High dielectric, high thermal conductivity, low loss electronic resin and application thereof

Abstract

The application relates to the technical field of high-frequency electronic communication materials, and specifically discloses an electronic resin with high dielectricity, high heat conductivity and low loss and an application thereof. The electronic resin comprises the following components: a hydrocarbon resin composition, a functional filler, a wetting dispersant, a flame retardant, an antioxidant and a crosslinking agent; wherein the hydrocarbon resin composition at least contains a styrene-butadiene-butene-styrene block copolymer, and the hydrocarbon resin composition further contains at least one of a styrene-butadiene copolymer, a styrene-divinylbenzene copolymer and a maleic anhydride grafted polyolefin; and the functional filler is pretreated by the wetting dispersant. The electronic resin can be used for preparing a high-frequency copper-clad plate, and the prepared high-frequency copper-clad plate has a dielectric constant of 6.15, a dielectric loss value reduced to 0.0035 and a heat conductivity coefficient of 0.8 W / (m.k) under a detection condition of 10GHz, and has more excellent dielectric performance and use performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high-frequency electronic communication materials, and more particularly to an electronic resin with high dielectric, high thermal conductivity and low loss and an application thereof. BACKGROUND

[0002] 5G communication has the characteristics of high-speed transmission, low latency and high connection density, which requires the copper-clad plate widely used in 5G devices to have excellent dielectric properties, high thermal conductivity, good heat resistance and high reliability. With the rapid development of 5G and 6G, there are higher requirements for the design and processing of high-frequency copper-clad plates, and there is a trend of high-speed information processing and high-frequency signal transmission.

[0003] At present, the electronic resin for high-frequency copper-clad plates generally selects polytetrafluoroethylene, polyphenyl ether and hydrocarbon resin as the base resin. Although the polytetrafluoroethylene resin has good electrical properties and excellent dielectric property stability, the copper-clad plate prepared therefrom needs to be specially treated in PCB processing, such as pre-treatment before plating. In addition, due to the extremely low surface energy of polytetrafluoroethylene, the obtained adhesive sheet usually needs to be pre-treated by plasma so that the interface of the adhesive sheet and the copper foil can be better combined when mixed and pressed.

[0004] The polyphenyl ether resin has the advantages of low specific gravity, low water absorption, excellent heat resistance and chemical resistance, good electrical insulation, excellent dielectricity, etc., but still has the following defects: first, the polyphenyl ether resin can prepare a copper-clad plate with a dielectric loss value D f in the range of 0.005-0.006, but as a high-frequency copper-clad plate, the dielectric loss value still has room for further reduction. Second, the polyphenyl ether resin is difficult to cure, and its processability needs to be improved.

[0005] The carbon-hydrogen resin also has good dielectric properties. Unlike polytetrafluoroethylene, the high-frequency copper-clad plate prepared therefrom does not need to be pre-treated. Unlike polyphenyl ether resin, the dielectric loss value of the copper-clad plate prepared therefrom can be controlled to be below 0.005. However, the thermal conductivity of carbon-hydrogen resin is low, and based on the need for high thermal conductivity of copper-clad plates, a thermal conductive filler is generally added to modify the carbon-hydrogen resin. The density of the thermal conductive filler is large, and the mass fraction of the thermal conductive filler in the electronic resin is large, so the thermal conductive filler is difficult to fully disperse in the carbon-hydrogen resin, which limits the improvement of the thermal conductivity of the final electronic resin, and also increases the dielectric constant of the electronic resin. In addition to the above defects, the addition of fillers will cause the bonding performance of the adhesive sheet prepared from the electronic resin and the metal substrate such as copper foil to decrease, and also easily cause the thermal expansion coefficient of the adhesive sheet to increase and the thermal stability to decrease.

[0006] In summary, the dielectric constant of the high-frequency copper-clad plate is generally below 5.75 (10 GHz), the thermal conductivity is below 0.50 w / mk, and the dielectric loss value is difficult to meet the requirement of below 0.0040 (10 GHz). Therefore, how to obtain a high-frequency copper-clad plate with high dielectric, low loss, high thermal conductivity and stable performance is still a technical difficulty in the industry. SUMMARY

[0007] In view of the above related problems, the present application provides a high-dielectric, high-thermal-conductivity and low-loss electronic resin and its application, and the copper-clad plate prepared therefrom has the characteristics of high dielectric, low loss and high thermal conductivity, and meets good processing performance and thermal stability.

