CN109517197A - A kind of moulding process of high-frequency high-speed cyano resin copper-clad plate - Google Patents
A kind of moulding process of high-frequency high-speed cyano resin copper-clad plate Download PDFInfo
- Publication number
- CN109517197A CN109517197A CN201811363162.6A CN201811363162A CN109517197A CN 109517197 A CN109517197 A CN 109517197A CN 201811363162 A CN201811363162 A CN 201811363162A CN 109517197 A CN109517197 A CN 109517197A
- Authority
- CN
- China
- Prior art keywords
- clad plate
- copper
- cyano resin
- speed
- cyano
- 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.)
- Granted
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- 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
- C08K7/14—Glass
-
- 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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2361/04, C08J2361/18, and C08J2361/20
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a kind of moulding process of high-frequency high-speed cyano resin copper-clad plate, the moulding process of main synthesis and cyano resin copper-clad plate including cyano resin, wherein solute is aromatic dicarboxylic phenol in the preparation of cyano resin, aromatic amine and paraformaldehyde, solvent are n,N-Dimethylformamide and toluene, and the molar ratio of the solute and the solvent is 1:(0.3-0.6), the cyano resin monomer of structure-controllable can be obtained according to certain proportion according to reaction structure formula.High-frequency high-speed cyano resin copper-clad plate can be directly obtained in conjunction with copper process for pressing is covered by optimization reaction step and response parameter later, have the characteristics that high-fire resistance, high TG, halogen-free flame-retardance are excellent.Compared to traditional copper-clad plate forming process, it is not required to mixed glue and particle modified and dispersion, step is simple, and efficiency is higher.
Description
Technical field
The present invention relates to polymer-based composites to prepare manufacturing technology field, and more particularly to a kind of high frequency is high
The moulding process of fast cyano resin copper-clad plate.
Background technique
As smart electronics product etc. is that the information industry of representative, electronics industry are advanced by leaps and bounds, digital circuit is gradually walked
Enter information processing high speed, signal transmission high frequency stage, entire electronic system is towards light and short, multifunction, high density
Change, high reliability, cost effective direction are developed.
The moulding process of baseplate material largely influences the electronic transmission performance of high-frequency high-speed copper-clad plate, reliability
And cost.The preparation process of traditional copper-clad plate include filler modified, the filler dispersion of resin matrix, resin pretreatment, gluing,
The processes such as resin solidification molding easily lead to the increasing of copper-clad plate defect ware amount wherein filler modified and dispersion steps are cumbersome, low efficiency
Add.
Therefore, how to provide that a kind of operating procedure is easy, high-efficient and excellent combination property high-frequency high-speed copper-clad plate is used
The problem of moulding process of cyano resin is those skilled in the art's urgent need to resolve.
Summary of the invention
In view of this, the present invention provides a kind of good high-frequency high-speed cyano resin molding of copper-clad plates works of comprehensive performance
Skill simplifies forming step cumbersome at present, improves copper-clad plate preparation efficiency.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of moulding process of high-frequency high-speed cyano resin copper-clad plate, comprising the following steps:
(1) polymerization reaction promotor and solvent are added into cyano resin, constant temperature is stirred to react under the conditions of 125-130 DEG C
0.5-3h obtains glue；
(2) it takes base fabric to be placed in glue groove and impregnates glue made from the step (1), base fabric after being impregnated；
(3) base fabric baking removes solvent after impregnating obtained in the step (2), obtains semi-solid preparation film；
(4) gelation time for measuring the prepreg that the step (3) obtains, covers copper, in the vacuum press after stacking
Compression moulding；
(5) natural cooling is cooled to room temperature, and cyano resin copper-clad plate can be obtained.
In above-mentioned technical proposal, a kind of present invention is simple using synthetic method, molecular structure is controllable cyano resin as
Suitable temperature range is arranged in copper-clad plate resin matrix, under the action of polymerization accelerant, realizes the prepolymerization of cyano resin
Reaction, obtain the cyano resin performed polymer with certain molecular weight and preferable film forming, using in molecular structure can reactive group
Group reacts with the effect of the interface cohesion of copper foil and the cyclic polymerization of itrile group functional group, under the synergistic effect of temperature and pressure,
Obtain that polymer architecture intensity is high, temperature tolerance is good, dielectric properties copper-clad plate material outstanding.
Preferably, the polymerization accelerant in the step (1) includes epoxy resin, cyanate ester resin, benzoxazine resin
One or both of mixing, the dosage of polymerization accelerant be the 8-25% of cyano resin total amount.
The beneficial effect of above-mentioned optimal technical scheme is: that there are auto polymerizations is anti-for the promotor of system of the present invention selection itself
It answers, when polymerization accelerant dosage is lower than this range, facilitation effect is weaker, can not obtain being able to satisfy high-frequency high-speed under this condition
The cyano resin substrate of copper-clad plate；When accelerator dosage is higher than the range, auto polymerization can occur for one side promotor itself
Reaction, leads to system split-phase；On the other hand, the higher promotor of content can reduce material of main part cyano resin to a certain extent
Heat resistance and mechanical strength are unable to satisfy the demand of targeted high frequency high speed copper-clad plate application.
Preferably, the solvent in the step (1) is the mixing of one or both of n,N-Dimethylformamide, acetone.
The beneficial effect of above-mentioned optimal technical scheme is: using two kinds of solvents to the high solubility of cyano resin, making to set
Resin system shows good immersion and uniformity；Using solvent itself and the low boiling point of mixed solvent, it is solid to be conducive to subsequent half
Change the removal of solvent in piece.In addition, the adjustable cyano resin performed polymer in volatilization process of dicyandiamide solution selected by the present invention
Strand aggregated form adjusts the dielectric property of cyano resin matrix to a certain extent.
Preferably, in the step (2) glue dipping when, control the glue content of dipping mass fraction account for dipping after
The 38-45% of base fabric gross mass.
