CN106273823B - A kind of preparation method of environmental protection flame retardant copper-clad plate - Google Patents
A kind of preparation method of environmental protection flame retardant copper-clad plate Download PDFInfo
- Publication number
- CN106273823B CN106273823B CN201610632198.4A CN201610632198A CN106273823B CN 106273823 B CN106273823 B CN 106273823B CN 201610632198 A CN201610632198 A CN 201610632198A CN 106273823 B CN106273823 B CN 106273823B
- Authority
- CN
- China
- Prior art keywords
- parts
- flame retardant
- environmental protection
- copper
- clad plate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
- B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
-
- 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
-
- 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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/544—Torsion strength; Torsion stiffness
-
- 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
Abstract
The invention discloses a kind of preparation methods of environmental protection flame retardant copper-clad plate, belong to technical field of electronic materials.The present invention first aoxidizes graphite by hydrogen peroxide; again with the substances such as ethylenediamine; reaction modifying is carried out under nitrogen protection; it is mixed again with dimethyl dichlorosilane (DMCS), antimony oxide, with mixture being made to be overlying on graphene surface after laser irradiation, obtains environmental protection flame retardant base-material; then flame-retardant adhesive is stirred to obtain with benzoxazine resin etc.; coated on Kapton, copper foil and its are then subjected to gluing, up to environmental protection flame retardant copper-clad plate after hot pressing, curing.The homemade environmental protection flame retardant base-material of the present invention, the anti-flammability of resin can be significantly improved, it is and not phosphorous, it not can cause environmental pollution, both the defects of traditional copper-clad plate flame retardant property is bad had been compensated for, it solves the problems, such as destruction of the copper-clad plate using neutralization after discarded to ecological environment again, there is preferable use value.
Description
Technical field
The invention discloses a kind of preparation methods of environmental protection flame retardant copper-clad plate, belong to technical field of electronic materials.
Background technology
Copper-clad plate abbreviation CCL is the basic material of electronic product.Copper-clad plate is covered with resin dipping glue lay-up
Upper copper foil is formed through hot pressing, and insulating layer is made of reinforcing material and resin, and conductive layer is made of copper foil.At present, electronics industry
It rapidly develops, exploitation and the research and development of various high performance copper clad laminate products also become hot spot.
At present, the technology of the fire-retardant copper-clad plate of production of comparative maturity, is to contain halogen, antimony by being introduced into resin matrix
Element etc. improves the flame-retardant compound of environment harmful element the anti-flammability of plank.Since 2006, European Union comes into effect
WEEE standards and RoHS standards, do not allow the electronic product containing fire retardants such as polybrominated diphenyl ethers, polybrominated biphenyls and heavy metals into
Enter EU market.Therefore, very urgent task is become to the research and development of halogen-free flame retardants.In recent years, to boron, nitrogen,
The research and development of silicon systems fire-retardant epoxy resin make some progress, however in the application aspect of fire-retardant copper-clad plate, domestic and state
There are still very big gaps outside.The environmentally friendly copper-clad plate for many good flame retardation effects reported is all poor there are performance
With cost it is excessively high the shortcomings that, be difficult to realize industrialized production.Phosphorus flame retardant has the fire-retardant highly effective of high polymer material
Inexpensive, lasting, less toxic, the features such as thermal stability is good.But phosphorus flame retardant easily corrodes mold, and noxious material is easily from product
Middle exudation, causes secondary pollution.For exclusive use some additive amounts greatly with resin matrix poor compatibility and influence product capability
The shortcomings of learning performance.Since nitrogenous flame ratardant has compared with high fire-retardance efficiency and heat decomposition temperature, decomposition product low toxicity, environment friend
Good, the trend of the compound current flame retardant products of recoverable is widely used.These civil electronic electric equipment products
It substantial amounts and updates fast, thereby produces a large amount of wastes, they are much by burning disposal, if processing is not
When easily causing seriously to pollute and endanger human health to environment.Therefore, environmental protection flame retardant copper-clad plate is developed, is not only to adapt to
The market demand, and be also environmental protection, pay close attention to the major action of human health, meaning is very great.It is but traditional at present
The traditional fire-retardant copper-clad plate heat resistance of copper-clad plate, anti-flammability are bad, and copper foil of copper-clad plate and support it base material between bonding
Intensity is relatively low, and causes considerable damage to ecological environments such as water quality and soil using process or after discarding.