[0008] In the first aspect, the present application provides a high-dielectric, high-thermal-conductivity and low-loss electronic resin, which adopts the following technical scheme:

[0009] A high-dielectric, high-thermal-conductivity and low-loss electronic resin comprises the following components by weight:

[0010] 25-45 parts of a hydrocarbon resin composition, 30-70 parts of a functional filler, 0.1-5 parts of a wetting dispersant, 10-30 parts of a flame retardant, 0.1-1 part of an antioxidant, and 0.5-5 parts of a crosslinking agent;

[0011] The hydrocarbon resin composition contains at least a styrene-butadiene-butene-styrene block copolymer, and further contains at least one of a styrene-butadiene copolymer, a styrene-divinylbenzene copolymer and a maleic anhydride grafted polyolefin.

[0012] The functional filler is pretreated by the wetting dispersant.

[0013] By adopting the above technical scheme, the styrene-butadiene-butene-styrene block copolymer is obtained by directional partial hydrogenation of a styrene-butadiene-styrene block copolymer, and the main chain still retains part of carbon-carbon double bonds, which has certain reaction crosslinking activity. The combination of the styrene-butadiene-butene-styrene block copolymer with high-reactivity resins such as a styrene-butadiene copolymer, a styrene-divinylbenzene copolymer and a maleic anhydride grafted polyolefin, on the one hand, is easy to form a three-dimensional crosslinked network structure under the action of a crosslinking agent, which endows the adhesive sheet formed by curing the electronic resin with excellent dielectric properties, low thermal expansion coefficient and relatively high glass transition temperature; on the other hand, the molecular weight of the styrene-butadiene-butene-styrene block copolymer is relatively large, and the more physical entanglement points of the long molecular chain, the better the toughness of the adhesive sheet, thereby improving the processing performance of the adhesive sheet.

[0014] The functional filler can be selected from high dielectric fillers such as titanium white powder, strontium titanate, calcium titanate, barium titanate, etc., and can also be selected from silicon powder, and a plurality of different functional powders can be compounded. The selection of the wetting dispersant includes but is not limited to modified amino silane, phenyl amino silane, vinyl silane coupling agent, epoxy silane coupling agent, methoxy silane, phenyl silane coupling agent, coordination type titanate coupling agent, and polyphosphate solution.

[0015] The functional filler used in the present application is modified by a wetting dispersant, which has the following advantages: first, whether the density of the functional filler is too large or too small, it can be stably dispersed in the hydrocarbon resin composition, which is beneficial to improve the tensile and compressive strength of the cured product formed by the electronic resin in the later stage, and improve the stability of the high-frequency copper-clad plate. Second, due to the sufficient dispersion of the functional filler, the more the interface between the filler and the hydrocarbon resin, the more the interface polarization effect in the polarization process, thereby improving the dielectric properties of the electronic resin. Third, during the curing process of the electronic resin, the electronic resin is not prone to delamination due to the density of the filler, thereby improving the overall bonding strength and thermal stability of the high-frequency copper-clad plate.

[0016] It should be noted that the selection of the flame retardant in the present application includes but is not limited to one or more of bromine-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, organic silicon-based flame retardants, and zinc stannate-based flame retardants; the present application uses organic flame retardants and inorganic flame retardants to improve the flame retardant efficiency, and can achieve UL-94 V0 level with less addition.

[0017] The selection of the antioxidant in the present application includes but is not limited to p-phenylenediamine, hydroxylamine, diphenylamine, alkyl polyphenol, thio-bisphenol, hindered phenol, etc. main antioxidant, also includes thioether and phosphite auxiliary antioxidant; the present application uses the above-mentioned main antioxidant and auxiliary antioxidant to compound, which has a good synergistic effect, greatly improves the thermal stability of the hydrocarbon resin composition in the processing and later application, especially inhibits the main chain oxidation of styrene-butadiene-butene-styrene block copolymer, improves the yellowing defect of the hydrocarbon resin composition, and improves the reliability of the high-frequency copper-clad plate.

[0018] The selection of the initiator in the present application includes but is not limited to azo initiators such as azobis isopropyl cyanide, benzoyl peroxide, 1,1-bis (tert-butyl peroxide) -3,3,5-trimethylcyclohexane, and other organic peroxide initiators, and inorganic initiators such as mixtures of thermal air vulcanization peroxide; the present application can also add diphenylstyrene, triallyl isocyanate, and other crosslinking agents, and the crosslinking rate of the electronic resin can be controlled within a suitable range by compounding the crosslinking agent and the initiator.