Preferably, the baking temperature in the step (3) is arranged at 175-195 DEG C, and baking duration is set as 8-15min.
The beneficial effect of above-mentioned optimal technical scheme is: when baking temperature is lower than this temperature, will lead to solvent removal not
Sufficiently, gummosis is serious during copper-clad plate compression moulding, causes the poor glue defect of copper-clad plate；When temperature is higher than this temperature range
When, excessive velocities occur for the polymerization reaction of cyano resin, cause molecular weight polyisoprene is poly- to increase, tree during copper-clad plate compression moulding
Aliphatic radical body cannot keep preferable mobility, and copper-clad plate is caused the defect of gel occurred.
Preferably, forming temperature is 180-200 DEG C, pressing pressure 15-20MPa, when compression moulding in the step (4)
Between be 100-200min.
The beneficial effect of above-mentioned optimal technical scheme is: when forming temperature is lower than this temperature range, cyano resin is being set
Condition of molding under can not be fully cured, the low danger that will lead to copper-clad plate and plate bursting occurs in subsequent use of curing degree；At
When shape temperature is higher than this temperature, the too fast polymerization of cyano resin, the molecular weight distribution that implode reaction will lead to polymer is wide, polymer
System shows the big defect of brittleness.
Preferably, the base fabric in the step (2) is glass fabric or non-woven fabrics, and the copper foil in the step (4) is
Electrolytic copper foil or rolled copper foil.
Preferably, the cyano resin in the step (1) includes solute and solvent, and solute is aromatic dicarboxylic phenol, fragrance
Amine and paraformaldehyde, solvent is n,N-Dimethylformamide and toluene, and the molar ratio of the solute and the solvent is 1:
(0.3-0.6), specific preparation method the following steps are included:
(1) aromatic dicarboxylic phenol, aromatic amine and paraformaldehyde are dried to 2h in 80 DEG C of drying box；
(2) successively aromatic dicarboxylic phenol, aromatic amine and paraformaldehyde are added to equipped with n,N-Dimethylformamide and first
In the there-necked flask of benzene, after stirring 10min at room temperature with the revolving speed of 120 turns/min, 90-120 is warming up to the rate of 5 DEG C/min
DEG C, 3-8h is stirred to react with the revolving speed constant temperature of 120 turns/min；
(3) temperature is increased after reaction to 120-140 DEG C, is kept constant temperature stirring the reaction was continued 2-5h, is obtained sticky
Dark liquid；
(4) the dark liquid cooled to room temperature in the step (3) can be used for the itrile group of copper-clad plate manufacture to obtain the final product
Resin.
The beneficial effect of above-mentioned optimal technical scheme is: the reaction that the preparation of above-mentioned cyano resin is related to is class Mannich
Annulation needs to control aromatic amine and first reacts to form imine structure with paraformaldehyde, then could shape with phenolic hydroxyl group addition cyclization
At target product；The presence of moisture can hinder the generation and progress of reaction in raw material in step (1), and drying process can make to synthesize
Reaction is prone to, to realize the structure-controllable of product；Slowly heating can promote paraformaldehyde and aromatic amine in step (2)
Sufficiently reaction, since the addition reaction of imine structure and paraformaldehyde needs just recur at 90 DEG C or more, setting should
Temperature range can promote effective progress of synthetic reaction；If paraformaldehyde reacts the Asia to be formed with aromatic amine when being lower than 90 DEG C
Amine structure cannot occur to reset deformation with phenolic hydroxyl group addition cyclization, be unable to get target product；When temperature is higher than 120 DEG C, mesh
Mark product can occur ring-opening reaction and generate new phenolic hydroxyl group, and the phenolic hydroxyl group of generation can seriously affect the progress of synthetic reaction, cause
Product structure is uncontrollable.
Preferably, n (aromatic dicarboxylic phenol): n (aromatic amine): (paraformaldehyde)=1:(2-3 in the step (2) :):
(3.8-4.2), n (n,N-Dimethylformamide): n (toluene)=1:(0.4-0.7).
The beneficial effect of above-mentioned optimal technical scheme is: solute will have a direct impact on the cyclization reacted with the molar ratio of solvent
Rate, specifically, form imine structure using the collision of paraformaldehyde and aromatic amine in synthetic reaction, later with phenolic hydroxyl group addition,
When solvent content is excessively high, the probability that phenolic hydroxyl group and polyformaldehyde reaction occur can be equal to the benefit of aromatic amine and polyformaldehyde reaction
Rate leads to the formation of phenolic structure, so that the purity of product is lower；When solvent content is too low, solute cannot be completely dissolved, shadow
The material ratio for ringing reaction, when furthermore solvent content is too low, it may appear that above-mentioned reaction and the uncontrollable problem of product structure；
Molar ratio and N, N- diformazan between aromatic dicarboxylic phenol disclosed by the invention, aromatic amine and paraformaldehyde
In the molar ratio range of base formamide and toluene, reaction can be normally carried out and product structure is controllable.But work as molar ratio
When lower than limiting range, more dihydric phenol can be remained in system, product is caused to be formed by the dielectric constant and damage of polymer
Consumption significantly increases；When molar ratio, which is higher than, limits range, excessive paraformaldehyde can react to form phenolic aldehyde knot prior to dihydric phenol
Structure is unfavorable for the structure control of product.
Preferably, the aromatic dicarboxylic phenol is bisphenol-A, bisphenol S, phenolphthalein, 2,6- bis- (4- hydroxyphenoxy) benzonitrile
One of or a variety of mixing；Specific structure specific structure is as follows:
The aromatic amine be selected from 4- (3- amino-benzene oxygen) phthalonitrile, 4- (4- amino-benzene oxygen) phthalonitrile,
4- (3- amino-benzene oxygen) benzonitrile, 4- (4- amino-benzene oxygen) benzonitrile, 2,6- bis- (4- amino-benzene oxygen) benzonitrile, aniline
In any two kinds or more of mixing, specific structure is as follows:
The beneficial effect of above-mentioned optimal technical scheme is: the conjunction of above-mentioned aromatic dicarboxylic phenol and aromatic amine provided by the invention
Optimal at product property, the dihydric phenol of other structures can also occur similar reaction with aromatic amine and obtain the production of structure-controllable
Object, but the performance of product is not able to satisfy the application requirement of high-frequency high-speed copper-clad plate.