Invention content
Present invention mainly solves the technical issues of：For current traditional copper-clad plate there are it is heat-resisting, flame retardant property is bad, even
Using process or after discarding, the defects of doing great damage to water quality and soil, a kind of system of environmental protection flame retardant copper-clad plate is provided
Preparation Method.The present invention first aoxidizes graphite by hydrogen peroxide, then with the substances such as ethylenediamine, carry out under nitrogen protection anti-
It should be modified, then be mixed with dimethyl dichlorosilane (DMCS), antimony oxide, with mixture being made to be overlying on graphene surface after laser irradiation, be obtained
Environmental protection flame retardant base-material then stirs to obtain flame-retardant adhesive, coated on Kapton, then by copper with benzoxazine resin etc.
Foil carries out gluing with it, up to environmental protection flame retardant copper-clad plate after hot pressing, curing.The homemade environmental protection flame retardant base-material of the present invention, Ke Yiming
The aobvious anti-flammability for improving resin, and it is not phosphorous, it not can cause environmental pollution, it is bad both to have compensated for traditional copper-clad plate flame retardant property
The defects of, and solve the problems, such as destruction of the copper-clad plate using neutralization after discarded to ecological environment, there is preferable use value.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
（1）By solid-to-liquid ratio 1:3, graphite and mass fraction is taken to be uniformly mixed for 26% hydrogen peroxide, and be heated to 110~
120 DEG C, cooled to room temperature after 40~50min is kept the temperature, filter and makes to be washed with distilled water filter residue to neutrality, in parts by weight
Meter, takes 32~35 parts of acetone, 28~29 parts of filter residues, 13~16 parts of ethylenediamines and 4~6 parts of sodium metavanadates, is put into blender
And it is uniformly mixed in the three-necked flask of thermometer；
（2）Above-mentioned three-necked flask is placed in water-bath, is protected using nitrogen, set temperature is 70~80 DEG C, with 200r/
After min stirs 1~2h, it is separately added into the dimethyl dichlorosilane (DMCS) of above-mentioned acetone volume 7~9% and above-mentioned filter residue quality 7~9%
Antimony oxide stirs evenly, and using laser irradiation three-necked flask, optical maser wavelength is 820~850nm, energy density for 42~
47mJ/cm2, frequency is 1.1~1.3kHz, irradiates 2~3min；
（3）After above-mentioned laser irradiation, the mixture in three-necked flask is filtered, uses 1~2 times of filtrate volume
Absolute ethyl alcohol rinses filter residue 1~2 time, reuses distilled water flushing filter residue to neutrality, then filter residue is placed in 90 DEG C of baking ovens and is done
Dry 5~6h obtains environmental protection flame retardant base-material；
（4）Count in parts by weight, take 26~29 parts of benzoxazine resins, 18~21 parts of brominated epoxy resins, 50~70 parts
Butanone, 18~22 parts of environmental protection flame retardant base-materials, 8~11 parts of silicon carbide, 1~2 part of phthalic anhydride and 1~2 part of triethanolamine, put
Enter in blender, 1~2h is stirred with 500r/min, obtains flame-retardant adhesive；
（5）Above-mentioned flame-retardant adhesive is coated on Kapton, coating thickness is 8~12 μm, is placed in 75 DEG C
Dry 7~9min in baking oven, then by copper foil with coated on the flame-retardant adhesive gluing on Kapton, being placed in hot press
In, set temperature is 140 DEG C, after preheating 22~25s, is warming up to 150 DEG C, and pressure is set as 5~10MPa, 2~4min of hot pressing,
It is subsequently placed at 185~190 DEG C of 1~2h of curing, you can obtain environmental protection flame retardant copper-clad plate.