[0019] In summary, the present application selects styrene-butadiene-butene-styrene block copolymer and other high-activity hydrocarbon resins for compounding, and then adds a functional filler modified by a wetting dispersant to the hydrocarbon resin composition, so that the electronic resin can form a bonding sheet with excellent dielectric performance, excellent heat resistance and excellent processing performance under the action of a crosslinking agent. The applicant made a copper-clad plate from the bonding sheet, and found through testing that the dielectric constant of the copper-clad plate was as high as 6.15 at a high frequency of 10 GHz, the dielectric loss value was reduced to 0.0035 (10 GHz), and the thermal conductivity was as high as 0.8 W / (m·k). Compared with the copper-clad plates on the market, the copper-clad plate has more excellent dielectric performance and use performance. Thus, the technical problem of the present application is successfully solved.

[0020] Further, the composition of the hydrocarbon resin composition is styrene-butadiene copolymer, styrene-divinylbenzene copolymer, styrene-butadiene-butene-styrene block copolymer, and maleic anhydride grafted polyolefin. Among them, the selection of maleic anhydride grafted polyolefin includes but is not limited to maleic anhydride grafted polybutadiene and maleic anhydride grafted polystyrene-butadiene.

[0021] Further, the weight ratio of styrene-butadiene copolymer, styrene-divinylbenzene copolymer, styrene-butadiene-butene-styrene block copolymer, and maleic anhydride grafted polyolefin in the hydrocarbon resin composition is (5-15):(5-10):(5-10):3.

[0022] By adopting the above technical solution, the above hydrocarbon resins jointly act and have the following advantages:

[0023] Firstly, the maleic anhydride grafted polyolefin can promote the compatibility between other hydrocarbon resins, so as to improve the toughness of the electronic resin and improve the processing performance of the bonding sheet. Secondly, due to the increased compatibility between the resins, the styrene-diene copolymer, styrene-divinylbenzene copolymer and styrene-diene-butene-styrene block copolymer all have good dielectric properties, which makes up for the defect that the addition of polar maleic anhydride grafted polyolefin easily leads to the increase of dielectric loss, so that the dielectric constant of the electronic resin is significantly increased, and the dielectric loss is not increased but decreased; the above-mentioned hydrocarbon resins are used together, which plays a synergistic effect in improving the dielectric properties of the electronic resin, so that the electronic resin is suitable for preparing higher frequency copper-clad plate. Thirdly, in the styrene-diene copolymer, the polybutadiene structure with high 1,2 polymerization; the divinylbenzene in the styrene-divinylbenzene copolymer has a crosslinkable side double bond, which increases the reactivity of the resin, so that the polymer has a high crosslinking density, and the high-frequency copper-clad plate has a high glass transition temperature, which greatly improves the heat resistance. Fourthly, the maleic anhydride grafted polyolefin can promote the bonding force between the hydrocarbon resin and the filler and the bonding force between the hydrocarbon resin and the metal substrate, so as to enhance the stability of the high-frequency copper-clad plate as a whole.

[0024] Further, the number average molecular weight of the styrene-diene-butene-styrene block copolymer in the hydrocarbon resin composition is 50000-200000, the number average molecular weight of the styrene-diene copolymer is 1000-100000, the number average molecular weight of the styrene-divinylbenzene copolymer is 5000-20000, and the number average molecular weight of the maleic anhydride grafted polyolefin is 1000-10000.

[0025] Further, the number average molecular weight of the styrene-diene-butene-styrene block copolymer in the hydrocarbon resin composition is 50000-200000, the number average molecular weight of the styrene-diene copolymer is 1000-100000, the number average molecular weight of the styrene-divinylbenzene copolymer is 5000-20000, and the number average molecular weight of the maleic anhydride grafted polyolefin is 1000-10000.

[0026] By adopting the above technical scheme, the lower the molecular weight of each resin in the hydrocarbon resin composition, the lower the viscosity, and the better the infiltration effect on the glass fiber in the later glass fiber cloth impregnation step, but when the molecular weight of the hydrocarbon resin is too low, especially when the molecular weight of the styrene-diene-butene-styrene block copolymer is too low, the overall toughness of the bonding sheet obtained by curing the electronic resin is reduced, which is not conducive to the later processing of the bonding sheet; therefore, within this number average molecular weight range, the comprehensive use performance of the electronic resin can be balanced.