It can be seen via above technical scheme that compared with prior art, the present disclosure provides a kind of high-frequency high-speed nitriles
The moulding process of base resin copper-clad plate is pressed by simple resins synthesis and performed polymer preparation and gluing process in conjunction with copper is covered
Technique can directly obtain high-frequency high-speed copper-clad plate, compared to traditional copper-clad plate forming process, be not required to mixed glue and particle modified
With dispersion, step is simple, and efficiency is higher, and cyano resin copper-clad plate obtained has more excellent performance.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
(1) synthesis of cyano resin
(1) first by bisphenol S, 4- (3- amino-benzene oxygen) phthalonitrile, paraformaldehyde is done in 80 DEG C of drying box
Dry processing 2 hours；
(2) successively by 28 grams of bisphenol Ss, 42 grams of 4- (3- amino-benzene oxygen) phthalonitriles, 3.5 grams of aniline, 12 grams of polies
Formaldehyde is added into the there-necked flask equipped with 23.2 grams of DMF and 11.6 gram of toluene, and 120 turns/min is stirred after ten minutes, with 5 at room temperature
DEG C/heating rate of min is warming up to 100 DEG C, it is kept stirring 120 turns/min of speed, constant temperature to reaction terminates, isothermal reaction duration
It is 6 hours；
(3) temperature is increased after reaction to 130 DEG C, and being kept stirring constant temperature, the reaction was continued 2.5 hours, steams 10 grams of toluene
Solvent；
(4) obtain after reaction sticky brown liquid to get to can be used for copper-clad plate manufacture cyano resin.
(2) preparation process of high-frequency high-speed copper-clad plate
(1) in the cyano resin that Xiang Shangshu is prepared be added account for cyano resin quality 8% epoxy resin and
15mLDMF, constant temperature is stirred to react 2 hours under the conditions of 125 DEG C, obtains dipping glue；
(2) glass fabric for taking suitable dimension, impregnates cyano resin glue in glue groove, and control dipping glue content accounts for leaching
The 40% of glue glass fabric total quality；
(3) glass fabric after impregnating passes through the baking channel of length 4m, and temperature setting is at 175-195 DEG C, baking
It is long to be set as 10min, solvent is removed, prepreg is obtained；
(4) gelation time for measuring prepreg, covers copper, in the vacuum press compression moulding, molding after stacking
Temperature is 200 DEG C, pressing pressure 20MPa, pressing forming time 120min；
(5) natural cooling is cooled to room temperature, obtains cyano resin copper-clad plate.
Gained is based on being in black inside the copper-clad plate of cyano resin, the defects of surfacing, bubble-free.Test result is such as
Under: glass transition temperature is 220 DEG C (DSC test), 265 DEG C (DMA test)；Thermal decomposition temperature is 420 DEG C (TGA test)；
Bending strength 580MPa, bending modulus 26GPa；Dielectric constant is 4.5 (3GHz), and dielectric loss is 0.007 (3GHz)；It can be very well
The application requirement for meeting high-frequency high-speed copper-clad plate cyano resin.
Embodiment 2
(1) synthesis of cyano resin
(1) first by bisphenol-A, 4- (3- amino-benzene oxygen) phthalonitrile, paraformaldehyde is done in 80 DEG C of drying box
Dry processing 2 hours；
(2) successively by 22.8 grams of bisphenol-As, 42 grams of 4- (3- amino-benzene oxygen) phthalonitriles, 3.5 grams of aniline, more than 12 grams
Polyformaldehyde is added into the there-necked flask equipped with 23.2 grams of DMF and 11.6 gram of toluene, and 120 turns/min is stirred after ten minutes at room temperature,
110 DEG C are warming up to the heating rate of 5 DEG C/min, is kept stirring 120 turns/min of speed, constant temperature to reaction terminates, isothermal reaction
Shi Changwei 5 hours；
(3) it is warming up to 135 DEG C of degree after reaction, being kept stirring constant temperature, the reaction was continued 2.5 hours, and it is molten to steam 10 grams of toluene
Agent；
(4) obtain after reaction sticky brown liquid to get to can be used for copper-clad plate manufacture cyano resin.
(2) preparation process of high-frequency high-speed copper-clad plate
(1) epoxy resin and 15mLDMF of cyano resin quality 15% are added in the cyano resin that Xiang Shangshu is prepared,
Constant temperature is stirred to react 1.5 hours under the conditions of 130 DEG C, obtains dipping glue；
(2) glass fabric for taking suitable dimension, impregnates cyano resin glue in glue groove, and control dipping glue content accounts for leaching
The 38% of glue glass fabric total quality；
(3) film after impregnating passes through the baking channel of length 4m, and temperature setting is at 175-195 DEG C, baking duration setting
For 10min, solvent is removed, prepreg is obtained；
(4) gelation time for measuring prepreg, covers copper, in the vacuum press compression moulding, molding after stacking
Temperature is 180 DEG C, pressing pressure 20MPa, pressing forming time 140min；
(5) natural cooling is cooled to room temperature, obtains cyano resin copper-clad plate.
Gained is based on being in black inside the copper-clad plate of cyano resin, the defects of surfacing, bubble-free.Test result is such as
Under: glass transition temperature is 200 DEG C (DSC test), 255 DEG C (DMA test)；Thermal decomposition temperature is 405 DEG C (TGA test)；
Bending strength 560MPa, bending modulus 25GPa；Dielectric constant is 4.6 (3GHz), and dielectric loss is 0.007 (3GHz)；It can be very well
The application requirement for meeting high-frequency high-speed copper-clad plate cyano resin.