The present invention physical property be：The amount of deflection of copper-clad plate produced by the present invention be 1.3~2.0mm, bending strength 400
~600N/mm2, dilatory intensity is resisted to be 300~500N, thermal conductivity is 0.03~0.17W/ (mK), resistance to 400~500 DEG C of high temperature.
The beneficial effects of the invention are as follows：
（1）Fire-retardant copper-clad plate produced by the present invention, resistance to 400~500 DEG C of high temperature, and excellent in bent-resistant performance；
（2）The homemade environmental protection flame retardant base-material of the present invention, can significantly improve the anti-flammability of resin, benzoxazine colophony is in itself
There is self-extinguishment, when itself and epoxy resin, phenolic resin can significantly improve resin when inflammable resin is mixed after polymerization
Anti-flammability；
（3）It is not phosphorous in benzoxazine colophony, it not can cause environmental pollution.
Specific embodiment
Solid-to-liquid ratio 1 is pressed first:3, graphite and mass fraction is taken to be uniformly mixed, and carry out being heated to 110 for 26% hydrogen peroxide
~120 DEG C, cooled to room temperature after 40~50min is kept the temperature, filter and makes to be washed with distilled water filter residue to neutrality, by weight
Number meter, takes 32~35 parts of acetone, 28~29 parts of filter residues, 13~16 parts of ethylenediamines and 4~6 parts of sodium metavanadates, is put into stirring
It is uniformly mixed in the three-necked flask of device and thermometer；Above-mentioned three-necked flask is placed in water-bath, is protected using nitrogen, setting temperature
It is 70~80 DEG C to spend, with 200r/min stir 1~2h after, be separately added into above-mentioned acetone volume 7~9% dimethyl dichlorosilane (DMCS) and
The antimony oxide of above-mentioned filter residue quality 7~9%, stirs evenly, using laser irradiation three-necked flask, optical maser wavelength for 820~
850nm, energy density are 42~47mJ/cm2, frequency is 1.1~1.3kHz, irradiates 2~3min；After above-mentioned laser irradiation,
Mixture in three-necked flask is filtered, filter residue is rinsed 1~2 time, then make using 1~2 times of absolute ethyl alcohol of filtrate volume
With distilled water flushing filter residue to neutrality, filter residue is then placed in 90 DEG C of baking ovens dry 5~6h, obtains environmental protection flame retardant base-material；By weight
Number meter is measured, takes 26~29 parts of benzoxazine resins, 18~21 parts of brominated epoxy resins, 50~70 parts of butanone, 18~22 parts of rings
Environment friendly flame-retardant base-material, 8~11 parts of silicon carbide, 1~2 part of phthalic anhydride and 1~2 part of triethanolamine, are put into blender, with
500r/min stirs 1~2h, obtains flame-retardant adhesive；Above-mentioned flame-retardant adhesive is coated on Kapton, coating thickness
It is 8~12 μm, is placed in 75 DEG C of baking ovens dry 7~9min, then by copper foil and coated on the fire retardant glue on Kapton
Glutinous agent gluing, is placed in hot press, and set temperature is 140 DEG C, after preheating 22~25s, is warming up to 150 DEG C, pressure is set as 5
~10MPa, 2~4min of hot pressing are subsequently placed at 185~190 DEG C of 1~2h of curing, you can obtain environmental protection flame retardant copper-clad plate.
