CN111471278A - Low-temperature high-radiant-heat epoxy resin composition and application thereof - Google Patents
Low-temperature high-radiant-heat epoxy resin composition and application thereof Download PDFInfo
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- CN111471278A CN111471278A CN202010396009.4A CN202010396009A CN111471278A CN 111471278 A CN111471278 A CN 111471278A CN 202010396009 A CN202010396009 A CN 202010396009A CN 111471278 A CN111471278 A CN 111471278A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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Abstract
The invention relates to a low-temperature high-radiant-heat epoxy resin composition and application thereof. The composition comprises an inorganic filling material, an epoxy resin, a hardening agent, a hardening accelerator, a coupling agent, an ion trapping agent, a release agent, a flame retardant, a stress modifier and a coloring agent. The inorganic filling material at least comprises boron nitride and carbon nano tube composite modified and coated modified silicon dioxide. The epoxy resin composition has excellent radiation heat dissipation capacity in a low-temperature environment, good thermal conductivity and stable electrical performance, and is suitable for packaging discrete devices and integrated circuits which are required by the development of miniaturization and high integration as a packaging material.
Description
Technical Field
The invention relates to an epoxy resin composition, in particular to a low-temperature high-radiation-heat epoxy resin composition and application thereof.
Background
With the development of electronic and electrical technologies, some large-scale electronic devices, communication devices, lighting fixtures, etc. are developing in smaller and smaller directions. The integration degree of the circuit in unit area is higher and higher, the heat generated during the circuit operation is larger, and the working efficiency of the equipment is low due to equipment failure, degradation and aging of high polymer materials and the like during the operation at higher temperature. Therefore, higher requirements are put on the heat conduction and dissipation capacity of the material, and if the extra heat generated in the operation process is not dissipated in time, serious potential damage can be caused to the use stability of the composite material.
In recent years, polymer composite materials using epoxy resin as matrix resin have been widely used in the packaging of the microelectronic industry due to their advantages of low cost, simple production process, suitability for automated production, excellent mechanical and electrical properties, etc., and have become the main packaging materials for consumer electronics packaging. With the development of electronic product equipment towards miniaturization, large-scale integration, high efficiency and high reliability, the heat productivity of chips becomes larger, and higher requirements are put forward on packaging materials and technologies. In general, silica having good insulating properties and thermal shock resistance is generally selected as the filler for the epoxy resin composition. However, the thermal conductivity of epoxy resin compositions filled with common silica is increasingly unable to meet the heat dissipation requirements of modern microelectronic circuits, especially for high-density and ultra-high-density packaging, the power consumption is large, and the heat generation is gradually increased, so that the epoxy resin composition is required to increase the filling content of the filler, but the increase of the filling content can cause pressure on the production processing dispersibility and the packaging operability. Therefore, the modified filling material with higher thermal conductivity and radiation emissivity is used as the filling material of the epoxy resin composition, so that the thermal conductivity of the material can be effectively improved, the radiation heat dissipation capability at low temperature can be enhanced, and the application of light and thin electronic packaging is facilitated.
Disclosure of Invention
The invention provides a low-temperature high-radiation-heat epoxy resin composition and application thereof, which show good low-temperature radiation heat dissipation and heat conduction capabilities.
The low temperature high radiation heat epoxy resin composition is prepared with inorganic stuffing, epoxy resin, hardening agent and hardening promoter.
The mass fraction of the inorganic filling material is 70-95%, preferably 75-89%. The inorganic filling material at least comprises modified silicon dioxide and can also comprise other inorganic filling materials. The modified silicon dioxide is obtained by compounding boron nitride and carbon nano tubes to modify and coat silicon dioxide, the type of the silicon dioxide is not limited, and spherical silicon dioxide is preferred; the other inorganic filling material comprises any one or more of oxide, nitride and carbide. Commonly spherical silica, angle silica, rounded silica, alumina, magnesia, zinc oxide, beryllium oxide, boron nitride, aluminum nitride, silicon carbide, boron carbide, carbon nanotubes.
The modified silicon dioxide in the inorganic filling material has the mass fraction of boron nitride and carbon nano tubes not more than 60 percent. When the mass fraction of the boron nitride and carbon nanotube composite modified silicon dioxide reaches a high degree, other characteristics of the epoxy resin composition are negatively affected.