Embodiment 3
(1) synthesis of cyano resin
(1) first by phenolphthalein, 4- (4- amino-benzene oxygen) phthalonitrile, paraformaldehyde drying in 80 DEG C of drying box
Processing 2 hours；
(2) successively by 31.8 grams of phenolphthalein, 40 grams of 4- (4- amino-benzene oxygen) phthalonitriles, 4.65 grams of benzene, 12 grams of polies
Formaldehyde is added into the there-necked flask equipped with 30.3 grams of DMF and 15.1 gram of toluene, and 120 turns/min is stirred after ten minutes at room temperature, and 5
DEG C/heating rate of min is warming up to 110 DEG C, it is kept stirring 120 turns/min of speed, constant temperature to reaction terminates, isothermal reaction duration
It is 4 hours；
(3) temperature is increased after reaction to 130 DEG C, and being kept stirring constant temperature, the reaction was continued 3 hours, and it is molten to steam 14 grams of toluene
Agent；
(4) sticky brown liquid is obtained after reaction, obtains the cyano resin that can be used for copper-clad plate manufacture.
(2) preparation process of high-frequency high-speed copper-clad plate
(1) in the cyano resin that Xiang Shangshu is prepared be added cyano resin quality 10% cyanate ester resin and
15mLDMF, constant temperature is stirred to react 2 hours under the conditions of 135 DEG C, obtains dipping glue；
(2) glass fabric for taking suitable dimension, impregnates cyano resin glue in glue groove, and control dipping glue content accounts for leaching
The 40% of glue glass fabric total quality；
(3) film after impregnating passes through the baking channel of length 4m, and temperature setting is at 175-195 DEG C, baking duration setting
For 12min, solvent is removed, prepreg is obtained；
(4) gelation time for measuring prepreg, covers copper, in the vacuum press compression moulding, molding after stacking
Temperature is 200 DEG C, pressing pressure 18MPa, pressing forming time 120min；
(5) natural cooling is cooled to room temperature, obtains cyano resin copper-clad plate.
Gained is based on being in black inside the copper-clad plate of cyano resin, the defects of surfacing, bubble-free.Test result is such as
Under: glass transition temperature is 218 DEG C (DSC test), 267 DEG C (DMA test)；Thermal decomposition temperature is 420 DEG C (TGA test)；
Bending strength 545MPa, bending modulus 24GPa；Dielectric constant is 4.5 (3GHz), and dielectric loss is 0.008 (3GHz)；It can be very well
The application requirement for meeting high-frequency high-speed copper-clad plate cyano resin.
Embodiment 4
(1) synthesis of cyano resin
(1) first by 2,6- bis- (4- hydroxyphenoxy) benzonitrile, 4- (4- amino-benzene oxygen) phthalonitrile, poly first
Aldehyde is dried 2 hours in 80 DEG C of drying box；
(2) successively by 31.9 grams of 2,6- bis- (4- hydroxyphenoxy) benzonitrile, the adjacent benzene of 35.2 grams of 4- (4- amino-benzene oxygen)
Dimethoxy nitrile, 5 grams of aniline, 12 grams of paraformaldehydes are added into the there-necked flask equipped with 30.3 grams of DMF and 15.1 gram of toluene, at room temperature
120 turns/min is stirred after ten minutes, and the heating rate of 5 DEG C/min is warming up to 115 DEG C, is kept stirring 120 turns/min of speed, constant temperature
Terminate to reaction, when isothermal reaction is 6 hours a length of；
(3) temperature is increased after reaction to 135 DEG C, and being kept stirring constant temperature, the reaction was continued 5 hours, and it is molten to steam 14 grams of toluene
Agent；
(4) sticky brown liquid is obtained after reaction, obtains the cyano resin that can be used for copper-clad plate manufacture.
(2) preparation process of high-frequency high-speed copper-clad plate
(1) in the cyano resin that Xiang Shangshu is prepared be added cyano resin quality 15% cyanate ester resin and
15mLDMF, constant temperature is stirred to react 2 hours under the conditions of 135 DEG C, obtains dipping glue；
(2) glass fabric for taking suitable dimension, impregnates cyano resin glue in glue groove, and control dipping glue content accounts for leaching
The 40% of glue glass fabric total quality；
(3) film after impregnating passes through the baking channel of length 4m, and temperature setting is at 175-195 DEG C, baking duration setting
For 15min, solvent is removed, prepreg is obtained；
(4) gelation time for measuring prepreg, covers copper, in the vacuum press compression moulding, molding after stacking
Temperature is 200 DEG C, pressing pressure 15MPa, pressing forming time 120min；
(5) natural cooling is cooled to room temperature, obtains cyano resin copper-clad plate.
Gained is based on being in black inside the copper-clad plate of cyano resin, the defects of surfacing, bubble-free.Test result is such as
Under: glass transition temperature is 198 DEG C (DSC test), 246 DEG C (DMA test)；Thermal decomposition temperature is 406 DEG C (TGA test)；
Bending strength 545MPa, bending modulus 24GPa；Dielectric constant is 4.5 (3GHz), and dielectric loss is 0.008 (3GHz)；It can be very well
The application requirement for meeting high-frequency high-speed copper-clad plate cyano resin.
Embodiment 5
(1) synthesis of cyano resin
(1) first by 2,6- bis- (4- hydroxyphenoxy) benzonitrile, 4- (4- amino-benzene oxygen) benzonitrile, paraformaldehyde exists
It is dried 2 hours in 80 DEG C of drying box；
(2) successively by 31.9 grams of 2,6- bis- (4- hydroxyphenoxy) benzonitrile, 42 grams of 4- (4- amino-benzene oxygen) benzonitriles,
8 grams of aniline, 12 grams of paraformaldehydes are added into the there-necked flask equipped with 30.3 grams of DMF and 15.1 gram of toluene, at room temperature 120 turns/min
After ten minutes, the heating rate of 5 DEG C/min is warming up to 110 DEG C for stirring, is kept stirring 120 turns/min of speed, and constant temperature is to reacting knot
Beam, when isothermal reaction, are 6 hours a length of；
(3) temperature is increased after reaction to 135 DEG C, and being kept stirring constant temperature, the reaction was continued 4 hours, and it is molten to steam 14 grams of toluene
Agent；
(4) obtain after reaction sticky brown liquid to get to can be used for copper-clad plate manufacture cyano resin.