Example 1
Solid-to-liquid ratio 1 is pressed first:3, graphite and mass fraction is taken to be uniformly mixed, and carry out being heated to 110 for 26% hydrogen peroxide
DEG C, cooled to room temperature after 40min is kept the temperature, filters and makes to be washed with distilled water filter residue to neutrality, count in parts by weight, take 32
Part acetone, 28 parts of filter residues, 13 parts of ethylenediamines and 4 parts of sodium metavanadates, are put into the three-necked flask with blender and thermometer and mix
It closes uniform；Above-mentioned three-necked flask is placed in water-bath, is protected using nitrogen, set temperature is 70 DEG C, is stirred with 200r/min
After 1h, the dimethyl dichlorosilane (DMCS) of above-mentioned acetone volume 7% and the antimony oxide of above-mentioned filter residue quality 7% are separately added into, is stirred
Uniformly, using laser irradiation three-necked flask, optical maser wavelength 820nm, energy density 42mJ/cm2, frequency 1.1kHz, photograph
Penetrate 2min；After above-mentioned laser irradiation, the mixture in three-necked flask is filtered, uses 1 times of anhydrous second of filtrate volume
Alcohol rinses filter residue 1 time, reuses distilled water flushing filter residue to neutrality, filter residue is then placed in 90 DEG C of baking ovens dry 5h, obtains ring
Environment friendly flame-retardant base-material；It counts in parts by weight, takes 26 parts of benzoxazine resins, 18 parts of brominated epoxy resins, 50 parts of butanone, 18 parts of environmental protection
Fire-retardant base-material, 8 parts of silicon carbide, 1 part of phthalic anhydride and 1 part of triethanolamine, are put into blender, are stirred with 500r/min
1h obtains flame-retardant adhesive；Above-mentioned flame-retardant adhesive is coated on Kapton, coating thickness is 8 μm, is placed in 75 DEG C
Dry 7min in baking oven, then by copper foil with coated on the flame-retardant adhesive gluing on Kapton, being placed in hot press,
Set temperature is 140 DEG C, after preheating 22s, is warming up to 150 DEG C, and pressure is set as 5MPa, hot pressing 2min, is subsequently placed at 185 DEG C admittedly
Change 1h, you can obtain environmental protection flame retardant copper-clad plate.
The present invention physical property be：The amount of deflection of copper-clad plate produced by the present invention is 1.3mm, bending strength 400N/
mm2, dilatory intensity is resisted to be 300N, thermal conductivity is 0.03W/ (mK), resistance to 400 DEG C of high temperature.
Example 2
Solid-to-liquid ratio 1 is pressed first:3, graphite and mass fraction is taken to be uniformly mixed, and carry out being heated to 115 for 26% hydrogen peroxide
DEG C, cooled to room temperature after 45min is kept the temperature, filters and makes to be washed with distilled water filter residue to neutrality, count in parts by weight, take 34
Part acetone, 28.5 parts of filter residues, 15 parts of ethylenediamines and 5 parts of sodium metavanadates, are put into the three-necked flask with blender and thermometer
It is uniformly mixed；Above-mentioned three-necked flask is placed in water-bath, is protected using nitrogen, set temperature is 75 DEG C, is stirred with 200r/min
After mixing 1.5h, the dimethyl dichlorosilane (DMCS) of above-mentioned acetone volume 8% and the antimony oxide of above-mentioned filter residue quality 8% are separately added into,
It stirs evenly, uses laser irradiation three-necked flask, optical maser wavelength 840nm, energy density 45mJ/cm2, frequency is
1.2kHz irradiates 2.5min；After above-mentioned laser irradiation, the mixture in three-necked flask is filtered, uses filtrate volume
1.5 times of absolute ethyl alcohol rinses filter residue 1.5 times, reuses distilled water flushing filter residue to neutrality, filter residue then is placed in 90 DEG C of bakings
Dry 5.5h, obtains environmental protection flame retardant base-material in case；Count in parts by weight, take 27 parts of benzoxazine resins, 20 parts of brominated epoxy resins,
60 parts of butanone, 22 parts of environmental protection flame retardant base-materials, 10 parts of silicon carbide, 1.5 parts of phthalic anhydrides and 1.5 parts of triethanolamines, are put into and stir
It mixes in machine, 1.5h is stirred with 500r/min, obtains flame-retardant adhesive；Above-mentioned flame-retardant adhesive is coated on Kapton,
Coating thickness is 10 μm, is placed in 75 DEG C of baking ovens dry 8min, then copper foil is fire-retardant on Kapton with being coated on
Adhesive gluing, is placed in hot press, and set temperature is 140 DEG C, after preheating 24s, is warming up to 150 DEG C, pressure is set as
7MPa, hot pressing 3min are subsequently placed at 187 DEG C of curing 1.5h, you can obtain environmental protection flame retardant copper-clad plate.
