Since 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, obtained copper-clad plate base
Inorganic nanoparticles and hole have uniform dispersion degree in system in material, and preparation process belongs to chemical process, the nothing of formation
The surface binding force of machine object and interlaminar resin is much stronger than the surface binding force of traditional physical mechanical blending.The original that the present invention utilizes
Material system composition is reasonable, and compatibility is good between each component, and flame-proof heat-resistant copper-clad plate has thus been prepared, and has good power
The property learned, heat resistance, meet the development and application of flame-proof heat-resistant copper-clad plate;The advantages of comprehensive polymer, two component of inorganic particulate, change
The shortcomings that kind two component, so as to improve to obtain the comprehensive performance of material;Solidification effect is good, and cross-linked structure is uniform, small molecule chemical combination
On the one hand object as the compatilizer of macromolecule organic, can increase the compatibility of system each component, on the other hand avoid hot pressing
The defects of crosslinking is uneven is formed during curing, ensures that resin system forms stable structure, mechanical property is strong, particularly improves cyanic acid
Still retain its heat-resisting, excellent dielectricity while the brittleness of ester resin, and after phosphorus-containing groups are introduced polymer segment,
By reasonable reaction, the defects of existing reactive phosphor-containing flame-proof molecule is hygroscopic is successfully avoided, achieves unexpected effect
Fruit.
Specific embodiment
With reference to embodiment, the invention will be further described:
Raw materials used the present embodiment is all purchased in market, belongs to industrial goods;
The molecular structural formula of DOPO is:
The chemical structural formula of the phenolic compounds is:
The chemical structural formula of the benzazolyl compounds is:
Wherein R1For hydrogen or methyl, R2For methyl or methyl formate base, R3For amino or cyanogen
Base.
The preparation of one filler of synthesis example
By 1Kg nano silicon dioxide foam dispersions in deionized water, 200g dodecyl benzene sulfonic acid, 200g are then added in
Five water bismuth nitrates and 350g methyl trichlorosilanes;Then hydro-thermal reaction 2 hours at 150 DEG C;Then filtering reacting liquid, filter cake add
Enter in ethyl alcohol, 50g Tween-80s are added after being uniformly dispersed, stir 2 hours in 60 DEG C, finally dry
Obtain filler (grain size is 560~880nm).
A kind of preparation method of one flame-proof heat-resistant copper-clad plate of embodiment, includes the following steps:
Mix 5gDOPO and 100g bisphenol A cyanate monomers, 95 DEG C of stirrings add in 20g phenolic compounds after 25 minutes, continue
Stirring 30 minutes;Then 8g m-nitrobenzene sulfonic acids pyridiniujm, 58g2 are added in, 3- epoxy group cyclopenta ring amyl ethers continue to stir
20 minutes;9g dimethylphosphites are added in, are stirred 30 minutes in 100 DEG C;Obtain resin prepolymer;It is adjacent that 32g fillers are added in into 12g
In phthalic acid 2-glycidyl ester, 125 DEG C are stirred 1 hour, obtain active filler;By 100g resin prepolymers and 9g indoles
Close object (R1For hydrogen, R2For methyl, R3For amino) mixing, it is stirred 30 minutes in 120 DEG C;Then active filler is added in, in 130 DEG C
Stirring 30 minutes;Then 1.5g isomery undecyl alcohol polyoxyethylene ether phosphate sylvite is added in, is answered within 50 minutes in 140 DEG C of stirrings
Zoarium system;Above-mentioned compound system butanone/ethylene glycol monomethyl ether is mixed into solvent dissolving, glue is made, then by E-glass cloth
It is immersed in above-mentioned glue, toasts 2min under the conditions of 170 DEG C in an oven, prepare prepreg, the mass fraction of glass cloth is
22%;Prepreg is cut out into burr removing;Take 5 lamella poststacks are two-sided to be covered with 1oz rolled copper foils, hot forming, you can to obtain the resistance
Fire heat-resistant copper-clad panel;For hot pressing condition by the way of gradually heating up and boosting, 10min temperature is raised to 180 DEG C from 50 DEG C, keeps
30min, then 10min be raised to 200 DEG C of holding 90min, then 5min is raised to 230 DEG C of holding 80min, and last 180min is cooled to
50℃.1min pressure is from 0Kg/cm2It is raised to 15Kg/cm2, then pressurize 25min, then 1min be raised to 20Kg/cm2Pressurize
50min, last 1min are raised to 35Kg/cm2, pressurize 120min.
