A semi-cured sheet using a hydrocarbon resin composition and a method for preparing the same

Abstract

The application belongs to the technical field of resin materials for copper-clad plates, and particularly relates to a carbon-hydrogen resin composition for prepreg and a preparation method thereof. The carbon-hydrogen resin composition is prepared from the following raw materials in parts by mass: hyperbranched modified prepolymer resin 90-100 parts, inorganic filler 15-25 parts, silane coupling agent 0.2-0.4 parts, crosslinking agent 10-20 parts, initiator 0.8-1.5 parts, dibutyltin dilaurate 0.1-0.3 parts, antioxidant 0.5-1 part, and toluene 50-80 parts. The carbon-hydrogen resin composition prepared by the application has low dielectricity, high thermal conductivity, high heat resistance, high toughness, and excellent processing forming property.

Description

Technical Field

[0001] This invention belongs to the technical field of resin materials for copper clad laminates, specifically relating to a hydrocarbon resin composition for prepreg and its preparation method. Background Technology

[0002] As a core material in electronic communications, copper-clad laminates (CCLs) face increasingly stringent performance requirements due to the rapid development of high-speed information processing and high-frequency signal transmission. Traditional epoxy resin / glass cloth-based prepregs, with their high dielectric constant and dielectric loss, suffer from severe signal attenuation and heat generation at high frequencies, rendering them unsuitable. Therefore, resin materials used in CCLs need to possess superior dielectric properties, heat resistance, and dimensional stability.

[0003] Materials represented by polytetrafluoroethylene (PTFE) have extremely low dielectric constant and dielectric loss. However, PTFE has problems such as a large difference in thermal expansion coefficient compared to copper foil, weak bonding force, poor processability, and high cost, which limit its application in high-frequency and high-speed electronic materials with complex and high reliability requirements.

[0004] To achieve a balance between performance, processability, and cost, hydrocarbon resin systems, represented by modified polybutadiene, styrene-butadiene copolymers, and cyclic olefin polymers, have emerged. The main molecular chains of these materials consist of nonpolar carbon-carbon and carbon-hydrogen bonds, exhibiting naturally low polarity. Furthermore, their processing technology is highly compatible with traditional epoxy resin systems, making them the mainstream choice for copper-clad laminates.

[0005] Chinese patent application CN115651128A discloses a hydrocarbon resin polymer and a method for preparing copper-clad laminate containing it. This method synthesizes a low molecular weight hydrocarbon resin polymer and introduces a benzene ring structure, which makes the resin system more stable during curing and reduces the coefficient of thermal expansion of the copper-clad laminate. However, the resin composition uses inorganic fillers of silica, hollow zirconium dioxide and hollow alumina in a 1:1:1 ratio. The hollow powder filler has poor surface wettability, is prone to agglomeration, and has weak bonding force with the resin matrix, which can easily lead to a decrease in the uniformity of the adhesive solution and affect the mechanical and dielectric properties of the copper-clad laminate. Summary of the Invention

[0006] In existing hydrocarbon resin compositions, inorganic fillers have poor compatibility with hydrocarbon resins. To solve this problem, the present invention provides a hydrocarbon resin composition for prepreg and its preparation method.

[0007] To achieve the objectives of this invention, the following technical solution is adopted:

[0008] In a first aspect, the present invention provides a hydrocarbon resin composition for prepreg, which is prepared from the following raw materials in parts by weight:

[0009] The composition includes 90-100 parts of hyperbranched modified prepolymer resin, 15-25 parts of inorganic filler, 0.2-0.4 parts of silane coupling agent, 10-20 parts of crosslinking agent, 0.8-1.5 parts of initiator, 0.1-0.3 parts of dibutyltin dilaurate, 0.5-1 part of antioxidant, and 50-80 parts of toluene.