The present invention physical property be：The amount of deflection of copper-clad plate produced by the present invention is 1.7mm, bending strength 500N/
mm2, dilatory intensity is resisted to be 400N, thermal conductivity is 0.09W/ (mK), resistance to 450 DEG C of high temperature.
Example 3
Solid-to-liquid ratio 1 is pressed first:3, graphite and mass fraction is taken to be uniformly mixed, and carry out being heated to 120 for 26% hydrogen peroxide
DEG C, cooled to room temperature after 50min is kept the temperature, filters and makes to be washed with distilled water filter residue to neutrality, count in parts by weight, take 35
Part acetone, 29 parts of filter residues, 16 parts of ethylenediamines and 6 parts of sodium metavanadates, are put into the three-necked flask with blender and thermometer and mix
It closes uniform；Above-mentioned three-necked flask is placed in water-bath, is protected using nitrogen, set temperature is 80 DEG C, is stirred with 200r/min
After 2h, the dimethyl dichlorosilane (DMCS) of above-mentioned acetone volume 9% and the antimony oxide of above-mentioned filter residue quality 9% are separately added into, is stirred
Uniformly, using laser irradiation three-necked flask, optical maser wavelength 850nm, energy density 47mJ/cm2, frequency 1.3kHz, photograph
Penetrate 3min；After above-mentioned laser irradiation, the mixture in three-necked flask is filtered, uses 2 times of anhydrous second of filtrate volume
Alcohol rinses filter residue 2 times, reuses distilled water flushing filter residue to neutrality, filter residue is then placed in 90 DEG C of baking ovens dry 6h, obtains ring
Environment friendly flame-retardant base-material；It counts in parts by weight, takes 29 parts of benzoxazine resins, 21 parts of brominated epoxy resins, 70 parts of butanone, 20 parts of environmental protection
Fire-retardant base-material, 11 parts of silicon carbide, 2 parts of phthalic anhydrides and 2 parts of triethanolamines, are put into blender, are stirred with 500r/min
2h obtains flame-retardant adhesive；Above-mentioned flame-retardant adhesive is coated on Kapton, coating thickness is 12 μm, is placed in 75
Dry 9min in DEG C baking oven, then by copper foil with coated on the flame-retardant adhesive gluing on Kapton, being placed in hot press
In, set temperature is 140 DEG C, after preheating 25s, is warming up to 150 DEG C, pressure is set as 10MPa, and hot pressing 4min is subsequently placed at 190
DEG C curing 2h, you can environmental protection flame retardant copper-clad plate.
The present invention physical property be：The amount of deflection of copper-clad plate produced by the present invention is 2.0mm, bending strength 600N/
mm2, dilatory intensity is resisted to be 500N, thermal conductivity is 0.17W/ (mK), resistance to 500 DEG C of high temperature.