A kind of preparation method of two flame-proof heat-resistant copper-clad plate of embodiment, includes the following steps:
Mix 5gDOPO and 100g bisphenol A cyanate monomers, 95 DEG C of stirrings add in 30g phenolic compounds after 25 minutes, continue
Stirring 30 minutes;Then 8.2g m-nitrobenzene sulfonic acids pyridiniujm, 63g2 are added in, 3- epoxy group cyclopenta ring amyl ethers continue to stir
It mixes 20 minutes;12g dimethylphosphites are added in, are stirred 30 minutes in 100 DEG C;Obtain resin prepolymer;45g fillers are added in
In 14g o-phthalic acid diglycidyl esters, 125 DEG C are stirred 1 hour, obtain active filler;By 100g resin prepolymers with
8.5g benzazolyl compounds (R1For hydrogen, R2For methyl, R3For cyano) mixing, it is stirred 30 minutes in 120 DEG C;Then activity is added in fill out
Material stirs 30 minutes in 130 DEG C;Then 1.5g isomery undecyl alcohol polyoxyethylene ether phosphate sylvite is added in, 50 are stirred in 140 DEG C
Minute obtains compound system;Above-mentioned compound system butanone/ethylene glycol monomethyl ether is mixed into solvent dissolving, glue is made, it then will be electric
Sub- grade glass cloth is immersed in above-mentioned glue, is toasted 2min under the conditions of 170 DEG C in an oven, is prepared prepreg, the matter of glass cloth
It is 21% to measure score;Prepreg is cut out into burr removing;Take 3 lamella poststacks are two-sided to be covered with 1oz rolled copper foils, hot forming, you can
To the flame-proof heat-resistant copper-clad plate;For hot pressing condition by the way of gradually heating up and boosting, 10min temperature is raised to 180 from 50 DEG C
DEG C, 40min is kept, then 10min is raised to 200 DEG C of holding 50min, and then 5min is raised to 230 DEG C of holding 90min, finally
180min is cooled to 50 DEG C.1min pressure is from 0Kg/cm2It is raised to 15Kg/cm2, then pressurize 20min, then 1min be raised to 20Kg/
cm2Pressurize 60min, last 1min are raised to 35Kg/cm2, pressurize 120min.
A kind of preparation method of three flame-proof heat-resistant copper-clad plate of embodiment, includes the following steps:
Mix 5gDOPO and 100g bisphenol A cyanate monomers, 95 DEG C of stirrings add in 25g phenolic compounds after 25 minutes, continue
Stirring 30 minutes;Then 8.1g m-nitrobenzene sulfonic acids pyridiniujm, 60g2 are added in, 3- epoxy group cyclopenta ring amyl ethers continue to stir
It mixes 20 minutes;10g dimethylphosphites are added in, are stirred 30 minutes in 100 DEG C;Obtain resin prepolymer;40g fillers are added in
In 15g o-phthalic acid diglycidyl esters, 125 DEG C are stirred 1 hour, obtain active filler;By 100g resin prepolymers with
8.2g benzazolyl compounds (R1For methyl, R2For methyl formate base, R3For cyano) mixing, it is stirred 30 minutes in 120 DEG C;Then plus
Enter active filler, stirred 30 minutes in 130 DEG C;Then 1.2g isomery undecyl alcohol polyoxyethylene ether phosphate sylvite is added in, in 140
DEG C stirring obtains compound system in 50 minutes;Above-mentioned compound system butanone/ethylene glycol monomethyl ether is mixed into solvent dissolving, glue is made,
Then E-glass cloth is immersed in above-mentioned glue, toasts 2min under the conditions of 170 DEG C in an oven, prepare prepreg, glass
The mass fraction of glass cloth is 20%;Prepreg is cut out into burr removing;It takes 5 lamella poststacks are two-sided to be covered with 0.5oz rolled copper foils, is hot pressed into
Shape, you can obtain the flame-proof heat-resistant copper-clad plate;Hot pressing condition is by the way of gradually heating up and boosting, and 10min temperature is from 50
180 DEG C DEG C are raised to, keeps 20min, then 10min is raised to 200 DEG C of holding 100min, and then 5min is raised to 230 DEG C of holdings
60min, last 180min are cooled to 50 DEG C.1min pressure is from 0Kg/cm2It is raised to 15Kg/cm2, then pressurize 20min, then
1min is raised to 20Kg/cm2Pressurize 60min, last 1min are raised to 35Kg/cm2, pressurize 120min.