[0010] By adopting the above technical solutions, the advantages of low dielectric and high toughness of hyperbranched modified prepolymer resin are fully utilized. Furthermore, the performance shortcomings of single components are made up for by the precise ratio of inorganic fillers, crosslinking agents and other components. The addition of silane coupling agents, dibutyltin dilaurate and antioxidants has achieved the effects of improved filler compatibility, controllable crosslinking reaction and enhanced heat resistance and oxidation resistance. The ratio of each raw material is scientific and reasonable and the synergistic effect is significant.

[0011] Furthermore, the preparation method of the hyperbranched modified prepolymer resin includes the following steps:

[0012] (1) Hydroxyl-terminated hyperbranched polyester, maleic anhydride, p-toluenesulfonic acid and N,N-dimethylformamide are mixed evenly and reacted at 60~90℃ for 3~5h under inert gas protection to obtain anhydride-modified hyperbranched polyester.

[0013] (2) Mix aromatic copolymer polybutadiene, anhydride-modified hyperbranched polyester, dicumyl peroxide and xylene evenly, and react at 110~130℃ for 2~4h under inert gas protection, then heat to 140~160℃ for 0.5~1h, cool and filter to obtain hyperbranched modified prepolymer resin.

[0014] By adopting the above technical solution, the appropriate grafting of anhydride groups in step (1) reduces the overall polarity of the hyperbranched polyester and retains some hydroxyl groups for subsequent reactions with other components; in step (2), dicumyl peroxide is slowly decomposed at 110~130℃ to initiate the grafting reaction between the anhydride-modified hyperbranched polyester and the aromatic copolymer polybutadiene, ensuring that the grafting reaction is uniform and sufficient and improving the grafting rate; then the temperature is raised to 140~160℃ to further promote the full reaction of unreacted active groups and improve the formation of the structure; finally, a prepolymer resin with low dielectric and high reactivity is obtained.

[0015] Furthermore, in step (1), the hydroxyl-terminated hyperbranched polyester has a hydroxyl value of 100~300mgKOH / g and a number-average molecular weight of 2000~3000g / mol.

[0016] By adopting the above technical solution, a hydroxyl value of 100~300mgKOH / g can ensure sufficient hydroxyl groups for reaction with maleic anhydride; the number average molecular weight is moderate, which can take into account the flowability and structural stability of hyperbranched polyester, and avoid the viscosity increase or incomplete reaction caused by excessive molecular weight.

[0017] Further, in step (1), the mass ratio of hydroxyl-terminated hyperbranched polyester, maleic anhydride, p-toluenesulfonic acid and N,N-dimethylformamide is (15~25):(2~6):(0.2~0.5):(50~90).

[0018] By adopting the above technical solution, this ratio introduces sufficient anhydride reaction sites, retains some hydroxyl groups for subsequent reaction with isocyanate crosslinking agents, and avoids the problem of unreacted monomer residues caused by excessive maleic anhydride, which would deteriorate the dielectric properties of the system.

[0019] Further, in step (2), the mass ratio of aromatic ring copolymer polybutadiene, anhydride-modified hyperbranched polyester, dicumyl peroxide and xylene is 100:(12~20):(0.4~1):(110~180).

[0020] By adopting the above technical solution, this ratio allows hyperbranched polyester to be uniformly grafted onto the aromatic copolymer polybutadiene molecular chain, forming a stable structure. If the grafting amount is too small, the viscosity-reducing and toughening advantages of the hyperbranched structure cannot be utilized, while if the grafting amount is too large, the dielectric properties of the system will increase. This range achieves structural uniformity and performance stability of the hyperbranched modified prepolymer resin.

[0021] Furthermore, the preparation method of the aromatic ring copolymer polybutadiene includes the following steps:

[0022] Styrene, 1,3-butadiene, and maleic anhydride are polymerized in an organic solvent at 75-80°C in an inert atmosphere and in the presence of an initiator at a mass ratio of (25-35):(62-74):(1-3) to obtain aromatic ring copolymer polybutadiene.