[0027] Further, the functional filler includes a high dielectric filler with a dielectric constant ≥100.

[0028] Further, the high dielectric filler is rutile titanium dioxide.

[0029] By adopting the above technical solution, the rutile titanium dioxide with high dielectric constant is selected as a functional filler component, so as to make the electronic resin have more excellent dielectric properties; the hydrocarbon resin and the wetting dispersant can be fully coated on the surface of the rutile titanium dioxide, so as to make up for the defect that the rutile titanium dioxide is easy to absorb moisture, and make the electronic resin also have good temperature stability and frequency stability of dielectric properties.

[0030] Further, the high dielectric filler is composed of titanium dioxide with an average particle size of 0.5-5 μm.

[0031] By adopting the above technical solution, the titanium dioxide with multiple particle sizes is compounded, which can improve the packing density of the dielectric filler and further reduce the moisture absorption rate of the dielectric filler. Meanwhile, the titanium dioxide with small particle size has a large specific surface area, and the interface between the titanium dioxide and the hydrocarbon resin composition is increased, so that the interface polarization effect is more significant in the polarization process, thereby greatly improving the dielectric properties.

[0032] Further, the titanium dioxide is pretreated with a polyphosphate solution.

[0033] By adopting the above technical solution, the polyphosphate solution has excellent wetting and dispersing effect on the titanium dioxide, and can also enhance the combination between the titanium dioxide and the hydrocarbon resin composition, so that the dispersion effect of the titanium dioxide in the electronic resin is excellent and stable, and the dielectric properties of the electronic resin are further improved.

[0034] Further, the functional filler further comprises silicon powder.

[0035] Further, the silicon powder is composed of angular silicon powder with an average particle size of 2-12 μm and spherical silicon powder with an average particle size of 3-10 μm.

[0036] Further, the silicon powder is pretreated with an acrylic silane coupling agent and an epoxy coupling agent.

[0037] By adopting the above technical solution, the silicon powder has excellent electrical insulation properties, and as a component of the functional filler, it can be added to the electronic resin to impart excellent insulation, thermal conductivity, and thermal stability to the copper-clad material, improve the bending strength and dimensional stability of the plate, reduce the thermal expansion rate of the plate, and improve the dielectric constant of the copper-clad plate.

[0038] The acrylic silane coupling agent and the epoxy coupling agent have good dispersing and improving effect on the silicon powder, and can also increase the crosslinking density inside the electronic resin, thereby assisting in improving the dielectric properties and heat resistance of the electronic resin.

[0039] In a second aspect, the application provides an application of an electronic resin with high dielectric, high thermal conductivity and low loss, which adopts the following technical scheme:

[0040] The application of the electronic resin with high dielectric, high thermal conductivity and low loss is prepared into a bonding sheet and a high-frequency copper-clad plate according to the following steps:

[0041] Preparation of the bonding sheet:

[0042] The hydrocarbon resin composition is added into a solvent for dispersion to obtain a resin dispersion liquid;

[0043] The wetting dispersant is first dispersed in the solvent, and then the functional filler and the flame retardant are added for dispersion to obtain a filler suspension;

[0044] The resin dispersion liquid and the filler suspension are blended, and the antioxidant and the crosslinking agent are added for dispersion to obtain the electronic resin;

[0045] The glass fiber base cloth is immersed in the electronic resin, and baking is performed to obtain the bonding sheet;

[0046] Preparation of the high-frequency copper-clad plate:

[0047] The bonding sheet is selected, copper foils are coated on both sides, and vacuum hot pressing is performed to obtain the high-frequency copper-clad plate.

[0048] Compared with the prior art, the application has the following beneficial technical effects:

[0049] In the application, the styrene-butadiene-butene-styrene block copolymer is compounded with other high-activity hydrocarbon resins, and the functional filler modified by the wetting dispersant is added into the hydrocarbon resin composition, so that the electronic resin can form the bonding sheet with excellent dielectric performance, excellent heat resistance and excellent processing performance under the action of the crosslinking agent. After the copper-clad plate made of the bonding sheet is detected, it is found that the dielectric constant of the copper-clad plate is as high as 6.15 under high frequency of 10 GHz, the dielectric loss value is reduced to 0.0035 (10 GHz), the thermal conductivity coefficient is as high as 0.8 W / (m·k), and the copper-clad plate has more excellent dielectric performance and use performance compared with the copper-clad plate on the market.