A kind of preparation method of flame-proof heat-resistant copper-clad plate of example IV, includes the following steps:
Mix 5gDOPO and 100g bisphenol A cyanate monomers, 95 DEG C of stirrings add in 24g phenolic compounds, then stir after 25 minutes
It mixes 30 minutes;Then 8.5g m-nitrobenzene sulfonic acids pyridiniujm, 62g2 are added in, 3- epoxy group cyclopenta ring amyl ethers continue to stir
20 minutes;11g dimethylphosphites are added in, are stirred 30 minutes in 100 DEG C;Obtain resin prepolymer;38g fillers are added in into 12g
In o-phthalic acid diglycidyl ester, 125 DEG C are stirred 1 hour, obtain active filler;By 100g resin prepolymers and 8.8g Yin
Indole compound (R1For methyl, R2For methyl formate base, R3For amino) mixing, it is stirred 30 minutes in 120 DEG C;Then activity is added in
Filler stirs 30 minutes in 130 DEG C;Then 1g isomery undecyl alcohol polyoxyethylene ether phosphate sylvite is added in, 50 are stirred in 140 DEG C
Minute obtains compound system;Above-mentioned compound system butanone/ethylene glycol monomethyl ether is mixed into solvent dissolving, glue is made, it then will be electric
Sub- grade glass cloth is immersed in above-mentioned glue, is toasted 2min under the conditions of 170 DEG C in an oven, is prepared prepreg, the matter of glass cloth
It is 22% to measure score;Prepreg is cut out into burr removing;Take 2 lamella poststacks are two-sided to be covered with 0.5oz rolled copper foils, hot forming, you can
Obtain the flame-proof heat-resistant copper-clad plate;For hot pressing condition by the way of gradually increasing temperature and pressure, 10min temperature is raised to 180 from 50 DEG C
DEG C, 60min is kept, then 10min is raised to 200 DEG C of holding 60min, and then 5min is raised to 230 DEG C of holding 50min, finally
180min is cooled to 50 DEG C.1min pressure is from 0Kg/cm2It is raised to 15Kg/cm2, then pressurize 80min, then 1min be raised to 20Kg/
cm2Pressurize 60min, last 1min are raised to 35Kg/cm2, pressurize 60min.