[0023] By adopting the above technical solution, styrene, as an aromatic monomer, can improve the heat resistance and rigidity of polybutadiene by using 25-35 parts, while avoiding excessive use that would lead to an increase in dielectric constant; 1,3-butadiene, as the main monomer, can ensure the low dielectric and high toughness advantages of polybutadiene by using 62-74 parts; maleic anhydride, used by using 1-3 parts, introduces a small amount of active groups on the polybutadiene molecular chain, providing sites for subsequent grafting reactions with anhydride-modified hyperbranched polyesters, while avoiding excessive use that would lead to an increase in system polarity and deterioration of dielectric properties.

[0024] Furthermore, the initiator is benzoyl peroxide; the amount of initiator is 0.3% to 0.7% of the total mass of styrene, 1,3-butadiene and maleic anhydride.

[0025] Furthermore, the inorganic filler is prepared by mixing flake boron nitride with a particle size of 10~20μm, flake boron nitride with a particle size of 1~2μm, and spherical boron nitride with a particle size of 1~3μm in a mass ratio of (4~5):(2~3):(3~4).

[0026] By adopting the above technical solutions, 10-20 μm lamellar boron nitride can serve as a thermally conductive framework, rapidly constructing a continuous thermally conductive network and improving the thermal conductivity of the system; 1-2 μm lamellar boron nitride can fill the gaps between large-diameter lamellar boron nitride particles, further densifying the thermally conductive network and increasing the contact area between the filler and the resin; 1-3 μm spherical boron nitride acts as a "filler and ball" between the lamellar boron nitride particles, improving processing fluidity, preventing the agglomeration of lamellar boron nitride, and simultaneously helping to improve thermal conductivity; the combination of the three boron nitride types maximizes the packing density and the connectivity of the thermal conductive pathways.

[0027] Furthermore, the crosslinking agent is prepared by mixing divinylbenzene and hexamethylene diisocyanate trimer at a mass ratio of (2~4):1.

[0028] By employing the above technical solutions, divinylbenzene possesses advantages such as low dielectric strength and high heat resistance. It can react with the double bonds on the molecular chains of hyperbranched modified prepolymer resins, increasing crosslinking density and heat resistance. Hexamethylene diisocyanate trimer can react with the hydroxyl groups in the prepolymer resin, further forming a network with good toughness and strong adhesion. The combined use of these two crosslinking agents forms a dense and stable crosslinking network, giving the cured product high heat resistance, high strength, low dielectric strength, and excellent toughness and interfacial adhesion.

[0029] In a first aspect, the present invention provides a method for preparing the above-mentioned hydrocarbon resin composition for prepreg, comprising the following steps:

[0030] S1: Mix the inorganic filler, silane coupling agent and 1 / 3 part of toluene evenly to obtain the inorganic filler slurry;

[0031] S2: Mix the hyperbranched modified prepolymer resin and 2 / 3 part of toluene evenly to obtain a resin solution;

[0032] S3: Add the inorganic filler slurry to the resin solution and mix evenly. Then add dibutyltin dilaurate, crosslinking agent, and antioxidant in sequence and mix evenly. Add an initiator to react and obtain a hydrocarbon resin composition for semi-cured sheets.

[0033] By adopting the above technical solution, a silane coupling agent is first grafted onto the surface of the inorganic filler to improve the surface polarity of the inorganic filler, enhance its compatibility with the subsequent resin solution, avoid the agglomeration of the inorganic filler, and facilitate the subsequent mixing of the slurry with the resin solution, thereby improving the dispersion efficiency. Then, the inorganic filler slurry is mixed with the resin solution to allow the inorganic filler to be slowly and uniformly dispersed in the resin solution. Finally, a hydrocarbon resin composition for prepreg with uniform dispersion, stable performance, low dielectric constant, high thermal conductivity, high heat resistance, and high toughness is obtained. Moreover, the entire preparation process has low industrial production cost and strong batch stability of the product.