Claims (1)
1. a kind of preparation method of environmental protection flame retardant copper-clad plate, it is characterised in that specifically preparation process is：
（1）By solid-to-liquid ratio 1:3, graphite and mass fraction is taken to be uniformly mixed, and carry out being heated to 110~120 for 26% hydrogen peroxide
DEG C, cooled to room temperature after 40~50min is kept the temperature, filters and makes to be washed with distilled water filter residue to neutrality, count in parts by weight,
32~35 parts of acetone, 28~29 parts of filter residues, 13~16 parts of ethylenediamines and 4~6 parts of sodium metavanadates are taken, are put into blender and temperature
It spends in the three-necked flask of meter and is uniformly mixed；
（2）Above-mentioned three-necked flask is placed in water-bath, is protected using nitrogen, set temperature is 70~80 DEG C, with 200r/min
Stir 1~2h after, be separately added into above-mentioned acetone volume 7~9% dimethyl dichlorosilane (DMCS) and above-mentioned filter residue quality 7~9% three
Aoxidize two antimony, stir evenly, using laser irradiation three-necked flask, optical maser wavelength is 820~850nm, energy density for 42~
47mJ/cm2, frequency is 1.1~1.3kHz, irradiates 2~3min；
（3）After above-mentioned laser irradiation, the mixture in three-necked flask is filtered, uses the anhydrous of 1~2 times of filtrate volume
Ethyl alcohol rinses filter residue 1~2 time, reuses distilled water flushing filter residue to neutrality, filter residue is then placed in 90 DEG C of baking ovens dry 5~
6h obtains environmental protection flame retardant base-material；
（4）Count in parts by weight, take 26~29 parts of benzoxazine resins, 18~21 parts of brominated epoxy resins, 50~70 parts of butanone,
18~22 parts of environmental protection flame retardant base-materials, 8~11 parts of silicon carbide, 1~2 part of phthalic anhydride and 1~2 part of triethanolamine, are put into and stir
It mixes in machine, 1~2h is stirred with 500r/min, obtains flame-retardant adhesive；
（5）Above-mentioned flame-retardant adhesive is coated on Kapton, coating thickness is 8~12 μm, is placed in 75 DEG C of baking ovens
Middle 7~9min of drying, then by copper foil with coated on the flame-retardant adhesive gluing on Kapton, being placed in hot press,
Set temperature is 140 DEG C, after preheating 22~25s, is warming up to 150 DEG C, pressure is set as 5~10MPa, 2~4min of hot pressing, then
It is placed in 185~190 DEG C of 1~2h of curing, you can obtain environmental protection flame retardant copper-clad plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610632198.4A CN106273823B (en) | 2016-08-04 | 2016-08-04 | A kind of preparation method of environmental protection flame retardant copper-clad plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610632198.4A CN106273823B (en) | 2016-08-04 | 2016-08-04 | A kind of preparation method of environmental protection flame retardant copper-clad plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106273823A CN106273823A (en) | 2017-01-04 |
| CN106273823B true CN106273823B (en) | 2018-06-26 |
Family
ID=57664753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610632198.4A Active CN106273823B (en) | 2016-08-04 | 2016-08-04 | A kind of preparation method of environmental protection flame retardant copper-clad plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106273823B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110482531B (en) * | 2019-08-16 | 2022-08-30 | 中国科学院宁波材料技术与工程研究所 | Preparation method and product of polybenzoxazine resin-based graphene |
| CN113927993B (en) * | 2021-11-10 | 2023-10-10 | 超越者新材料科技河北有限公司 | Light flame-retardant fireproof plate and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834155A (en) * | 2014-03-18 | 2014-06-04 | 铜陵浩荣电子科技有限公司 | Preparation method of resin glue liquid for producing high-frequency copper-clad plate |
| CN103963414A (en) * | 2014-05-27 | 2014-08-06 | 铜陵浩荣华科复合基板有限公司 | Method for preparing halogen-free and lead-free high-flame-retardant Tg copper-clad laminate |