A kind of preparation method of five flame-proof heat-resistant copper-clad plate of embodiment, includes the following steps:
Mix 5gDOPO and 100g bisphenol A cyanate monomers, 95 DEG C of stirrings add in 26g phenolic compounds after 25 minutes, continue
Stirring 30 minutes;Then 8.1g m-nitrobenzene sulfonic acids pyridiniujm, 59g2 are added in, 3- epoxy group cyclopenta ring amyl ethers continue to stir
It mixes 20 minutes;9.5g dimethylphosphites are added in, are stirred 30 minutes in 100 DEG C;Obtain resin prepolymer;34g fillers are added in
In 15g o-phthalic acid diglycidyl esters, 125 DEG C are stirred 1 hour, obtain active filler;By 100g resin prepolymers with
8.2g benzazolyl compounds (R1For hydrogen, R2For methyl formate base, R3For cyano) mixing, it is stirred 30 minutes in 120 DEG C;Then it adds in
Active filler is stirred 30 minutes in 130 DEG C;Then 1.3g isomery undecyl alcohol polyoxyethylene ether phosphate sylvite is added in, in 140 DEG C
Stirring obtains compound system in 50 minutes;Above-mentioned compound system butanone/ethylene glycol monomethyl ether is mixed into solvent dissolving, glue is made, so
E-glass cloth is immersed in above-mentioned glue afterwards, 2min is toasted under the conditions of 170 DEG C in an oven, prepares prepreg, glass
The mass fraction of cloth is 22%;Prepreg is cut out into burr removing;Take 4 lamella poststacks are two-sided to be covered with 1oz rolled copper foils, hot forming,
It can obtain the flame-proof heat-resistant copper-clad plate;By the way of gradually heating up and boosting, 10min temperature rises hot pressing condition from 50 DEG C
To 180 DEG C, 40min is kept, then 10min is raised to 200 DEG C of holding 80min, and then 5min is raised to 230 DEG C of holding 80min, finally
180min is cooled to 50 DEG C.1min pressure is from 0Kg/cm2It is raised to 15Kg/cm2, then pressurize 80min, then 1min be raised to 20Kg/
cm2Pressurize 60min, last 1min are raised to 35Kg/cm2, pressurize 80min.
Comparative example one
(1) 300g bisphenol A cyanate ester monomers are added in beaker by the preparation of resin matrix, and 90 DEG C of oil bath reacts 8 points
Clock is warming up to 150 DEG C, adds in 0.07g monoethanolamines, reacts 20 minutes, liquid is poured into pallet, natural cooling obtains white
Solid;
(2) product, 12g phosphor nitrogen combustion inhibitors, 80g butanone solvents prepared by 100g steps (1) are added in into beaker, unlatching is stirred
It mixes, 0.5h is up to glue;Then E-glass cloth is immersed in above-mentioned glue, toasted under the conditions of 170 DEG C in an oven
2min prepares prepreg, and the mass fraction of glass cloth is 20%;Prepreg is cut out into burr removing;Take 4 lamella poststacks are two-sided to be covered with
1oz rolled copper foils, hot forming, you can obtain the flame-proof heat-resistant copper-clad plate.Pressing condition uses what is gradually heated up and boost
Mode, 20min temperature are raised to 150 DEG C from 50 DEG C, keep 120min, and then 10min is raised to 200 DEG C of holding 90min, then 5min
It is raised to 240 DEG C of holdings 100min, last 180min and is cooled to 50 DEG C.1min pressure is from 0Kg/cm2It is raised to 5Kg/cm2, then pressurize
25min, then 1min be raised to 15Kg/cm2Pressurize 50min, last 1min are raised to 25Kg/cm2, pressurize 100min.
Comparative example two
100g bisphenol A epoxide resins, 10gDOPO, 80g butanone solvent are added in into beaker, opens stirring, 0.5h is up to glue
Liquid;E-glass cloth is immersed in above-mentioned glue, 2min is toasted at 170 DEG C in an oven, prepares prepreg, glass cloth
Mass fraction is 22%;Prepreg is cut out into burr removing;Take 4 lamella poststacks are two-sided to be covered with 1oz rolled copper foils, hot forming, you can
Obtain the flame-proof heat-resistant copper-clad plate.By the way of gradually heating up and boosting, 20min temperature is raised to pressing condition from 50 DEG C
150 DEG C, 120min is kept, then 10min is raised to 200 DEG C of holding 60min, and then 5min is raised to 220 DEG C of holding 110min, finally
180min is cooled to 50 DEG C.1min pressure is from 0Kg/cm2It is raised to 5Kg/cm2, then pressurize 25min, then 1min be raised to 15Kg/
cm2Pressurize 50min, last 1min are raised to 25Kg/cm2, pressurize 100min.