[0034] Further, in step S1, the mixing step is as follows: mix at a speed of 1000~1500 rpm for 15~30 min, and then grind and disperse for 1~2 h.

[0035] Furthermore, in step S3, the reaction temperature is 30~35℃ and the reaction time is 1~2h.

[0036] Furthermore, the method for preparing the above-mentioned hydrocarbon resin composition for prepreg includes the following steps:

[0037] S1: Add inorganic filler, silane coupling agent and 1 / 3 part of toluene to a high-speed disperser and disperse at 1000~1500 rpm for 15~30 min. Then transfer to a grinder and grind and disperse for 1~2 h to obtain inorganic filler slurry.

[0038] S2: Add the hyperbranched modified prepolymer resin and 2 / 3 part of toluene to the mixing tank, and stir at 300-600 rpm for 1-2 hours at 40-50℃ to obtain a resin solution.

[0039] S3: Slowly add the inorganic filler slurry to the resin solution, maintain the temperature, increase the speed to 800~1200 rpm and stir continuously for 30~60 min; maintain the temperature, decrease the speed to 400~600 rpm, add dibutyltin dilaurate and stir for 10~15 min; maintain the speed, raise the temperature to 50~55℃, add the crosslinking agent and stir for 10~15 min; maintain the speed, lower the temperature to 40~45℃, add the antioxidant and stir for 10~15 min; lower the temperature to 30~35℃, decrease the speed to 200~400 rpm, add the initiator and continue stirring for 1~2 h; degas under vacuum, filter with a 200~300 mesh filter to obtain the hydrocarbon resin composition for semi-cured sheets.

[0040] In summary, the beneficial effects of this invention are:

[0041] 1. The hydrocarbon resin composition obtained by the present invention has low dielectric constant, high thermal conductivity, high heat resistance, high toughness and excellent processability, and is suitable for the needs of processes such as impregnation and pre-drying of prepreg.

[0042] 2. This invention uses chemical grafting to bond the hyperbranched polyester "core" to the non-polar hydrocarbon resin "shell", achieving two-phase compatibility at the molecular level and avoiding phase separation caused by physical blending; the rigid hyperbranched core improves the glass transition temperature and thermal stability of the resin, while the flexible hydrocarbon shell ensures low dielectric loss and toughness.

[0043] 3. This invention uses three different boron nitride particles with different sizes and morphologies as inorganic fillers to form a gradient particle size distribution and complementary morphologies, avoiding problems such as uneven thermal conductivity, excessive viscosity, and increased dielectric properties caused by boron nitride with a single morphology and particle size. At the same time, the synergistic effect of the plate-like and spherical structures can improve the interfacial bonding force between the filler and the resin, and enhance the mechanical properties of the resin composition. Attached Figure Description

[0044] Figure 1 The image shows the infrared spectrum of the hyperbranched modified prepolymer resin. Detailed Implementation

[0045] The present invention will be further described below with reference to specific embodiments.

[0046] Unless otherwise specified, the experimental methods used in the following examples and comparative examples are conventional methods. Unless otherwise specified, the materials and reagents used in the following examples and comparative examples are commercially available.

[0047] Preparation example: Preparation of aromatic ring copolymer polybutadiene

[0048] Preparation Example 1

[0049] The preparation method of the aromatic ring copolymer polybutadiene in this example includes the following specific steps:

[0050] 320g of styrene, 710g of 1,3-butadiene, 20g of maleic anhydride, 6.3g of benzoyl peroxide and toluene were added to a reaction vessel, nitrogen gas was introduced, and the temperature was raised to 76℃ and reacted for 16h to obtain aromatic ring copolymer polybutadiene.

[0051] Preparation Example 2

[0052] The preparation method of the aromatic ring copolymer polybutadiene in this example includes the following specific steps:

[0053] 280g of styrene, 650g of 1,3-butadiene, 30g of maleic anhydride, 3.9g of benzoyl peroxide and toluene were added to a reaction vessel, nitrogen gas was introduced, and the temperature was raised to 78℃ and reacted for 16h to obtain aromatic ring copolymer polybutadiene.