(2) preparation process of high-frequency high-speed copper-clad plate
(1) cyanate ester resin and the itrile group tree of cyano resin quality 10% are added in the cyano resin that Xiang Shangshu is prepared
The benzoxazine resin and 20mLDMF of lipid amount 10%, constant temperature is stirred to react 2 hours under the conditions of 135 DEG C, obtains dipping glue
Liquid；
(2) non-woven fabrics for taking suitable dimension, in glue groove impregnate cyano resin glue, control dipping glue content account for impregnation without
The 40% of woven fabric total quality；
(3) film after impregnating passes through the baking channel of length 4m, and temperature setting is at 175-195 DEG C, baking duration setting
For 10min, solvent is removed, prepreg is obtained；
(4) gelation time for measuring prepreg, covers copper, in the vacuum press compression moulding, molding after stacking
Temperature is 190 DEG C, pressing pressure 20MPa, pressing forming time 150min；
(5) natural cooling is cooled to room temperature, obtains the copper-clad plate based on cyano resin.
Gained is based on being in black inside the copper-clad plate of cyano resin, the defects of surfacing, bubble-free.Test result is such as
Under: glass transition temperature is 210 DEG C (DSC test), 266 DEG C (DMA test)；Thermal decomposition temperature is 432 DEG C (TGA test)；
Bending strength 550MPa, bending modulus 28GPa；Dielectric constant is 4.4 (3GHz), and dielectric loss is 0.007 (3GHz)；It can be very well
The application requirement for meeting high-frequency high-speed copper-clad plate cyano resin.
Case study on implementation 6
(1) synthesis of cyano resin
(1) first by phenolphthalein, 4- (4- amino-benzene oxygen) phthalonitrile, paraformaldehyde drying in 80 DEG C of drying box
Processing 2 hours；
(2) successively by 31.8 grams of phenolphthalein, 40 grams of 4- (4- amino-benzene oxygen) phthalonitriles, 4.65 grams of benzene, 12 grams of polies
Formaldehyde is added into the there-necked flask equipped with 30.3 grams of DMF and 15.1 gram of toluene, and 120 turns/min is stirred after ten minutes at room temperature, and 5
DEG C/heating rate of min is warming up to 110 DEG C, it is kept stirring 120 turns/min of speed, constant temperature to reaction terminates, isothermal reaction duration
It is 4 hours；
(3) temperature is increased after reaction to 130 DEG C, and being kept stirring constant temperature, the reaction was continued 3 hours, and it is molten to steam 14 grams of toluene
Agent；
(4) sticky brown liquid is obtained after reaction, obtains the cyano resin that can be used for copper-clad plate manufacture.
(2) preparation process of high-frequency high-speed copper-clad plate
(1) cyanate ester resin and the itrile group tree of cyano resin quality 10% are added in the cyano resin that Xiang Shangshu is prepared
The benzoxazine resin of lipid amount 15%, 20mLDMF, constant temperature is stirred to react 2 hours under the conditions of 135 DEG C, obtains dipping glue；
(2) glass fabric for taking suitable dimension, impregnates cyano resin glue in glue groove, and control dipping glue content accounts for leaching
The 45% of glue glass fabric total quality；
(3) film after impregnating passes through the baking channel of length 4m, and temperature setting is at 175-195 DEG C, baking duration setting
For 10min, solvent is removed, prepreg is obtained；
(4) gelation time for measuring prepreg, covers copper, in the vacuum press compression moulding, molding after stacking
Temperature is 190 DEG C, pressing pressure 20MPa, pressing forming time 150min；
(5) natural cooling is cooled to room temperature, obtains cyano resin copper-clad plate.
Gained is based on being in black inside the copper-clad plate of cyano resin, the defects of surfacing, bubble-free.Test result is such as
Under: glass transition temperature is 240 DEG C (DSC test), 270 DEG C (DMA test)；Thermal decomposition temperature is 438 DEG C (TGA test)；
Bending strength 568MPa, bending modulus 27GPa；Dielectric constant is 4.5 (3GHz), and dielectric loss is 0.007 (3GHz)；It can be very well
The application requirement for meeting high-frequency high-speed copper-clad plate cyano resin.
Comparative example 1
This comparative example provides a kind of moulding process of high-frequency high-speed copper-clad plate cyano resin, specific steps and embodiment 1
It is almost the same, it the difference is that only: step (1) in the moulding process (two) of this comparative example, the itrile group that Xiang Shangshu is prepared
The epoxy resin and 15mLDMF of mass fraction 5% are added in resin, constant temperature is stirred to react 2 hours under the conditions of 125 DEG C, is obtained
Impregnate glue；
Gained is based on being in black inside the copper-clad plate of cyano resin, the defects of surfacing, bubble-free.Test result is such as
Under: glass transition temperature is 212 DEG C (DSC test), 258 DEG C (DMA test)；Thermal decomposition temperature is 390 DEG C (TGA test)；
Bending strength 524MPa, bending modulus 22GPa；Dielectric constant is 4.7 (3GHz), and dielectric loss is 0.009 (3GHz)；
Although can satisfy the application requirement of high-frequency high-speed copper-clad plate cyano resin, comprehensive performance is lower than implementation case
Example.