The modified material used by the modified silicon dioxide is an intercalation structure compound formed by arranging boron nitride and carbon nano tubes. The boron nitride layer contains carbon nano tubes, and the high radiation emissivity of the carbon nano tubes and the high heat conductivity of the boron nitride are fully combined. The boron nitride and the carbon nano tube are not limited by type, crystal form and size.
The mass fraction of the epoxy resin is 2-15%, preferably 6-12%.
The mass fraction of the hardening agent is 2-10%, preferably 3-8%.
The mass fraction of the hardening accelerator is 0.01-1%.
The epoxy resin composition with low temperature and high radiant heat can also comprise one or more of a coupling agent, an ion trapping agent, a release agent, a flame retardant, a stress modifier and a coloring agent besides an inorganic filling material, an epoxy resin, a hardening agent and a hardening accelerator.
The low-temperature high-radiation-heat epoxy resin composition can be used as an encapsulating material and is suitable for encapsulating discrete devices and integrated circuits which are required by the development of volume miniaturization and high integration.
The invention has the advantages that: the invention relates to a low-temperature high-radiant-heat epoxy resin composition, wherein an adopted inorganic filler contains a modified material which is obtained by coating a silicon dioxide surface with boron nitride and carbon nano tubes after pre-intercalation compounding. The crystal structure of the boron nitride is a reticular lamellar layer consisting of boron and nitrogen, and the boron nitride has the characteristics of excellent high-temperature stability, low thermal expansion coefficient, low friction coefficient and the like. The carbon nano tube is a polyhedral carbon cluster with the characteristic of a closed multilayer graphite structure, and has good mechanical property, thermal conductivity and chemical stability. The boron nitride provides a good heat conduction path, and the carbon nano tube effectively enhances the radiation heat dissipation. The silicon dioxide coated by the composite modified silicon dioxide can effectively increase the heat conduction capability and improve the heat radiation emission and heat transfer capability in a low-temperature environment. The epoxy resin composition can effectively form a heat conduction path, simultaneously strengthens the radiation heat exchange between a heat source and a heated body, has obvious cooling effect and good stability in long-term use, obviously improves the problem of temperature rise and heat dissipation, effectively improves the heat dissipation capability of a packaged product, and reduces the defects caused by high temperature and high heat generated by the operation of the packaged product.
Drawings
Fig. 1(a) to 1(b) show SEM images (magnification: fig. 1(a)7K times, fig. 1(b)15K times) of a modified silica according to one embodiment of the present invention.
Fig. 1(c) shows an SEM image of ordinary silica.
Detailed Description
In order to enhance the understanding of the present invention, the present invention will be described in further detail with reference to the following examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the present invention. In the following embodiments, the constituent elements are not essential, and the numerical values and ranges thereof are not intended to limit the present invention.
The embodiment provides a low-temperature high-radiation-heat epoxy resin composition which is prepared from 70-95% of an inorganic filling material, 2-15% of epoxy resin, 2-10% of a hardening agent, 0.01-1% of a hardening accelerator, 0.1-0.8% of a coupling agent, 0.1-0.5% of an ion capture agent, 0.1-1% of a release agent, 0.1-1% of a flame retardant, 0.1-1% of a stress modifier and 0.01-1% of a coloring agent in percentage by mass; wherein the inorganic filling material at least comprises boron nitride and carbon nano tube composite modified and coated modified silicon dioxide.
The epoxy resin composition with low temperature and high radiant heat of the embodiment is prepared by the following steps: weighing the components, uniformly mixing the coupling agent and the inorganic filling material, uniformly mixing the mixture with the epoxy resin, the hardening agent, the hardening accelerator, the ion trapping agent, the release agent, the stress modifier and the coloring agent, mixing the mixture for 2 to 10 minutes at 90 to 115 ℃ by a rubber mixing mill, pulling a piece, cooling, crushing and cake forming after uniform mixing.