[0054] Preparation Example 3

[0055] The preparation method of the aromatic ring copolymer polybutadiene in this example includes the following specific steps:

[0056] 350g of styrene, 620g of 1,3-butadiene, 10g of maleic anhydride, 4.6g of benzoyl peroxide and toluene were added to a reaction vessel, nitrogen gas was introduced, and the temperature was raised to 80℃ and reacted for 16h to obtain aromatic ring copolymer polybutadiene.

[0057] Preparation examples: Preparation of hyperbranched modified prepolymer resins

[0058] Preparation Example 4

[0059] The preparation method of the hyperbranched modified prepolymer resin in this example includes the following specific steps:

[0060] (1) 18g of hydroxyl-terminated hyperbranched polyester and 65g of N,N-dimethylformamide were added to a four-necked flask, nitrogen gas was introduced for protection, and the temperature was raised to 80℃ and stirred for 30min; 4g of maleic anhydride and 0.3g of p-toluenesulfonic acid were added, and the reaction was carried out at a constant temperature for 4h; after the reaction was completed, N,N-dimethylformamide and a small amount of unreacted maleic anhydride were removed under reduced pressure to obtain anhydride-modified hyperbranched polyester;

[0061] (2) 100g of the aromatic copolymer polybutadiene prepared in Preparation Example 1 and 170g of xylene were added to a four-necked flask, nitrogen gas was introduced for protection, and the temperature was raised to 110°C and stirred until completely dissolved; 15g of anhydride-modified hyperbranched polyester was added, and after stirring evenly, 0.4g of dicumyl peroxide was added, the temperature was raised to 120°C and reacted for 3h, and then the temperature was raised to 150°C and reacted for 0.5h; after the reaction was completed, the mixture was cooled to room temperature, filtered, and the solvent was removed under reduced pressure to obtain hyperbranched modified prepolymer resin.

[0062] Infrared test results of hyperbranched modified prepolymer resin are as follows: Figure 1 As shown. By Figure 1 It can be seen that 2992cm -1 The peak of the stretching vibration of CH is located at 1744 cm⁻¹. -1 The peak at 1584 cm⁻¹ represents the stretching vibration of C=O. -1 The vicinity is near the benzene ring skeletal vibration peak; 1231 cm⁻¹ -1 The peak value for the stretching vibration of COC is 931 cm⁻¹. -1 The nearby peaks are out-of-plane bending vibration peaks of the aromatic ring CH. The appearance of these characteristic peaks indicates that the hyperbranched modified prepolymer resin has been successfully synthesized.

[0063] Preparation Example 5

[0064] The preparation method of the hyperbranched modified prepolymer resin in this example includes the following specific steps:

[0065] (1) 15g of hydroxyl-terminated hyperbranched polyester and 85g of N,N-dimethylformamide were added to a four-necked flask, nitrogen gas was introduced for protection, and the temperature was raised to 70℃ and stirred for 30min; 2g of maleic anhydride and 0.2g of p-toluenesulfonic acid were added, and the reaction was carried out at a constant temperature for 4h; after the reaction was completed, N,N-dimethylformamide and a small amount of unreacted maleic anhydride were removed under reduced pressure to obtain anhydride-modified hyperbranched polyester;

[0066] (2) 100g of the aromatic copolymer polybutadiene prepared in Preparation Example 1 and 120g of xylene were added to a four-necked flask, nitrogen gas was introduced for protection, and the temperature was raised to 110°C and stirred until completely dissolved; 12g of anhydride-modified hyperbranched polyester was added, and after stirring evenly, 0.7g of dicumyl peroxide was added, the temperature was raised to 110°C and reacted for 2h, and then the temperature was raised to 140°C and reacted for 1h; after the reaction was completed, the temperature was cooled to room temperature, filtered, and the solvent was removed under reduced pressure to obtain hyperbranched modified prepolymer resin.