Comparative example 2
This comparative example provides a kind of moulding process of high-frequency high-speed copper-clad plate cyano resin, specific steps and embodiment 2
It is almost the same, it the difference is that only: step (1) in the moulding process (two) of this comparative example, the itrile group that Xiang Shangshu is prepared
The epoxy resin and 15mLDMF of mass fraction 30% are added in resin, constant temperature is stirred to react 1.5 hours under the conditions of 130 DEG C, is obtained
To dipping glue；
Gained is based on being in black inside the copper-clad plate of cyano resin, the defects of surfacing, bubble-free.Test result is such as
Under: glass transition temperature is 195 DEG C (DSC test), 235 DEG C (DMA test)；Thermal decomposition temperature is 388 DEG C (TGA test)；
Bending strength 546MPa, bending modulus 21.8GPa；Dielectric constant is 4.8 (3GHz), and dielectric loss is 0.009 (3GHz)；
Although can satisfy the application requirement of high-frequency high-speed copper-clad plate cyano resin, comprehensive performance is lower than implementation case
Example.
Comparative example 3
This comparative example provides a kind of moulding process of high-frequency high-speed copper-clad plate cyano resin, specific steps and embodiment 3
It is almost the same, it the difference is that only: step (1) in the moulding process (two) of this comparative example, the itrile group that Xiang Shangshu is prepared
The cyanate ester resin and 15mLDMF of mass fraction 10% are added in resin, constant temperature is stirred to react 2 hours under the conditions of 115 DEG C, is obtained
To dipping glue；
Gained is based on, in black, surfacing has the poor glue phenomenon in part, and bubble-free etc. lacks inside the copper-clad plate of cyano resin
It falls into.Test result is as follows: glass transition temperature is 215 DEG C (DSC test), 260 DEG C (DMA test)；Thermal decomposition temperature is 408
DEG C (TGA test)；Bending strength 502MPa, bending modulus 20.5GPa；Dielectric constant is 4.7 (3GHz), and dielectric loss is
0.009(3GHz)；
Although can satisfy the application requirement of high-frequency high-speed copper-clad plate cyano resin, comprehensive performance is lower than implementation case
Example.
Comparative example 4
This comparative example provides a kind of moulding process of high-frequency high-speed copper-clad plate cyano resin, specific steps and embodiment 4
Almost the same, the difference is that only: step (3) in the moulding process (two) of this comparative example, the film after dipping pass through length
The baking channel of 4m, for temperature setting at 175-195 DEG C, baking duration is set as 8min, removes solvent, obtains prepreg；
Gained is based on being in black inside the copper-clad plate of cyano resin, and surfacing, inside has the non-uniform stomata of size to lack
It falls into, it may be possible to the defect as caused by remaining solvent.Test result is as follows: glass transition temperature is 200 DEG C (DSC test),
248 DEG C (DMA test)；Thermal decomposition temperature is 410 DEG C (TGA test)；Bending strength 525MPa, bending modulus 21GPa；Dielectric is normal
Number is 4.7 (3GHz), and dielectric loss is 0.009 (3GHz)；
Although can satisfy the application requirement of high-frequency high-speed copper-clad plate cyano resin, comprehensive performance is lower than implementation case
Example.
Comparative example 5
This comparative example provides a kind of moulding process of high-frequency high-speed copper-clad plate cyano resin, specific steps and embodiment 4
Almost the same, the difference is that only: step (3) in the moulding process (two) of this comparative example, the film after dipping pass through length
The baking channel of 4m, for temperature setting at 175-195 DEG C, baking duration is set as 18min, removes solvent, obtains prepreg；
Gained the defects of bubble-free, but removes the composite plate after copper foil based on being in black inside the copper-clad plate of cyano resin
There is lines on material surface, it may be possible to since drying time is too long, prepreg be caused to cross gel, mobility is deteriorated.Test result is such as
Under: glass transition temperature is 195 DEG C (DSC test), 240 DEG C (DMA test)；Thermal decomposition temperature is 415 DEG C (TGA test)；
Bending strength 515MPa, bending modulus 20.5GPa；Dielectric constant is 4.8 (3GHz), and dielectric loss is 0.009 (3GHz)；
Although can satisfy the application requirement of high-frequency high-speed copper-clad plate cyano resin, comprehensive performance is lower than implementation case
Example.
1-6 and comparative example 1-5 can analyze and obtain through the foregoing embodiment: compared to comparative example 1-5, the embodiment of the present invention
The cyano resin copper-clad plate with most excellent properties can be made in the molding technique parameter selected in 1-7；That chooses in the present invention is anti-
Technique and parameter setting is answered to play an important role the effect of final cyano resin copper-clad plate.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so being described relatively simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of moulding process of high-frequency high-speed cyano resin copper-clad plate, which comprises the following steps:
(1) polymerization reaction promotor and solvent are added into cyano resin, constant temperature is stirred to react 0.5- under the conditions of 125-130 DEG C
3h obtains glue；
(2) it takes base fabric to be placed in glue groove and impregnates glue made from the step (1), base fabric after being impregnated；
(3) base fabric baking removes solvent after impregnating obtained in the step (2), obtains semi-solid preparation film；
(4) gelation time for measuring the prepreg that the step (3) obtains, covers copper, suppresses in the vacuum press after stacking
Molding；
(5) natural cooling is cooled to room temperature, and cyano resin copper-clad plate can be obtained.
2. a kind of moulding process of high-frequency high-speed cyano resin copper-clad plate according to claim 1, which is characterized in that described
Polymerization accelerant in step (1) includes the mixing of one or both of epoxy resin, cyanate ester resin, benzoxazine resin,
The dosage of polymerization accelerant is the 8-25% of cyano resin total amount.
3. a kind of moulding process of high-frequency high-speed cyano resin copper-clad plate according to claim 1, which is characterized in that described
Solvent in step (1) is the mixing of one or both of N,N-dimethylformamide, acetone.
4. a kind of moulding process of high-frequency high-speed cyano resin copper-clad plate according to claim 1, which is characterized in that described
When glue in step (2) impregnates, the mass fraction for controlling the glue content of dipping accounts for the 38- of base fabric gross mass after dipping
45%.
5. a kind of moulding process of high-frequency high-speed cyano resin copper-clad plate according to claim 1, which is characterized in that described
Baking temperature in step (3) is arranged at 175-195 DEG C, and baking duration is set as 8-15min.
6. a kind of moulding process of high-frequency high-speed cyano resin copper-clad plate according to claim 1, which is characterized in that described
Forming temperature is 180-200 DEG C, pressing pressure 15-20MPa, pressing forming time 100-200min in step (4).
7. a kind of moulding process of high-frequency high-speed cyano resin copper-clad plate according to claim 1, which is characterized in that described
Base fabric in step (2) is glass fabric or non-woven fabrics, and the copper foil in the step (4) is electrolytic copper foil or rolled copper foil.
8. a kind of moulding process of high-frequency high-speed cyano resin copper-clad plate according to claim 1, which is characterized in that described
Cyano resin in step (1) includes solute and solvent, and solute is aromatic dicarboxylic phenol, aromatic amine and paraformaldehyde, and solvent is
N,N-Dimethylformamide and toluene, and the molar ratio of the solute and the solvent is 1:(0.3-0.6), specific preparation side
Method the following steps are included:
(1) aromatic dicarboxylic phenol, aromatic amine and paraformaldehyde are dried to 2h in 80 DEG C of drying box；
(2) successively by aromatic dicarboxylic phenol, aromatic amine and paraformaldehyde are added to equipped with n,N-Dimethylformamide and toluene
In there-necked flask, after stirring 10min at room temperature with the revolving speed of 120 turns/min, it is warming up to 90-120 DEG C with the rate of 5 DEG C/min, with
The revolving speed constant temperature of 120 turns/min is stirred to react 3-8h；
(3) temperature is increased after reaction to 120-140 DEG C, is kept constant temperature stirring the reaction was continued 2-5h, is obtained sticky dark color
Fluid；
(4) the dark liquid cooled to room temperature in the step (3) can be used for the cyano resin of copper-clad plate manufacture to obtain the final product.
9. a kind of moulding process of high-frequency high-speed cyano resin copper-clad plate according to claim 7, which is characterized in that described
N (aromatic dicarboxylic phenol) in step (2): n (aromatic amine): (paraformaldehyde)=1:(2-3 :): (3.8-4.2), n (N, N- diformazan
Base formamide): n (toluene)=1:(0.4-0.7).
10. a kind of moulding process of high-frequency high-speed cyano resin copper-clad plate according to claim 7, which is characterized in that institute
It is one of bisphenol-A, bisphenol S, phenolphthalein, 2,6- bis- (4- hydroxyphenoxy) benzonitrile or a variety of mixed for stating aromatic dicarboxylic phenol
It closes, the aromatic amine is selected from 4- (3- amino-benzene oxygen) phthalonitrile, 4- (4- amino-benzene oxygen) phthalonitrile, 4- (3-
Amino-benzene oxygen) benzonitrile, 4- (4- amino-benzene oxygen) benzonitrile, 2,6- bis- (4- amino-benzene oxygen) benzonitrile, in aniline
Any two kinds or more of mixing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811363162.6A CN109517197B (en) | 2018-11-14 | 2018-11-14 | Forming process of high-frequency high-speed nitrile-based resin copper-clad plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811363162.6A CN109517197B (en) | 2018-11-14 | 2018-11-14 | Forming process of high-frequency high-speed nitrile-based resin copper-clad plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109517197A true CN109517197A (en) | 2019-03-26 |
| CN109517197B CN109517197B (en) | 2021-04-30 |
Family
ID=65778186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811363162.6A Active CN109517197B (en) | 2018-11-14 | 2018-11-14 | Forming process of high-frequency high-speed nitrile-based resin copper-clad plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109517197B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111761753A (en) * | 2020-07-08 | 2020-10-13 | 铜陵华科电子材料有限公司 | Prepreg coated glass cloth soaking device |
| CN113292455A (en) * | 2021-05-18 | 2021-08-24 | 电子科技大学 | Benzoxazine-nitrile-group-containing resin curing agent and preparation method and application thereof |
| WO2021201046A1 (en) * | 2020-03-31 | 2021-10-07 | 日鉄ケミカル＆マテリアル株式会社 | Polyhydric hydroxy resin, epoxy resin, method for producing same, epoxy resin composition using same and cured product |
| CN114506098A (en) * | 2022-02-24 | 2022-05-17 | 四川金象赛瑞化工股份有限公司 | Resin-based fiber reinforced composite material for copper-clad plate and preparation method thereof |
| CN116333491A (en) * | 2023-05-26 | 2023-06-27 | 汕头超声覆铜板科技有限公司 | Halogen-free resin composition suitable for high-speed communication and application thereof |
| CN118755127A (en) * | 2024-09-09 | 2024-10-11 | 汕头超声覆铜板科技有限公司 | A polyarylether nitrile-based film material for flexible copper-clad laminate and a preparation method thereof |
| CN118755127B (en) * | 2024-09-09 | 2025-02-07 | 汕头超声覆铜板科技有限公司 | A polyarylether nitrile-based film material for flexible copper-clad laminate and a preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700705A (en) * | 2009-06-08 | 2010-05-05 | 电子科技大学 | A kind of thermosetting resin glass fiber laminated composite material and preparation method thereof |
| CN103980704A (en) * | 2014-05-28 | 2014-08-13 | 苏州生益科技有限公司 | Halogen-free resin composition for high-frequency and high-speed substrate as well as prepreg and laminated plate |
-
2018
- 2018-11-14 CN CN201811363162.6A patent/CN109517197B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700705A (en) * | 2009-06-08 | 2010-05-05 | 电子科技大学 | A kind of thermosetting resin glass fiber laminated composite material and preparation method thereof |