[0050] In the application, the rutile titanium dioxide with different particle sizes is compounded, which can improve the packing density of the filler and further reduce the moisture absorption rate of the filler. At the same time, the specific surface area of the titanium dioxide with small particle size is large, and the interface between the titanium dioxide and the hydrocarbon resin composition is increased. In the polarization process, the interface polarization effect is more significant, thereby greatly improving the dielectric performance.

[0051] 3. The raw materials in the application are easy to obtain, and the process is easy to implement, which is similar to the conventional thermosetting vertical gluing process and pressing, and facilitates batch production. DETAILED DESCRIPTION

[0052] In order to make the objects, technical solutions and advantages of the present application clearer, the technical solutions of the present application are further described below in combination with examples, comparative examples and application examples.

[0053] The raw materials used in the following examples, comparative examples and application examples are as follows unless otherwise specified:

[0054] Styrene-butadiene-butene-styrene block copolymer is a custom product:

[0055] SBBS1: number average molecular weight 50000; SBBS2: number average molecular weight 100000; SBBS3: number average molecular weight 200000;

[0056] Styrene-butadiene copolymer is a custom product:

[0057] SBS1: number average molecular weight 1000; SBS2: number average molecular weight 2000; SBS3: number average molecular weight 10000;

[0058] Styrene-divinylbenzene copolymer is a custom product:

[0059] ST-DVB1: number average molecular weight 5000; ST-DVB2: number average molecular weight 10000; ST-DVB3: number average molecular weight 20000;

[0060] Maleic anhydride grafted polybutadiene is a custom product:

[0061] MLPB1: number average molecular weight 1000; MLPB2: number average molecular weight 5000; MLPB3: number average molecular weight 10000;

[0062] Epoxy silane coupling agent: brand KH560, from Shandong Silicon;

[0063] Acrylic silane coupling agent: brand Z-6030, from Dow Corning;

[0064] Polyphosphate solution: brand DISPERBYK-110, from Byk Chem;

[0065] Coordination type titanate coupling agent: brand TYZOR 726, from Nanjing Pinning;

[0066] Bromine-based flame retardant: brand 8010, from Yaba;

[0067] Hydroxylamine antioxidant: brand Revonox 420, from Shanghai Puzhan Industry.

[0068] Examples

[0069] A high dielectric, high thermal conductivity, low loss electronic resin is prepared according to the following steps:

[0070] Styrene-butadiene copolymer (SBS2), styrene-divinylbenzene copolymer (ST-DVB2), styrene-butadiene-butene-styrene block copolymer (SBBS2), maleic anhydride grafted polybutadiene (MLPB2) are prepared as hydrocarbon resin composition;

[0071] Toluene is used as solvent, and the hydrocarbon resin composition is slowly added under the condition of stirring speed of 400 r / min. After mixing and stirring for 75 min, the hydrocarbon resin composition is completely dispersed in toluene to form a uniform resin dispersion liquid;

[0072] Toluene is used as solvent, and the stirring speed is set to 200 r / min. Epoxy silane coupling agent KH560, acrylic silane coupling agent Z-6030 and polyphosphate wetting dispersant DISPERBYK-110 are added, and stirred for 20 min. Silicon powder, titanium dioxide, and flame retardant 8010 are sequentially added, and the stirring speed is set to 1200 r / min. The stirring is continued for 90 min to prepare a filler suspension;

[0073] The silicon powder is composed of angular silicon powder with average particle sizes of 2 μm, 5 μm and 12 μm, and spherical silicon powder with average particle sizes of 3 μm, 6 μm and 10 μm. The titanium dioxide is composed of rutile titanium dioxide with average particle sizes of 0.5 μm, 2 μm and 5 μm;

[0074] The resin dispersion liquid and the filler suspension are mixed together, and the stirring speed is set to 600 r / min. Antioxidant Revonox 420, crosslinking agent divinylbenzene and dicumyl peroxide are sequentially added, and the stirring is continued for 160 min to obtain an electronic resin;

[0075] Examples 1-3 are all prepared according to the above scheme, and the only difference is that the addition amount of each raw material is different. The specific addition amount is shown in Table 1.