[0067] Preparation Example 6

[0068] The preparation method of the hyperbranched modified prepolymer resin in this example includes the following specific steps:

[0069] (1) 20g of hydroxyl-terminated hyperbranched polyester and 50g of N,N-dimethylformamide were added to a four-necked flask, nitrogen gas was introduced for protection, and the temperature was raised to 85℃ and stirred for 30min; 5g of maleic anhydride and 0.5g of p-toluenesulfonic acid were added, and the reaction was kept at a constant temperature for 3h; after the reaction was completed, N,N-dimethylformamide and a small amount of unreacted maleic anhydride were removed under reduced pressure to obtain anhydride-modified hyperbranched polyester;

[0070] (2) 100g of the aromatic copolymer polybutadiene prepared in Preparation Example 3 and 160g of xylene were added to a four-necked flask, nitrogen gas was introduced for protection, and the temperature was raised to 110°C and stirred until completely dissolved; 18g of anhydride-modified hyperbranched polyester was added, and after stirring evenly, 1g of dicumyl peroxide was added, and the temperature was raised to 120°C and reacted for 4h, and then the temperature was raised to 145°C and reacted for 0.5h; after the reaction was completed, the temperature was cooled to room temperature, filtered, and the solvent was removed under reduced pressure to obtain hyperbranched modified prepolymer resin.

[0071] Preparation Example 7

[0072] The preparation method of the hyperbranched modified prepolymer resin in this example includes the following specific steps:

[0073] (1) 25g of hydroxyl-terminated hyperbranched polyester and 75g of N,N-dimethylformamide were added to a four-necked flask, nitrogen gas was introduced for protection, and the temperature was raised to 60℃ and stirred for 30min; 6g of maleic anhydride and 0.3g of p-toluenesulfonic acid were added, and the reaction was carried out at a constant temperature for 5h; after the reaction was completed, N,N-dimethylformamide and a small amount of unreacted maleic anhydride were removed under reduced pressure to obtain anhydride-modified hyperbranched polyester;

[0074] (2) 100g of the aromatic copolymer polybutadiene prepared in Preparation Example 1 and 155g of xylene were added to a four-necked flask, nitrogen gas was introduced for protection, and the temperature was raised to 110°C and stirred until completely dissolved; 15g of anhydride-modified hyperbranched polyester was added, and after stirring evenly, 0.5g of dicumyl peroxide was added, the temperature was raised to 125°C and reacted for 3h, and then the temperature was raised to 160°C and reacted for 0.5h; after the reaction was completed, the mixture was cooled to room temperature, filtered, and the solvent was removed under reduced pressure to obtain hyperbranched modified prepolymer resin.

[0075] Example

[0076] Example 1

[0077] A hydrocarbon resin composition for a semi-cured sheet according to this embodiment is prepared from the following raw materials by weight:

[0078] Preparation Example 6 prepared 98g of hyperbranched modified prepolymer resin, 25g of inorganic filler, 0.3g of silane coupling agent, 15g of crosslinking agent, 1.5g of initiator, 0.3g of dibutyltin dilaurate, 0.8g of antioxidant, and 75g of toluene;

[0079] The inorganic filler is prepared by mixing plate-shaped boron nitride with a particle size of 10~20μm, plate-shaped boron nitride with a particle size of 1~2μm, and spherical boron nitride with a particle size of 1~3μm in a mass ratio of 5:2:4.

[0080] The crosslinking agent was prepared by mixing divinylbenzene and hexamethylene diisocyanate trimer in a mass ratio of 3:1;

[0081] The initiator is dicumyl peroxide;

[0082] The antioxidant is prepared by mixing antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

[0083] The preparation method of the hydrocarbon resin composition for prepreg in this embodiment includes the following specific steps:

[0084] S1: Add inorganic filler, silane coupling agent and 1 / 3 part of toluene to a high-speed disperser and disperse at 1000 rpm for 15 min. Then transfer to a grinder and grind and disperse for 2 h to obtain inorganic filler slurry.