The inorganic filling material used in the invention must contain boron nitride and carbon nano tube composite modified and coated modified silicon dioxide, wherein the mass fraction of the boron nitride and the carbon nano tube is not more than 60%. The modified material is an intercalation structure compound formed by arranging boron nitride and carbon nano tubes. The modification synthesis method can be common methods such as a solution method, a coating method, a sol-gel method, an intercalation method, a dispersion polymerization method, an emulsion polymerization method or a low-temperature plasma polymerization method. The boron nitride and the carbon nano tube used for modification are not limited by the characteristics of the shape, the size, the crystal form and the like. From the attached drawings, comparing fig. 1(a) with fig. 1(c), the modified silica surface has a layer of hairy coating, and the intercalation structure compound of boron nitride and carbon nano tube is successfully grafted.
Other inorganic filler materials that can be used in the present invention are mixtures of one or more of oxides, nitrides, carbides, obtained in any ratio, such as (but not limited to) silica, alumina, magnesia, zinc oxide, silicon nitride, boron nitride, aluminum nitride, and silicon carbide, and all of them should be electronic grade raw materials, with high purity and low ion content.
From the viewpoints of hygroscopicity, reduction of linear expansion coefficient, strength improvement and easiness in processing, the inorganic filler filling content is preferably 75-89%, so that good die flow property, dispersibility and processability can be ensured, and good heat conduction and heat dissipation capability can be obtained.
The epoxy resin which can be used in the composition of the present invention is well known to those skilled in the art, and its kind is not particularly limited as long as it has an epoxy group in the molecule. Including, but not limited to, bisphenol a type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, dicyclopentadiene epoxy resins, biphenyl type epoxy resins, naphthol type epoxy resins, triazine core structure-containing epoxy resins, trisphenol methane type epoxy resins, stilbene type epoxy resins, cyclopentadiene-modified epoxy resins, linear aliphatic epoxy resins, aralkyl type epoxy resins, phenol aldehyde-modified epoxy resins, silicon-containing epoxy resins, or mixtures of any of a plurality thereof.
Epoxy resin is subjected to ring opening reaction of epoxy groups under the action of a hardening accelerator at high temperature and is subjected to crosslinking reaction of phenolic hydroxyl groups in a hardening agent to form a network structure, and in the high-temperature reaction process, the surface wetting and dispersion of the inorganic filling material are increased. The epoxy equivalent (molecular weight/number of epoxy groups) of the epoxy resin used in the present invention is not particularly limited. From the viewpoint of balance among various properties such as reactivity, electric properties, moisture resistance, moldability and reflow resistance, it is preferably 100g/eq to 500 g/eq. The epoxy resin is generally used in an amount of between 2 and 15% by weight, preferably between 6 and 12% by weight, relative to the total weight of the composition.
The curing agent usable in the present invention is used in combination with an epoxy resin, and is well known to those skilled in the art, and examples thereof include a phenol curing agent, an amine curing agent, an acid anhydride curing agent, a polythiol curing agent, a polyaminoamide curing agent, an isocyanate curing agent, a blocked isocyanate curing agent, and the like. The curing agent is preferably a phenol curing agent from the viewpoint of improving heat resistance and reactivity. Phenolic curing agents, i.e., phenolic resins containing two or more hydroxyl functional groups; it includes, but is not limited to, a novolac resin, a cresol novolac resin, a multifunctional trisphenol methane type phenol resin, a naphthalene type phenol resin, a cyclopentadiene type phenol resin, a biphenyl type phenol resin, a polycyclic aromatic ring modified phenol resin, an indene compound or a mixture thereof, preferably a cresol novolac resin, a naphthalene type phenol resin, a biphenyl type phenol resin or a mixture thereof.
According to the invention, the hardener is used in an amount of between 2 and 10% by weight, preferably between 3 and 8% by weight, relative to the total weight of the composition.