According to mechanical performance of the IPC standard methods to the plank 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 1 flame-proof heat-resistant copper-clad plate of table
Flame retardant rating | Wicking/second | tanδ | ε | Td/℃ | Peel strength/1b/in | Tg/℃ | |
Embodiment one | V0 | > 300 | 0.007 | 3.68 | 412 | 8.6 | 244 |
Embodiment two | V0 | > 300 | 0.008 | 3.60 | 414 | 8.6 | 246 |
Embodiment three | V0 | > 300 | 0.006 | 3.54 | 419 | 8.8 | 245 |
Example IV | V0 | > 300 | 0.006 | 3.65 | 411 | 8.7 | 251 |
Embodiment five | V0 | > 300 | 0.007 | 3.61 | 412 | 8.6 | 247 |
Comparative example one | V1 | > 300 | 0.011 | 3.82 | 401 | 8.1 | 240 |
Comparative example two | V1 | 254 | 0.016 | 4.12 | 369 | 7.5 | 212 |
To sum up, flame-proof heat-resistant copper-clad plate composition disclosed by the invention is reasonable, and compatibility is good between each component, thus prepares
Flame-proof heat-resistant copper-clad plate has been obtained, there is good anti-flammability, excellent heat resistance, especially with low hydroscopicity, has been implemented
Example hydroscopicity is less than 0.05%;Meet the development and application of flame-proof heat-resistant copper-clad plate.
Claims (6)
1. a kind of flame-proof heat-resistant copper-clad plate, which is characterized in that the preparation method of the flame-proof heat-resistant copper-clad plate includes the following steps:
(1) by nano silicon dioxide foam dispersion in deionized water, then add in dodecyl benzene sulfonic acid, five water bismuth nitrates and
Methyl trichlorosilane;Then hydro-thermal reaction 2 hours at 150 DEG C;Then filtering reacting liquid, filter cake are added in ethyl alcohol, and dispersion is equal
Tween-80 is added after even, is stirred in 60 DEG C 2 hours, finally drying obtains filler;
(2) mixing DOPO and bisphenol A cyanate monomer, 95 DEG C of stirrings add in phenolic compounds after 25 minutes, continue stirring 30 minutes;
Then m-nitrobenzene sulfonic acid pyridiniujm, 2,3- epoxy group cyclopenta ring amyl ethers are added in, continues stirring 20 minutes;Add in phosphorous acid
Dimethyl ester stirs 30 minutes in 100 DEG C;Obtain resin prepolymer;
(3) filler is added in o-phthalic acid diglycidyl ester, 125 DEG C are stirred 1 hour, obtain active filler;By resin
Prepolymer is mixed with benzazolyl compounds, is stirred 30 minutes in 120 DEG C;Then active filler is added in, is stirred 30 minutes in 130 DEG C;
Then isomery undecyl alcohol polyoxyethylene ether phosphate sylvite is added in, compound system is obtained within 50 minutes in 140 DEG C of stirrings;
(4) glue is made in the dissolving of above-mentioned compound system solvent, then reinforcing material is immersed in above-mentioned glue;After dipping
The heated drying of reinforcing material after, obtain prepreg;Prepreg is cut out into burr removing;Take the prepreg of 2~5 sanction burr removings
Poststack is two-sided to be covered with metal foil, hot forming, you can obtains the flame-proof heat-resistant copper-clad plate;In the prepreg, reinforcing material
Mass fraction be 20~22%;
The chemical structural formula of the phenolic compounds is:
The chemical structural formula of the benzazolyl compounds is:
Wherein R1For hydrogen or methyl, R2For methyl or methyl formate base, R3For amino or cyano.
2. flame-proof heat-resistant copper-clad plate according to claim 1, it is characterised in that:In step (1), the nano silicon dioxide bubble
Foam, dodecyl benzene sulfonic acid, five water bismuth nitrates and methyl trichlorosilane, the mass ratio of Tween-80 are
1∶0.2∶0.2∶0.35∶0.05;The grain size of the filler is 560~880nm.