[0085] S2: Add hyperbranched modified prepolymer resin and 2 / 3 part of toluene to the reactor, and stir at 300 rpm for 1 hour at 50°C to obtain resin solution;

[0086] S3: Slowly add the inorganic filler slurry to the resin solution, maintain the temperature, increase the speed to 800 rpm and stir continuously for 50 min; maintain the temperature, decrease the speed to 400 rpm, add dibutyltin dilaurate and stir for 15 min; maintain the speed, raise the temperature to 55℃, add the crosslinking agent and stir for 10 min; maintain the speed, lower the temperature to 40℃, add the antioxidant and stir for 15 min; lower the temperature to 30℃, decrease the speed to 300 rpm, add the initiator and continue stirring for 1 h; degas under vacuum, filter with a 200~300 mesh filter to obtain a hydrocarbon resin composition for semi-cured sheets.

[0087] Example 2

[0088] A hydrocarbon resin composition for a semi-cured sheet according to this embodiment is prepared from the following raw materials by weight:

[0089] Preparation Example 4 prepared 90g of hyperbranched modified prepolymer resin, 20g of inorganic filler, 0.4g of silane coupling agent, 16g of crosslinking agent, 1.2g of initiator, 0.15g of dibutyltin dilaurate, 0.5g of antioxidant, and 53g of toluene;

[0090] The inorganic filler is prepared by mixing plate-shaped boron nitride with a particle size of 10~20μm, plate-shaped boron nitride with a particle size of 1~2μm, and spherical boron nitride with a particle size of 1~3μm in a mass ratio of 4:2:4.

[0091] The crosslinking agent was prepared by mixing divinylbenzene and hexamethylene diisocyanate trimer in a mass ratio of 3:1;

[0092] The initiator is dicumyl peroxide;

[0093] The antioxidant is prepared by mixing antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

[0094] The preparation method of the hydrocarbon resin composition for prepreg in this embodiment includes the following specific steps:

[0095] S1: Add inorganic filler, silane coupling agent and 1 / 3 part of toluene to a high-speed disperser and disperse at 1400 rpm for 25 min. Then transfer to a grinder and grind and disperse for 2 h to obtain inorganic filler slurry.

[0096] S2: Add the hyperbranched modified prepolymer resin and 2 / 3 part of toluene to the reactor, and stir at 550 rpm for 1.5 h at 40 °C to obtain a resin solution.

[0097] S3: Slowly add the inorganic filler slurry to the resin solution, maintain the temperature, increase the speed to 1000 rpm and stir continuously for 60 min; maintain the temperature, decrease the speed to 450 rpm, add dibutyltin dilaurate and stir for 15 min; maintain the speed, raise the temperature to 50℃, add the crosslinking agent and stir for 10 min; maintain the speed, lower the temperature to 45℃, add the antioxidant and stir for 10 min; lower the temperature to 30℃, decrease the speed to 400 rpm, add the initiator and continue stirring for 2 h; degas under vacuum, filter with a 200~300 mesh filter to obtain a hydrocarbon resin composition for semi-cured sheets.

[0098] Example 3

[0099] A hydrocarbon resin composition for a semi-cured sheet according to this embodiment is prepared from the following raw materials by weight:

[0100] Preparation Example 4 prepared 95g of hyperbranched modified prepolymer resin, 15g of inorganic filler, 0.25g of silane coupling agent, 12g of crosslinking agent, 0.8g of initiator, 0.2g of dibutyltin dilaurate, 0.6g of antioxidant, and 70g of toluene;

[0101] The inorganic filler is prepared by mixing plate-shaped boron nitride with a particle size of 10~20μm, plate-shaped boron nitride with a particle size of 1~2μm, and spherical boron nitride with a particle size of 1~3μm in a mass ratio of 4:3:3.