The hardening accelerator can be used for accelerating the crosslinking reaction between the epoxy group of the epoxy resin and the phenolic hydroxyl group in the hardening agent. Hardening accelerators that may be used in the present invention include, but are not limited to, phosphorus-based compounds, nitrogen-containing heterocyclic compounds, imidazole compounds. According to the invention, the hardening accelerator is used in an amount of 0.01 to 1% by weight, preferably 0.1 to 0.3% by weight, based on the total weight of the composition. Mention may be made of: 1, 8-diazabicyclo [5,4,0] undec-7-ene, 1, 5-diaza-bicyclo (4,3,0) nonene, 5, 6-dibutylamino-1, 8-diaza-bicyclo (5,4,0) undec-7-ene, triphenylphosphine, tributylphosphine, diphenylphosphine, triphenylphosphine borate, triphenylphosphine triphenylborane, tetraphenylphosphonium tetraphenylborate, triphenylphosphine-1, 4-benzoquinone adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, 1-cyanoethyl-4-methylimidazole. These curing accelerators may be used alone or in combination of two or more.
In addition, various additives well known to those skilled in the art, such as coupling agents, ion trapping agents, mold release agents, flame retardants, stress modifiers, and colorants, may optionally be included in the present invention.
The coupling agent can enhance the wettability between the inorganic filler and the organic resin and effectively improve the dispersion. The coupling agent may comprise epoxy silanes, amino silanes, ureido silanes, mercapto silanes, alkyl silanes, and titanates. These coupling agents may be used alone or in combination thereof.
The ion trapping agent can effectively inhibit the migration of the impurity ions and reduce the risk of electrical failure. The ion scavenger may be selected from one or more of the following: hydrotalcite, hydroxides or oxides of magnesium, aluminum, antimony, bismuth and zirconium, preferably hydrotalcite, magnesium aluminum carbonate hydroxide or combinations thereof.
The release agent is beneficial to being separated from the die and is an additive for enhancing internal and external lubrication. The release agent should have good heat resistance and not be easily decomposed, and the release agent includes, but is not limited to, silicon series, wax series, surfactant series, polyether series. The wax family is preferred and can be either natural or synthetic. Such as carnauba wax, montan wax, metal salts of higher fatty acids, paraffin waxes, oxidized polyethylene, fatty acid ester waxes, fatty acid waxes, polypropylene waxes, montanic acid waxes, amide waxes, and combinations thereof.
Flame retardants are functional aids that can impart flame retardancy to the composite material, including reactive flame retardants and additive flame retardants, suitable flame retardants for the epoxy resin compositions of the present invention include, but are not limited to, brominated epoxy resins, zinc oxide, zinc borate, magnesium hydroxide, antimony oxide, and phosphine-containing compounds or combinations thereof.
The epoxy resin composition may further comprise a stress moderator. By including the stress modifier, the warp deformation of the package and the generation of cracks in the package can be further reduced. Examples thereof include silicone oil, silicone rubber particles, synthetic rubber, and core-shell structured rubber particles.
Colorants can impart color to the epoxy resin composition, and colorants useful in the present invention include primarily inorganic and organic pigments. Including but not limited to carbon black, titanium dioxide, and the like.
The additive component is not particularly limited as long as the effect of the present invention is exerted. In addition to the above additive components, it is within the scope of the present invention that other additives, such as antioxidants, are not added, such as those that do not significantly improve the heat transfer and heat dissipation properties.
The epoxy resin composition with low temperature and high radiant heat has excellent radiation heat dissipation and heat conduction capability, excellent flow forming property and curing property, good moisture resistance and good operability. When the epoxy molding compound is used at an application end of the epoxy molding compound, the heat conduction and radiation heat dissipation capability under a low-temperature environment can be obviously improved, and the heat accumulation generated by the operation of an integrated circuit is effectively improved. The packaging method has excellent improvement effect on packaging forms with higher heat dissipation requirements.
Next, the present invention will be described in more detail with reference to examples. It should be noted, however, that these examples are provided for illustration only and should not be construed as limiting the invention in any way.
Examples 1 to 14 and comparative example
Preparation examples 1-14 and comparative examples, the compositions of which are listed in Table 1.
TABLE 1 examples 1-14 and comparative examples
The composition data in table 1 are as follows:
epoxy resin A: HP-7200, melting Point: 60 ℃, epoxy equivalent: 258 g/eq.
The epoxy resin B is YS L V-80XY, the melting point is 70 ℃, and the epoxy equivalent is 191 g/eq.
Phenol resin: SH-4064, softening point: 70 ℃, OH equivalent: 167 g/eq.
Silicon dioxide: DQ 1150.