| CN105175995A (en) * | 2015-08-03 | 2015-12-23 | 广东生益科技股份有限公司 | Epoxy resin composition for copper-clad plate and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103509329B (en) * | 2012-06-28 | 2016-01-20 | 中山台光电子材料有限公司 | Low dielectric resin constituent and apply its copper clad laminate and printed circuit board (PCB) |
-
2016
- 2016-08-04 CN CN201610632198.4A patent/CN106273823B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834155A (en) * | 2014-03-18 | 2014-06-04 | 铜陵浩荣电子科技有限公司 | Preparation method of resin glue liquid for producing high-frequency copper-clad plate |
| CN103963414A (en) * | 2014-05-27 | 2014-08-06 | 铜陵浩荣华科复合基板有限公司 | Method for preparing halogen-free and lead-free high-flame-retardant Tg copper-clad laminate |
| CN105175995A (en) * | 2015-08-03 | 2015-12-23 | 广东生益科技股份有限公司 | Epoxy resin composition for copper-clad plate and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106273823A (en) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104292753B (en) | High-CTI halogen-free epoxy resin composition for copper-clad plate and application of high-CTI halogen-free epoxy resin composition | |
| CN104177809B (en) | Low-dielectric halogen-free resin composition and application thereof | |
| EP3093315B1 (en) | Halogen-free epoxy resin composition, prepreg and laminate using same | |
| CN105936745B (en) | A kind of resin combination | |
| CN102975430B (en) | A kind of anti-flammability copper coated foil plate applying the solid content of phosphor-containing halogen-free element and preparation method thereof | |
| FI96035B (en) | Epoksidihartsimuovausmassoja | |
| TW201524989A (en) | Vinylbenzyl-etherified-dopo compound resin composition and preparation and application thereof | |
| CN105669952B (en) | Composition epoxy resin uses its prepreg, band supporter resin film, metal layers of foil lamination and multilayer board | |
| CN106273823B (en) | A kind of preparation method of environmental protection flame retardant copper-clad plate | |
| KR101830560B1 (en) | Epoxy resin composition, prepreg and laminate using same | |
| CN102206397A (en) | Resin composition as well as semi-solidified rubber sheet, laminating board and circuit board containing same | |
| CN104130289B (en) | Vinylated phosphazene compound and application and preparation method thereof | |
| TW201139496A (en) | Halogen-free flame-retardant epoxy resin composition, and prepreg and printed wiring board using the same | |
| CN103992622A (en) | Halogen-free resin composition, prepreg prepared from halogen-free resin composition and laminated board prepared from halogen-free resin composition and used for printed circuit | |
| CN103360764B (en) | Compositions of thermosetting resin and the prepreg using it to make and veneer sheet | |
| CN101717481A (en) | Phosphorus-containing phenolic aldehyde and preparation method thereof | |
| JP2017110014A (en) | Dopo derivative and epoxy resin composition applied in high-frequency substrate | |
| KR101813527B1 (en) | Phosphorus epoxy compound and method for preparing the same, epoxy composition comprising the same | |
| CN105131597A (en) | Halogen-free resin composition and prepreg using halogen-free resin composition and printed circuit laminated board | |
| WO2020161926A1 (en) | Resin composition and method for producing same | |
| CN113667276A (en) | Halogen-free high-Tg copper-clad substrate and preparation method thereof | |
| CN102702678B (en) | Halogen-free flame retardant toughened epoxy resin based composite material and preparation method thereof | |
| CN105017641B (en) | A kind of light flame-retardant plate and its processing method | |
| KR101945088B1 (en) | Varnishes and prepregs and laminates made therefrom | |
| CN103627146A (en) | Preparation and application of high-flexibility phosphorus-containing halogen-free epoxy resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Peng Jiadeng Inventor before: Chen Yizhong Inventor before: Song Qi Inventor before: Lu Na |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180402 Address after: 341600 Xinfeng Industrial Park, Ganzhou, Jiangxi Applicant after: Xinfeng Pu Yuan Electronic Material Co., Ltd. Address before: 213164 Jiangsu Province, Changzhou Tianning Hongmei Street liberation Village Village No. 222 edge mining Applicant before: Chen Yizhong |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |