CN109370497B - Preparation method of glue for producing high-speed copper-clad plate and product thereof - Google Patents
Preparation method of glue for producing high-speed copper-clad plate and product thereof Download PDFInfo
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- CN109370497B CN109370497B CN201811259120.8A CN201811259120A CN109370497B CN 109370497 B CN109370497 B CN 109370497B CN 201811259120 A CN201811259120 A CN 201811259120A CN 109370497 B CN109370497 B CN 109370497B
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- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
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- 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
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- 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
- C09J11/08—Macromolecular additives
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- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
- H05K1/053—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an inorganic insulating layer
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/14—Glass
- C09J2400/143—Glass in the substrate
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Abstract
The invention relates to a preparation method of glue for producing a high-speed copper-clad plate, which is characterized in that barbituric acid, brominated bisphenol A epoxy resin and bismaleimide resin are subjected to blending modification to prepare modified bismaleimide resin; butyrolactone is used as a solvent of the mixture, so that the modified bismaleimide resin forms a stable and uniform mixture; further adding other materials to prepare special glue for producing the high-speed copper-clad plate; the high-speed copper-clad plate produced by the glue prepared by the invention has low dielectric constant and dielectric loss factor, can meet other performance requirements of the copper-clad plate, and can be suitable for manufacturing high-speed printed wiring boards.
Description
Technical Field
The invention relates to the field of production and preparation of copper-clad plates, in particular to a preparation method of glue for producing a high-speed copper-clad plate and a product thereof.
Background
With the rapid advancement of intelligent electronic products and the revolution of information technology, global information technology is rapidly developing towards digitization and networking, and ultra-large capacity information transmission, ultra-fast speed and ultra-high density information processing become the pursuit targets of information and communication equipment (ICT) technology development. Digital circuits are gradually moving into the stages of high speed information processing and high frequency signal transmission, and the frequency of electronic devices is becoming higher and higher to process increasing data, and at this time, the performance of the substrate will seriously affect the characteristics of the digital circuits. With the progress of high density of Printed Circuit Board (PCB) wiring and high speed of electrical signal transmission, higher demands are made on the performance of a Printed Circuit Board (PCB) substrate. The basic properties of high-speed substrate materials must meet two requirements, namely, the dielectric constant (Dk) must be small and stable, usually the smaller the dielectric constant is, the better the signal transmission rate is, the inverse proportion of the square root of the dielectric constant of the material, and the high dielectric constant is liable to cause signal transmission delay. Secondly, the dielectric loss (Df) must be small, which mainly affects the quality of signal transmission, and the smaller the dielectric loss, the smaller the signal loss.
The high-frequency high-speed substrate material mainly solves the defects of unstable transmission performance and large loss of high-frequency characteristics of common copper-clad plates in the fields of microwave, millimeter wave and the like in communication, and is a mainstream technology developed in the industry at present, so that higher and more urgent requirements on the low dielectric performance and the like of resin are provided. In order to meet the development requirements of the two high-speed copper-clad plates, the development of the copper-clad plates used for the high-speed PCB needs to apply a novel and high-performance resin material as a support, and the development of the application technology of the novel resin material is used as a key and core technology of the development problem of the copper-clad plates and a powerful weapon for developing an intellectual property strategy.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing a glue for producing a high-speed copper-clad plate and a product obtained thereby.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a preparation method of glue for producing a high-speed copper-clad plate comprises the following steps:
1) modification of bismaleimide resin: putting barbituric acid, brominated bisphenol A epoxy resin, bismaleimide resin and butyrolactone into a reactor, and reacting after uniformly mixing; adding dimethylformamide and curing agent ethylenediamine, and uniformly mixing to obtain a resin A solution;
2) dissolving polyphenyl ether resin in toluene, adding dicyclopentadiene phenol epoxy resin and benzoyl peroxide, uniformly mixing, reacting for 2-3 hours at 85-95 ℃, and obtaining a resin B solution after the reaction is finished;
3) mixing the resin A solution and the resin B solution together, and adding a catalyst to prepare the glue for producing the high-speed copper-clad plate.
Further, the reaction condition in the step 1) is 130-150 ℃, the reaction is carried out for 2-4 hours, and the temperature is reduced to 60-70 ℃ after the reaction is stopped.
Further, by mass, 0.05-0.07 part of barbituric acid, 4-12 parts of brominated bisphenol A epoxy resin, 1 part of bismaleimide resin, 0.9-2.4 parts of curing agent ethylenediamine, 4-11 parts of polyphenyl ether resin, 0-0.6 part of dicyclopentadiene phenol epoxy resin, 0.2-0.6 part of benzoyl peroxide and 0.06-0.08 part of catalyst.
Furthermore, butyrolactone, dimethylformamide and toluene are all solvents, and the addition amount is 5-7 times of the mass of the corresponding resin.
Further, the catalyst is dimethyl imidazole.
Further, the bromine content in the brominated bisphenol A epoxy resin is 18-25%.
Provides a glue obtained by any preparation method.
The invention also aims to provide a high-speed copper-clad plate with low dielectric constant and dielectric loss factor, which is prepared from the glue, and the preparation method comprises the following steps:
a. pretreating the glass fiber cloth serving as a reinforcing material;
b. coating the glue on the pretreated glass fiber cloth, and preparing a high-speed copper-clad plate bonding sheet after drying and exhausting;
c. and (3) stacking the bonding sheets, covering copper foils on the bonding sheets, and pressing the bonding sheets for 5 hours at the temperature of 180 ℃ and 220 ℃ under the pressure of 3-4Mpa to prepare the high-speed copper-clad plate.
Further, the pretreatment method comprises the following steps: burning the glass fiber cloth at 30-50 deg.C for 20-50min, and naturally cooling to room temperature; soaking in the treating solution for 10-15min, taking out, air drying for 30-45min, and oven drying at 90-120 deg.C for 1.5-2.5 h; the treating fluid is 1.5% w/v silane coupling agent water solution, and the pH value is adjusted to 3-4 by glacial acetic acid.
The invention has the beneficial effects that: the invention provides a preparation method of glue for producing a high-speed copper-clad plate, which is characterized in that barbituric acid, brominated bisphenol A epoxy resin and bismaleimide resin are subjected to blending modification to prepare modified bismaleimide resin; the brominated bisphenol A type epoxy resin exists in the form of a flame retardant, and is also used as a co-modified resin with bismaleimide resin; butyrolactone is used as a solvent of the mixture, so that the modified bismaleimide resin forms a stable and uniform mixture; further adding other materials to prepare special glue for producing the high-speed copper-clad plate; the dicyclopentadiene phenol epoxy resin and the polyphenyl ether are mixed together, the molecular weight of the dicyclopentadiene phenol epoxy resin can be reduced, and a relatively high crosslinking density can be obtained. And finally, reacting the mixed solution with bismaleimide to obtain a semi-interpenetrating polymer network structure. The high-speed copper-clad plate produced by the glue prepared by the invention has low dielectric constant and dielectric loss factor, can meet other performance requirements of the high-speed copper-clad plate, and can be suitable for manufacturing high-speed printed wiring boards.
Detailed Description
The following describes in detail preferred embodiments of the present invention. The experimental procedures, in which specific conditions are not specified in the examples, are generally carried out under conventional conditions or under conditions recommended by the manufacturers.
Example 1
Special glue for high-speed copper-clad plate:
1. modification of bismaleimide resin: putting 0.65g of barbituric acid, 123.5g of brominated bisphenol A epoxy resin, 11.2g of bismaleimide resin and 77g of butyrolactone into a reactor to form a stable and uniform mixture, then reacting for 2-3 hours at 135 ℃, and cooling to 65 ℃ after the reaction is stopped; wherein, butyrolactone is only used as a solvent and is added together with the bismaleimide resin and the barbituric acid, and only the bismaleimide resin and the barbituric acid are reacted. The reaction is carried out at the temperature of 130-150 ℃ for 2-4 hours, and the temperature is reduced to 60-70 ℃ after the reaction is stopped. The bromine element in the brominated bisphenol A type epoxy resin accounts for 18 to 25 percent.
2. Then 75g of dimethylformamide and 24.93g of curing agent ethylenediamine are added and mixed together to form a uniform resin A solution;
3. dissolving 122g of polyphenylene ether resin in toluene (heating), adding 6.05g of benzoyl peroxide to form a stable mixture, reacting at 85-95 ℃ for 2-3 hours to form a stable resin B solution after the reaction is finished;
4. and uniformly mixing the resin A solution and the resin B solution together, and adding 0.67g of catalyst dimethylimidazole (2-MI) to prepare the special glue for producing the high-speed copper-clad plate.
In the above steps, toluene, butyrolactone and Dimethylformamide (DMF) are all solvents, do not participate in the reaction, and are used for dissolving the resin and the filler, and the adding amount is 5-7 times of the mass of the corresponding resin, which is the same as the following steps.
Example 2
Preparing a high-speed copper-clad plate:
1. pretreatment of the reinforcing material: selecting low-dielectric-constant glass fiber cloth as a reinforcing material, burning the glass fiber cloth at 40 ℃ for 30min, and naturally cooling the glass fiber cloth to room temperature; soaking the low-dielectric-constant glass fiber cloth subjected to heating treatment in the treatment solution for 10-15min, naturally air-drying for 30-45min, and then placing the low-dielectric-constant glass fiber cloth in an electric heating blast box at 100 ℃ to dry for 2H; the glass cloth treating solution is a 1.5% aqueous solution prepared from silane coupling agent, the pH value is adjusted to 3-4 by glacial acetic acid, and the reaction is carried out for 45min under stirring at normal temperature. The dielectric constant of the glass fiber cloth used in the examples is between 4.2 and 4.5.
2. Preparation of adhesive sheets (in semi-cured state): coating the special glue for the high-speed copper-clad plate prepared in the embodiment 1 on the treated low-dielectric-constant glass fiber cloth through a pipeline of a soaking machine, and preparing a special bonding sheet (in a semi-cured state) for the high-speed copper-clad plate through unit operations such as drying, exhausting and the like;
3. hot-press molding: the adhesive sheets were stacked, covered with copper foil, and pressed at 200 ℃ under 3.2MPa for 5 hours.
The dielectric constant DK is the ratio of the capacitance when a substance is charged between the electrodes to the capacitance of a vacuum capacitor of the same construction, and generally indicates the magnitude of the capacity of a material to store electrical energy. The direction of the current passing through the electric signal on the printed board is usually changed alternately in positive and negative directions, which is equivalent to the process of continuously charging and discharging the substrate. In the interchange, the capacitance affects the signal transmission speed. This effect is more pronounced in high-speed conveyor systems. When DK is large, it means that the capacity of storing electric energy is large, and the transmission speed of electric signals in the circuit becomes slow. When DK is small, it shows that the capacity of storing electric energy is small, and the charging and discharging process is quick, so that the transmission speed is accelerated. Therefore, in high frequency transmission, the dielectric constant DK is required to be low, and the dielectric constant DK of the low dielectric glass fiber cloth is 4.4, which is lower than that of the conventional E-type glass fiber cloth and 6.6.
Dielectric loss factor Df, also called dielectric loss tangent, in an alternating electric field, an insulating material or a dielectric medium generates a certain phase difference between a current vector and a voltage vector flowing in the dielectric medium due to the hysteresis effect of dielectric conductance and dielectric polarization, namely, a certain phase angle is formed, the tangent value of the phase angle is the dielectric loss factor Df, and the energy loss caused by the hysteresis effect of the dielectric conductance and the dielectric polarization is called as dielectric loss. The higher the Df is, the more obvious the dielectric conductance and dielectric polarization hysteresis effect is, the more the electric energy loss or signal loss is, the capability of dielectric to lose electric energy is, and the characterization physical quantity of the capability of insulating materials to lose signals is also.
Example 3
1. Modification of bismaleimide resin: putting 1.68g of barbituric acid, 116.3g of brominated bisphenol A epoxy resin, 25g of bismaleimide resin and 160g of butyrolactone into a reactor to form a stable and uniform mixture, then reacting for 2-3 hours at 135 ℃, and cooling to 65 ℃ after the reaction is stopped;
2. then adding 23.12g of dimethylformamide and curing agent ethylenediamine according to the mass ratio of 1:5-7 of the resin, and mixing the materials together to form a uniform resin A solution;
3. dissolving 115.5g of polyphenylene ether resin in toluene (heating), adding 6.05g of dicyclopentadiene phenol epoxy resin and 5.75g of benzoyl peroxide to form a stable mixture, reacting for 2-3 hours at the temperature of 85-95 ℃, and forming a stable resin B solution after the reaction is finished;
4. and uniformly mixing the resin A solution and the resin B solution together, and adding 0.67g of catalyst dimethylimidazole to prepare the special glue for producing the high-speed copper-clad plate.
5. Preparing a high-speed copper-clad plate: the preparation method is the same as example 2.
Example 4
Special glue for high-speed copper-clad plate:
1. modification of bismaleimide resin: putting 0.65g of barbituric acid, 123.5g of brominated bisphenol A epoxy resin, 11.2g of bismaleimide resin and butyrolactone into a reactor to form a stable and uniform mixture, then reacting for 2-3 hours at 135 ℃, and cooling to 65 ℃ after the reaction is stopped;
2. then adding proper amount of dimethylformamide and 24.93g of curing agent ethylenediamine according to a certain proportion, and mixing together to form a uniform resin A solution;
3. dissolving 122g of polyphenylene oxide resin in toluene (heating), then adding 6.05g of dicyclopentadiene phenol epoxy resin and 6.05g of benzoyl peroxide to form a stable mixture, reacting for 2-3 hours at 85-95 ℃, and forming a stable resin B solution after the reaction is finished;
4. and uniformly mixing the resin A solution and the resin B solution together, and adding 0.77g of dimethyl imidazole serving as a catalyst to prepare the special glue for producing the high-speed copper-clad plate.
5. Preparing a high-speed copper-clad plate: the preparation method is the same as example 2.
Example 5
Physical property tests are respectively carried out on the high-speed copper-clad plates prepared in the embodiment 2, the embodiment 3 and the embodiment 4, and the results of the physical property tests are shown in the table 1;
table 1 physical property test results of each high-speed copper-clad plate
| Physical Properties | Example 2 | Example 3 | Example 4 |
| Glass transition temperature | 182 | 190 | 186 |
| Solder resistance | Good effect | Good effect | Good effect |
| Z-axis coefficient of thermal expansion, ppm/. degree.C | 3.4 | 3.5 | 3.3 |
| Dielectric constant (1MHZ) | 3.75 | 3.51 | 3.20 |
| Dielectric loss factor (1MHZ) | 0.0045 | 0.0046 | 0.0040 |
In examples 2 and 3, 3% and 7% of the solid content of the modified bismaleimide (calculated according to the solid content of the resin) was added, and the glass transition temperature was 182 ℃ and 190 ℃, respectively, whereby it is apparent that the Tg value of the substrate was increased by using the modified bismaleimide modified with barbituric acid: and the dimensional stability, electrical properties and heat resistance of the sample are relatively improved. In example 4, dicyclopentadiene phenol epoxy resin was used to significantly improve the electrical properties of the samples, which had a dielectric constant of 3.20 and a loss tangent of 0.0040, which were the lowest values of the experiment, and satisfied the product performance requirements.
Comparative example
According to the preparation method and the steps of the embodiment 3, wherein the addition amount of substances is shown in the table 2, the copper-clad plates of the comparative examples 1 to 3 are respectively prepared, and the physical property test is carried out under the same conditions of the same embodiment, and the physical property test results are shown in the table 3;
TABLE 2 addition of various comparative components
TABLE 3 results of various comparative physical property tests
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (7)
1. The preparation method of the glue for producing the high-speed copper-clad plate is characterized by comprising the following steps:
1) modification of bismaleimide resin: putting barbituric acid, brominated bisphenol A epoxy resin, bismaleimide resin and butyrolactone into a reactor, and reacting after uniformly mixing; adding dimethylformamide and curing agent ethylenediamine, and uniformly mixing to obtain a resin A solution; the reaction condition is 130-150 ℃, the reaction is carried out for 2-4 hours, and the temperature is reduced to 60-70 ℃ after the reaction is stopped;
2) dissolving polyphenyl ether resin in toluene, adding dicyclopentadiene phenol epoxy resin and benzoyl peroxide, uniformly mixing, reacting for 2-3 hours at 85-95 ℃, and obtaining a resin B solution after the reaction is finished;
3) mixing the resin A solution and the resin B solution together, and adding a catalyst to prepare glue for producing the high-speed copper-clad plate;
wherein, the composition comprises, by mass, 0.05-0.07 part of barbituric acid, 4-12 parts of brominated bisphenol A epoxy resin, 1 part of bismaleimide resin, 0.9-2.4 parts of curing agent ethylenediamine, 4-11 parts of polyphenyl ether resin, 0-0.6 part of dicyclopentadiene phenol epoxy resin, 0.2-0.6 part of benzoyl peroxide and 0.06-0.08 part of catalyst.