Modified silica A: the mass fraction ratio of each component of SiO2@ (BN + CNT) is 99:0.99: 0.01.
Modified silica B: the mass fraction ratio of each component of SiO2@ (BN + CNT) is 99:0.95: 0.05.
Modified silica C: the mass fraction ratio of each component of SiO2@ (BN + CNT) is 99:0.9: 0.1.
Modified silica D: the mass fraction ratio of each component of SiO2@ (BN + CNT) is 99:0.8: 0.2.
Modified silica E: the mass fraction ratio of each component of SiO2@ (BN + CNT) is 95:4: 1.
Modified silica F: the mass fraction ratio of each component of SiO2@ (BN + CNT) is 80:16: 4.
Modified silica G: the mass fraction ratio of each component of SiO2@ (BN + CNT) is 40:48: 12.
Hardening accelerator: TPP.
Coupling agent: mercaptopropyl trimethoxysilane.
An ion scavenger: IXE-100.
The release agent consists of E wax (L ICOWAX E PWD) and polyethylene/olefin synthetic wax (PED-522).
Flame retardant: aluminum hydroxide.
Stress modifier: p52.
Colorant: carbon black, MA-600.
The test method comprises the following steps:
spiral flow length: the measurement is carried out according to EMMI-1-66 using a mould to measure the spiral flow, the length of which is expressed in cm, measured at a moulding temperature of 175 ℃ at an injection clamping pressure of 6.9MPa and a hardening time of 120 seconds.
Gel time: the method measures the curing characteristics and mixing uniformity of the epoxy resin composition. The above composition was poured onto the center of an electric hot plate at 175. + -. 2 ℃ and immediately ground with a tongue-pressing rod to an area of about 5cm2A stopwatch was pressed down from the start of melting of the composition, and the powder was discharged at a frequency of 1 time/sec using a spatula, and the time taken was read as the end point when the powder gradually changed from a fluid to a gel state. The same procedure was carried out twice (the difference between the two values measured was not more than 2s) and the gelation time was averaged over the two values measured.
The length of flash: the mold temperature was 175. + -. 2 ℃ and the transfer pressure was 70 kg. + -.2 kg/cm, measured on a transfer molding press with the aid of a flash metal mold220g +/-2 g of sample powder is poured into a material cavity of a plastic packaging machine for molding, after the mold is opened for 120 seconds, the mold is moved to an operation table, an F L ASH mold measures the length of a flash, the length of the flash starts to measure the size of the longest part in an air groove from the circular edge, and the depths of different air grooves are measured respectively and expressed by mm.
Coefficient of thermal conductivity: the molded thermal conductivity coefficient sample strips (the length of the lower bottom is 100mm, the width of the lower bottom is 50mm, the length of the upper bottom is 97mm, the width of the upper bottom is 47mm, the thickness is 20mm) are subjected to post-curing treatment at 175 ℃ for 4 hours, then the sample strips are placed in a test zone of a thermal conductivity meter (KYOTO QTM-500), test conditions are set, and the thermal conductivity coefficients of different samples are tested.
Cl-PH, conductivity: taking a proper amount of epoxy molding compound, flattening the epoxy molding compound on an electric hot plate at the temperature of 175 +/-3 ℃, solidifying the epoxy molding compound, shoveling the solidified material from the electric hot plate, putting the solidified material in an oven at the temperature of 175 +/-5 ℃, solidifying the solidified material for 6 hours, cooling the post-solidified material piece to room temperature, grinding and crushing the material piece, and sieving the material piece by a 80-mesh sieve to prepare extract liquor. Taking the extract, and measuring Cl by titration-The ion content, the pH value and the conductivity were measured by a pH meter and a conductivity meter, respectively.
Volume impedance: the test pieces were pressed by transfer molding (round. phi. 100 mm. H:2mm in test piece size) under the following conditions: the temperature of the metal mold is 175 plus or minus 3 ℃, and the injection pressure is 70 plus or minus 5kg/cm2Cure time 2 minutes. Post-curing the molded sample strips at 175 ℃ for 6hrs, storing the sample strips in a PCT high-pressure cooking instrument for 168hrs under the conditions of high temperature, high humidity, 121 ℃, 2 atmospheres and 100% humidity, taking out the sample strips, placing the sample strips into a dryer, cooling the sample strips to room temperature, wiping the front and back surfaces of the sample strips clean by using a copper brush or gauze, and testing by using a volume resistance instrument under the test condition that the charge voltage is usually set to be 500V; the impedance range is set to 106 omega-7M omega, and the test can be directly read.