[0076] Table 1. Raw material composition of Examples 1-3 (unit: g)

[0077]

[0078] Examples 4-8

[0079] A high dielectric, high thermal conductivity, low loss electronic resin is prepared based on Example 1, and the difference from Example 1 is that the composition of the hydrocarbon resin is different. The specific composition is shown in Table 2.

[0080] Table 2. Selection of hydrocarbon resin composition of Examples 4-8 (unit: g)

[0081]

[0082] Example 9-12

[0083] A high dielectric, high thermal conductivity, low loss electronic resin, based on Example 1, differs from Example 1 in that the composition of the functional filler is different, and is as follows:

[0084] In Example 9, 40 g of rutile titanium dioxide with an average particle size of 5 μm is used to replace the titanium dioxide in Example 1.

[0085] In Example 10, 0.5 μm, 2 μm, 5 μm anatase titanium dioxide with an average particle size of 0.5 μm, 2 μm, 5 μm is used to replace the titanium dioxide in Example 1, and the weight ratio of the 0.5 μm, 2 μm, 5 μm anatase titanium dioxide is 3:3:2.

[0086] In Example 11, 6 g of angular silicon powder with an average particle size of 2 μm and 6 g of 10 μm spherical silicon powder are used to replace the silicon powder in Example 1.

[0087] In Example 12, the silicon powder is replaced by 12 g of 3 μm, 6 μm, 10 μm spherical silicon powder with an average particle size of 3 μm, 6 μm, 10 μm, and the weight ratio of the 3 μm, 6 μm, 10 μm spherical silicon powder is 1:1:1.

[0088] Example 13

[0089] A high dielectric, high thermal conductivity, low loss electronic resin, based on Example 1, differs from Example 1 in that the composition of the functional filler is different, and is as follows:

[0090] In this example, 12 g of 3 μm, 6 μm, 10 μm aluminum oxide powder with an average particle size of 3 μm, 6 μm, 10 μm is used to replace the silicon powder, and the weight ratio of the 3 μm, 6 μm, 10 μm aluminum oxide powder is 1:1:1.

[0091] Example 14

[0092] A high dielectric, high thermal conductivity, low loss electronic resin, based on Example 1, differs from Example 1 in that the wetting dispersant used in the pretreatment of the titanium dioxide is different, and is as follows:

[0093] In this example, a coordination type titanate coupling agent TYZOR 726 is used instead of the polyphosphate solution.

[0094] Examples 15-17

[0095] A kind of electronic resin of high dielectric, high thermal conductivity, low loss, based on example 1, the difference point with example 1 is as follows: the wetting dispersant used in the pretreatment of silicon powder is different, as follows:

[0096] In example 15, 3g of silane coupling agent Z-6030 is used instead of 2g of silane coupling agent Z-6030 and 1g of epoxy silane coupling agent KH560;

[0097] In example 16, 3g of epoxy silane coupling agent KH560 is used instead of 2g of silane coupling agent Z-6030 and 1g of epoxy silane coupling agent KH560;

[0098] In example 17, 3g of vinyl silane coupling agent KH-172 is used instead of 2g of silane coupling agent Z-6030 and 1g of epoxy silane coupling agent KH560.

[0099] Comparative example

[0100] Comparative example 1-4

[0101] An electronic resin, based on example 1, the difference point with example 1 is that the composition of the hydrocarbon resin composition is different,

[0102] In comparative example 1, maleic anhydride grafted polybutadiene MLPB2 is used instead of styrene-butadiene-butene-styrene block copolymer SBBS2;

[0103] In comparative example 2, styrene-butadiene copolymer SBS2 is used instead of styrene-butadiene-butene-styrene block copolymer SBBS2;

[0104] In comparative example 3, SEBS (number average molecular weight 10000) is used instead of styrene-butadiene-butene-styrene block copolymer SBBS2;

[0105] In comparative example 4, 2.5g of styrene-butadiene copolymer SBS2 and 2.5g of SEBS (number average molecular weight 10000) are used instead of styrene-butadiene-butene-styrene block copolymer SBBS2.

[0106] Comparative example 5

[0107] An electronic resin, based on example 1, the difference point with example 1 is that no wetting dispersant is added to the electronic resin, i.e. the functional filler is not treated with a wetting dispersant.