2. The method according to claim 1, wherein butyrolactone, dimethylformamide and toluene are all solvents and are added in an amount of 5 to 7 times the mass of the corresponding resin.
3. The method of claim 1, wherein the catalyst is dimethylimidazole.
4. The method according to claim 1, wherein the brominated bisphenol A epoxy resin contains 18 to 25% of bromine.
5. Glue obtainable by the process according to any one of claims 1 to 4.
6. The high-speed copper-clad plate prepared by the glue according to claim 5 is characterized in that the preparation method comprises the following steps:
a. pretreating the glass fiber cloth serving as a reinforcing material;
b. coating the glue on the pretreated glass fiber cloth, and preparing a high-speed copper-clad plate bonding sheet after drying and exhausting;
c. and (3) stacking the bonding sheets, covering copper foils on the bonding sheets, and pressing the bonding sheets for 5 hours at the temperature of 180 ℃ and 220 ℃ under the pressure of 3-4MPa to prepare the high-speed copper-clad plate.
7. The glue for preparing the high-speed copper-clad plate according to claim 6, wherein the pretreatment method comprises the following steps: burning the glass fiber cloth at 30-50 deg.C for 20-50min, and naturally cooling to room temperature; soaking in the treating solution for 10-15min, taking out, air drying for 30-45min, and oven drying at 90-120 deg.C for 1.5-2.5 h; the treating fluid is 1.5% w/v silane coupling agent water solution, and the pH value is adjusted to 3-4 by glacial acetic acid.
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| CN110317541B (en) * | 2019-06-19 | 2021-07-13 | 南亚新材料科技股份有限公司 | Bonding sheet and preparation method of high-speed copper-clad plate |
| CN113502141A (en) * | 2021-07-19 | 2021-10-15 | 安徽鸿海新材料股份有限公司 | Copper-clad plate glue synthesis preparation method |
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| CN1493610A (en) * | 2003-08-19 | 2004-05-05 | 梁国正 | Modified dimaleimide resin and its preparation method and application in cladding copper plate |
| CN101659721A (en) * | 2008-08-26 | 2010-03-03 | 财团法人工业技术研究院 | Method and formula for forming hyper branched polymer |
| CN103937156A (en) * | 2014-03-05 | 2014-07-23 | 浙江华正新材料股份有限公司 | Thermosetting resin composition and method for manufacturing prepreg and laminated board by using thermosetting resin composition |
| CN105461927A (en) * | 2015-11-27 | 2016-04-06 | 国联汽车动力电池研究院有限责任公司 | Bismaleimide polymer allowing long-term storage and preparation method thereof |
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| CN105172270A (en) * | 2014-05-27 | 2015-12-23 | 广东生益科技股份有限公司 | Thermosetting resin sandwich preimpregnation body and preparation method thereof, and copper-clad plate |
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| CN1493610A (en) * | 2003-08-19 | 2004-05-05 | 梁国正 | Modified dimaleimide resin and its preparation method and application in cladding copper plate |
| CN101659721A (en) * | 2008-08-26 | 2010-03-03 | 财团法人工业技术研究院 | Method and formula for forming hyper branched polymer |
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| CN105461927A (en) * | 2015-11-27 | 2016-04-06 | 国联汽车动力电池研究院有限责任公司 | Bismaleimide polymer allowing long-term storage and preparation method thereof |
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