| CN103980704A (en) * | 2014-05-28 | 2014-08-13 | 苏州生益科技有限公司 | Halogen-free resin composition for high-frequency and high-speed substrate as well as prepreg and laminated plate |
Non-Patent Citations (4)
| Title |
|---|
| MINGZHEN XU ET AL.: ""Copolymerizing Behavior and Processability of Benzoxazine/Epoxy Systems and Their Applications for Glass Fiber Composite Laminates"", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| MINGZHEN XU ET AL.: ""Design of low temperature self-cured phthalonitrile-based polymers for advanced glass fiber composite laminates"", 《JOURNAL OF MATERIALS SCIENCE》 * |
| MINGZHEN XU ET AL.: ""Understanding of the polymerization mechanism of the phthalonitrile-based resins containing benzoxazine and their thermal stability"", 《POLYMER》 * |
| 赵鑫 等: ""双邻苯二甲腈改性环氧及其玻纤复合材料制备"", 《热固性树脂》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021201046A1 (en) * | 2020-03-31 | 2021-10-07 | 日鉄ケミカル＆マテリアル株式会社 | Polyhydric hydroxy resin, epoxy resin, method for producing same, epoxy resin composition using same and cured product |
| CN111761753A (en) * | 2020-07-08 | 2020-10-13 | 铜陵华科电子材料有限公司 | Prepreg coated glass cloth soaking device |
| CN113292455A (en) * | 2021-05-18 | 2021-08-24 | 电子科技大学 | Benzoxazine-nitrile-group-containing resin curing agent and preparation method and application thereof |
| CN114506098A (en) * | 2022-02-24 | 2022-05-17 | 四川金象赛瑞化工股份有限公司 | Resin-based fiber reinforced composite material for copper-clad plate and preparation method thereof |
| CN114506098B (en) * | 2022-02-24 | 2023-07-21 | 四川金象赛瑞化工股份有限公司 | Resin-based fiber reinforced composite material for copper-clad plate and preparation method thereof |
| CN116333491A (en) * | 2023-05-26 | 2023-06-27 | 汕头超声覆铜板科技有限公司 | Halogen-free resin composition suitable for high-speed communication and application thereof |
| CN116333491B (en) * | 2023-05-26 | 2023-08-04 | 汕头超声覆铜板科技有限公司 | Halogen-free resin composition suitable for high-speed communication and application thereof |
| CN118755127A (en) * | 2024-09-09 | 2024-10-11 | 汕头超声覆铜板科技有限公司 | A polyarylether nitrile-based film material for flexible copper-clad laminate and a preparation method thereof |
| CN118755127B (en) * | 2024-09-09 | 2025-02-07 | 汕头超声覆铜板科技有限公司 | A polyarylether nitrile-based film material for flexible copper-clad laminate and a preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109517197B (en) | 2021-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109517197A (en) | A kind of moulding process of high-frequency high-speed cyano resin copper-clad plate | |
| CN101955666B (en) | Preparation method of glass fiber reinforced thermosetting resin-based composite material | |
| CN103897346B (en) | A kind of compositions of thermosetting resin | |
| CN108219371A (en) | Composition epoxy resin, prepreg, laminate and printed circuit board | |
| CN110724261B (en) | High-heat-resistance low-dielectric polyphenylene ether type bismaleimide resin, laminated board and preparation method thereof | |
| CN105542396A (en) | High-modulus epoxy resin composition, preparation method thereof, prepreg and laminated board manufactured from same and preparation method of prepreg and laminated board | |
| CN103012790B (en) | Bisphthalonitrile-aminophenoxyphthalonitrile copolymer, cured product, glass fiber composite material and preparation method thereof | |
| CN102850766A (en) | Halogen-free resin composition, prepreg and laminated board made from the same | |
| CN108559209A (en) | Resin combination, prepreg, laminate and metal-clad laminate | |
| CN103396666B (en) | A kind of compositions of thermosetting resin and the prepreg using it to make and veneer sheet | |
| CN104448820B (en) | Cyanate modified composition, cyanate prepreg, metamaterial substrate, its preparation method and the Meta Materials including it | |
| CN102286151B (en) | Thermosetting modified cyanate ester resin and preparation method thereof | |
| CN101570599B (en) | Cyanate/bisoxazoline co-cured resin and preparation method and application thereof | |
| CN115584025B (en) | Modified BT resin and preparation method thereof | |
| CN112979856B (en) | Random copolymer and preparation method thereof, modified PBO fiber and preparation method thereof, resin-based wave-transmitting composite material and preparation method thereof | |
| CN108219134B (en) | Prepolymer and resin composition of modified composite bismaleimide resin, and prepreg and laminated board manufactured by using prepolymer and resin composition | |
| CN116425937A (en) | Resin composition and application thereof | |
| CN109593070A (en) | Nitrile-based resin for high-frequency and high-speed copper-clad plate and preparation method thereof | |
| CN114805883A (en) | Bismaleimide modified basalt fiber cloth and poly (arylene ether nitrile) composite material and preparation method thereof | |
| CN108084930A (en) | A kind of LED display binding agent and preparation method thereof | |
| CN103172858B (en) | Preparation method of electronic material for transmitting high-frequency signals | |
| CN108102072B (en) | Castor oil modified benzoxazine resin and preparation method thereof | |
| JP4748695B2 (en) | Epoxy resin composition and cured product thereof | |
| CN113637133A (en) | Low-dielectric high-heat-resistance benzoxazine resin containing hydrocarbon chain segment and polyphenyl ether chain segment and preparation method thereof | |
| CN101367936A (en) | A kind of alkyl xylene type cyanate resin and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230116 Address after: No. 28, Guangshun Road, Haojiang District, Shantou City, Guangdong Province, 515000 Patentee after: Shantou Ultrasonic Copper Clad Plate Technology Co.,Ltd. Address before: 515000 lot E04, Shantou Free Trade Zone, Shantou City, Guangdong Province Patentee before: GUANGDONG SHANTOU ULTRASONIC ELECTRONIC CO.,LTD. COPPER CLAD FACTORY |