[0108] Application example

[0109] Application example 1

[0110] A high-frequency copper-clad plate is prepared according to the following steps:

[0111] A single 0.101 mm adhesive sheet is prepared by using 1080 electronic grade glass fiber cloth as a reinforcing material, coating the electronic resin prepared in Example 1 on both sides, and drying;

[0112] Sixteen adhesive sheets are selected, and both sides are covered with 10Z TWS copper foil. A high-frequency copper-clad plate with high dielectric constant, high thermal conductivity, and low loss is prepared by using a vacuum press at a temperature of 240°C and a pressure of 900 psi for 240 min.

[0113] Application Examples 2-17 and Application Comparative Examples 1-5

[0114] A high-frequency copper-clad plate is prepared based on Application Example 1, and the difference from Application Example 1 is that the source of the electronic resin is different, as shown in Table 3 below.

[0115] Table 3. Source of electronic resin in application examples and application comparative examples

[0116]

[0117] Performance testing

[0118] The following tests are performed on Application Examples 1-17 and Application Comparative Examples 1-5:

[0119] 1. Dielectric constant D k : The dielectric constant at 10 GHz is measured by the SPDR (split post dielectric resonator) dielectric material characteristic parameter test method;

[0120] 2. Temperature change rate of dielectric constant:

[0121] According to the following formula: α ε =(1 / ε)×(d ε / d t );

[0122] When the relationship between ε and t is considered as a straight line within a certain test temperature range, α ε =(1 / ε1)×(Δε / Δt), where Δε=ε2-ε1, Δt=t2-t1, and ε2, ε1 are the capacitances at temperatures t2 and t1;

[0123] 3. Dielectric loss value D f : The dielectric loss value at 10 GHz is measured by the SPDR (split post dielectric resonator) dielectric material characteristic parameter test method;

[0124] 4. Z-axis thermal conductivity coefficient: The Z-axis thermal conductivity coefficient is tested according to the test method described in ASTM D5470, with the unit being W / mK;

[0125] 5. Coefficient of thermal expansion: Refer to GB / T 36800.2-2018 Plastics - Thermomechanical analysis - Part 2: Determination of coefficient of thermal expansion, measure the coefficient of thermal expansion on Z axis, test temperature range 50-260℃, unit ppm / ℃;

[0126] 6. Peel strength: Refer to the method specified in GB / 15821-1995, unit (lb / inch) / 1oz copper foil;

[0127] 7. Water absorption: Refer to the method specified in IPC-TM-650 2.6.2.1, unit %.

[0128] Test results

[0129] Table 4. Test results of application examples 1-3 and application comparative examples 1-5

[0130]

[0131] Table 5. Test results of application examples 4-10

[0132]

[0133] Table 6. Test results of application examples 11-17

[0134]

[0135] It can be seen from the combination of application example 1 and application comparative example 1 and in combination with Table 4 that in application comparative example 1, maleic anhydride grafted polybutadiene is used instead of styrene-butadiene-butene-styrene block copolymer (i.e. partially hydrogenated styrene-butadiene-styrene copolymer), although the peel strength of application comparative example 1 is higher than that of application example 1, but its dielectric properties are significantly reduced.

[0136] It can be seen from the combination of application example 1 and application comparative examples 2-4 and in combination with Table 4 that in application comparative examples 2-4, styrene-butadiene-styrene copolymer and fully hydrogenated styrene-butadiene-styrene copolymer are used instead of partially hydrogenated styrene-butadiene-styrene copolymer, respectively, but the dielectric properties, mechanical properties and thermal stability of application comparative examples 2-4 are not as good as those of application example 1, and the possible reason is that the styrene-butadiene-styrene copolymer and the fully hydrogenated styrene-butadiene-styrene copolymer are not fully crosslinked during the crosslinking process in this system, the reactivity is reduced, resulting in a decrease in the crosslinking density of the final electronic resin, and a decrease in the dielectric properties, mechanical properties and thermal stability.

[0137] It can be seen from the combination of application example 1 and application comparative example 5 and Table 4 that the dielectric filler and the heat-conducting filler in application comparative example 5 are not modified by the wetting dispersant, and the dispersing performance thereof in the hydrocarbon resin composition is poor, which leads to a significant decrease in the comprehensive performance of the copper-clad plate.