3. flame-proof heat-resistant copper-clad plate according to claim 1, it is characterised in that:In step (2), DOPO, bisphenol A cyanate list
Body, phenolic compounds, m-nitrobenzene sulfonic acid pyridiniujm, 2,3- epoxy group cyclopenta rings amyl ether, dimethylphosphite mass ratio
It is 0.05: 1;0.2~0.3: 0.08~0.085: 0.58~0.63: 0.09~0.12.
4. flame-proof heat-resistant copper-clad plate according to claim 1, it is characterised in that:In step (3), filler, phthalic acid two
Ethylene oxidic ester, resin prepolymer, benzazolyl compounds, isomery undecyl alcohol polyoxyethylene ether phosphate sylvite mass ratio be 0.32
~0.45: 0.12~0.15: 1: 0.08~0.09: 0.01~0.015.
5. flame-proof heat-resistant copper-clad plate according to claim 1, it is characterised in that:In step (4), the solvent is butanone, second
The mixture of glycol methyl ether;The reinforcing material is electronic-grade glass fiber cloth;The metal foil is 18~35 μm by thickness
Rolled copper foil is prepared after etching.
6. flame-proof heat-resistant copper-clad plate according to claim 1, it is characterised in that:In step (4), pressure condition during hot pressing is
15~35kg/cm2, pressing-in temp is 180~230 DEG C, and pressing time is 170~200min.
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KR20210063345A (en) * | 2018-09-24 | 2021-06-01 | 에이에스엠엘 네델란즈 비.브이. | target forming device |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102975430A (en) * | 2012-11-27 | 2013-03-20 | 上海南亚覆铜箔板有限公司 | Flame-retarding copper clad laminate coated with solid content containing phosphorous and no halogen and preparation method thereof |
CN103626467A (en) * | 2013-12-11 | 2014-03-12 | 北京建筑材料科学研究总院有限公司 | Preparation method of aerosil composite glass cotton fiber needled felt |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003147171A (en) * | 2001-11-15 | 2003-05-21 | Hitachi Chem Co Ltd | Method for producing insulating resin composition, insulating resin composition, and copper-foil laminated insulating material and copper-clad laminate |
CN101580627B (en) * | 2009-06-11 | 2011-09-21 | 中国科学院广州化学研究所 | Halogen-free phosphorus-containing fire retardant epoxy base material for printed circuit copper clad laminate and preparation method thereof |
CN102850984A (en) * | 2012-09-19 | 2013-01-02 | 江苏华海诚科新材料有限公司 | Low-stress epoxy resin composition applicable to packaging small-size surface mounted devices |
CN103059517A (en) * | 2012-12-31 | 2013-04-24 | 金安国纪科技股份有限公司 | Environmentally-friendly copper-clad plate glue solution, copper-clad plate and preparation method thereof |
CN103923487B (en) * | 2013-01-14 | 2015-11-25 | 广东先导稀材股份有限公司 | Preparation method of bismuth vanadate pigment |
CN104692401B (en) * | 2015-03-11 | 2017-04-12 | 江苏视客新材料股份有限公司 | Silicon dioxide composite microspheres of metal or metal oxide nanoparticles and preparation method thereof |
-
2015
- 2015-09-02 CN CN201711164020.2A patent/CN107973934A/en active Pending
- 2015-09-02 CN CN201711164016.6A patent/CN108146035A/en active Pending
- 2015-09-02 CN CN201510551973.9A patent/CN105172297A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102975430A (en) * | 2012-11-27 | 2013-03-20 | 上海南亚覆铜箔板有限公司 | Flame-retarding copper clad laminate coated with solid content containing phosphorous and no halogen and preparation method thereof |
CN103626467A (en) * | 2013-12-11 | 2014-03-12 | 北京建筑材料科学研究总院有限公司 | Preparation method of aerosil composite glass cotton fiber needled felt |
Non-Patent Citations (1)
Title |
---|
张培阳: "新型铋系光催化剂的制备及其光催化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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