Testing the heat dissipation capacity: the sample was prepared as a circular coupon having a diameter of 10mm and a thickness of 3 mm. The ambient temperature is room temperature; a 60 x 15mm long heater was attached to the center of each sample, and the heater power was set at 0.47A x 10.5V-4.935W, and the center temperature of the molding compound at equilibrium was measured.
TABLE 2 test results of examples 1-14 and comparative examples
As shown in the results of Table 2, when the modified silica is added, the thermal conductivity of the obtained epoxy resin composition is greatly improved, and the radiation heat dissipation capability is obviously enhanced. The heat conduction capability is obviously enhanced along with the increase of the mass fraction of the boron nitride, and the epoxy resin composition forms an excellent heat conduction path; the radiation emissivity is increased along with the increase of the mass fraction of the carbon nano tube, the radiation heat dissipation capability is enhanced, and the temperature drop is obvious. Simultaneously has excellent flowing property and excellent electrical property, and keeps proper Cl of the epoxy resin composition-Content, PH, conductivity and volume impedance. An epoxy resin composition suitable for the development requirements of miniaturization and high integration of a package can be provided.
Although the preferred embodiments of the present invention have been described above, it should be understood that they may be embodied in many different forms without departing from the spirit or scope of the invention.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. The epoxy resin composition comprises an inorganic filling material, epoxy resin, a hardening agent and a hardening accelerator, and is characterized in that the inorganic filling material at least comprises boron nitride and carbon nano tube composite modified and coated modified silicon dioxide.
2. The low-temperature high-radiant-heat epoxy resin composition as claimed in claim 1, wherein the modified silica has a mass fraction of boron nitride and carbon nanotubes of not more than 60%.
3. The low-temperature high-radiant-heat epoxy resin composition as claimed in claim 1, wherein the modified material used for the modified silica is an intercalation structure composite formed by aligning boron nitride and carbon nanotubes.
4. The low-temperature high-radiant-heat epoxy resin composition according to claim 1, wherein the inorganic filler further comprises any one or more of an oxide, a nitride, and a carbide.
5. The low-temperature high-radiant-heat epoxy resin composition according to claim 1, further comprising any one or more of a coupling agent, an ion scavenger, a mold release agent, a flame retardant, a stress modifier, and a colorant.
6. The application of the low-temperature high-radiant heat epoxy resin composition is characterized in that: the epoxy resin composition of low temperature and high radiant heat according to any one of claims 1 to 5 can be used as a packaging material for discrete devices and integrated circuit packages which are required for the development of volume miniaturization and high integration.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113174185A (en) * | 2021-05-24 | 2021-07-27 | 上海涂固安高科技有限公司 | Fireproof flame-retardant coating for corrosion-resistant steel structure |
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| CN109135193A (en) * | 2018-08-22 | 2019-01-04 | 广东生益科技股份有限公司 | Compositions of thermosetting resin, prepreg, laminate and printed circuit board |
| CN110835098A (en) * | 2018-08-16 | 2020-02-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Boron nitride nanosheet/carbon nanotube composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108659537A (en) * | 2018-04-12 | 2018-10-16 | 中科广化（重庆）新材料研究院有限公司 | A kind of carbon nanotube and boron nitride collaboration enhancing organosilicon Heat Conduction Material and its preparation method and application |
| CN110835098A (en) * | 2018-08-16 | 2020-02-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Boron nitride nanosheet/carbon nanotube composite material and preparation method thereof |
| CN109135193A (en) * | 2018-08-22 | 2019-01-04 | 广东生益科技股份有限公司 | Compositions of thermosetting resin, prepreg, laminate and printed circuit board |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113174185A (en) * | 2021-05-24 | 2021-07-27 | 上海涂固安高科技有限公司 | Fireproof flame-retardant coating for corrosion-resistant steel structure |
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Application publication date: 20200731 |