[0138] It can be seen from the combination of examples 4-8 and Table 5 that the complex of the rutile titanium dioxide powders with multiple particle sizes significantly improves the dielectric performance of the copper-clad plate, and the improvement effect of the rutile titanium dioxide powders on the dielectric performance of the copper-clad plate is better than that of the anatase titanium dioxide powders.

[0139] It can be seen from the combination of examples 9-17 and Tables 5-6 that the complex of the silicon micropowders with multiple particle sizes and different shapes can significantly improve the heat-conducting performance and the thermal stability of the copper-clad plate.

[0140] In addition to the above detection data, the applicant also detects the flame-retardant performance of the adhesive sheet made of the electronic resin, and the detection method refers to the UL 94 standard. Through the detection, the flame-retardant grade of the adhesive sheet made of the electronic resin of the applicant can reach the V0 level.

[0141] The technical features of the above-described examples can be combined arbitrarily, and in order to make the description simple, all possible combinations of the technical features in the above-described examples are not described, however, as long as the combination of the technical features does not exist contradictory, it should be considered as the scope of the present disclosure.

[0142] Moreover, the above-described examples only express several embodiments of the present application, and the description is more specific and detailed, but it should not be understood as a limitation on the scope of the patent. It should be pointed out that for ordinary skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of the present application. Therefore, the protection scope of the present application patent should be subject to the appended claims.

Claims

1. An electronic resin having high dielectric, high thermal conductivity, and low loss, characterized by, The composition comprises the following components by weight: hydrocarbon resin composition 25-45 parts, functional filler 30-70 parts, wetting dispersant 0.1-5 parts, flame retardant 10-30 parts, antioxidant 0.1-1 part, crosslinking agent and initiator 0.5-5 parts; The functional filler is pretreated by the wetting dispersant; The hydrocarbon resin composition is composed of styrene-butadiene-butene-styrene block copolymer, styrene-butadiene copolymer, styrene-divinylbenzene copolymer, and maleic anhydride grafted polyolefin.

2. The electronic resin of high dielectric, high thermal conductivity and low loss according to claim 1, characterized in that: The number average molecular weight of the styrene-butadiene-butene-styrene block copolymer in the hydrocarbon resin composition is 50000-200000, the number average molecular weight of the styrene-butadiene copolymer is 1000-100000, the number average molecular weight of the styrene-divinylbenzene copolymer is 5000-20000, and the number average molecular weight of the maleic anhydride grafted polyolefin is 1000-10000.

3. The electronic resin of high dielectric, high thermal conductivity and low loss according to claim 1, characterized in that: The functional filler includes high dielectric filler with dielectric constant ≥100.

4. The electronic resin of high dielectric, high thermal conductivity and low loss according to claim 3, characterized in that: The high dielectric filler is composed of titanium white powder with an average particle size of 0.5μm-5μm.

5. The electronic resin of high dielectric, high thermal conductivity and low loss according to claim 4, characterized in that: The titanium white powder is pretreated with polyphosphate solution.

6. The electronic resin of high dielectric, high thermal conductivity and low loss according to claim 1, characterized in that: The functional filler also includes silicon powder.

7. The electronic resin of high dielectric, high thermal conductivity and low loss according to claim 6, characterized in that: The silicon powder is composed of angular silicon powder with an average particle size of 2μm-12μm and spherical silicon powder with an average particle size of 3μm-10μm.

8. The electronic resin of high dielectric, high thermal conductivity and low loss according to claim 7, characterized in that: The silicon powder is pretreated with silane coupling agent and epoxy coupling agent.

9. The use of an electronic resin with high dielectric, high thermal conductivity and low loss according to any one of claims 1-8, characterized in that, The adhesive sheet and high-frequency copper-clad plate are prepared according to the following steps: Preparation of the adhesive sheet: The hydrocarbon resin composition is added to the solvent for dispersion to obtain a resin dispersion liquid; The wetting dispersant is first dispersed in the solvent, and then the functional filler and the flame retardant are added for dispersion to obtain a filler suspension liquid; The resin dispersion liquid and the filler suspension liquid are blended, and the antioxidant, crosslinking agent and initiator are added for dispersion to obtain an electronic resin; The glass fiber base cloth is immersed in the electronic resin, and baked to obtain the adhesive sheet; Preparation of the high-frequency copper-clad plate: The adhesive sheet is selected, and copper foil is coated on both sides, and vacuum hot pressing is performed to obtain the high-frequency copper-clad plate.

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