[0102] The crosslinking agent was prepared by mixing divinylbenzene and hexamethylene diisocyanate trimer in a mass ratio of 4:1;

[0103] The initiator is dicumyl peroxide;

[0104] The antioxidant is prepared by mixing antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

[0105] The preparation method of the hydrocarbon resin composition for prepreg in this embodiment includes the following specific steps:

[0106] S1: Add inorganic filler, silane coupling agent and 1 / 3 part of toluene to a high-speed disperser and disperse at 1500 rpm for 15 min. Then transfer to a grinder and grind and disperse for 1.5 h to obtain inorganic filler slurry.

[0107] S2: Add hyperbranched modified prepolymer resin and 2 / 3 part of toluene to the reactor, and stir at 400 rpm for 2 hours at 45°C to obtain resin solution;

[0108] S3: Slowly add the inorganic filler slurry to the resin solution, maintain the temperature, increase the speed to 900 rpm and stir continuously for 45 min; maintain the temperature, decrease the speed to 600 rpm, add dibutyltin dilaurate and stir for 10 min; maintain the speed, raise the temperature to 50℃, add the crosslinking agent and stir for 15 min; maintain the speed, lower the temperature to 45℃, add the antioxidant and stir for 15 min; lower the temperature to 30℃, reduce the speed to 250 rpm, add the initiator and continue stirring for 2 h; degas under vacuum, filter with a 200~300 mesh filter to obtain a hydrocarbon resin composition for semi-cured sheets.

[0109] Example 4

[0110] A hydrocarbon resin composition for a semi-cured sheet according to this embodiment is prepared from the following raw materials by weight:

[0111] Preparation Example 5 prepared 100g of hyperbranched modified prepolymer resin, 22g of inorganic filler, 0.25g of silane coupling agent, 10g of crosslinking agent, 1.1g of initiator, 0.2g of dibutyltin dilaurate, 1g of antioxidant, and 80g of toluene;

[0112] The inorganic filler is prepared by mixing plate-shaped boron nitride with a particle size of 10~20μm, plate-shaped boron nitride with a particle size of 1~2μm, and spherical boron nitride with a particle size of 1~3μm in a mass ratio of 5:3:3.

[0113] The crosslinking agent was prepared by mixing divinylbenzene and hexamethylene diisocyanate trimer in a mass ratio of 2:1;

[0114] The initiator is dicumyl peroxide;

[0115] The antioxidant is prepared by mixing antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

[0116] The preparation method of the hydrocarbon resin composition for prepreg in this embodiment includes the following specific steps:

[0117] S1: Add inorganic filler, silane coupling agent and 1 / 3 part of toluene to a high-speed disperser and disperse at 1200 rpm for 20 min. Then transfer to a grinder and grind and disperse for 2 h to obtain inorganic filler slurry.

[0118] S2: Add hyperbranched modified prepolymer resin and 2 / 3 part of toluene to the reactor, and stir at 350 rpm for 2 hours at 40°C to obtain resin solution;

[0119] S3: Slowly add the inorganic filler slurry to the resin solution, maintain the temperature, increase the speed to 1200 rpm and stir continuously for 30 min; maintain the temperature, decrease the speed to 500 rpm, add dibutyltin dilaurate and stir for 15 min; maintain the speed, raise the temperature to 50℃, add the crosslinking agent and stir for 10 min; maintain the speed, lower the temperature to 45℃, add the antioxidant and stir for 10 min; lower the temperature to 35℃, decrease the speed to 200 rpm, add the initiator and continue stirring for 2 h; degas under vacuum, filter with a 200~300 mesh filter to obtain a hydrocarbon resin composition for semi-cured sheets.

[0120] Example 5

[0121] A hydrocarbon resin composition for a semi-cured sheet according to this embodiment is prepared from the following raw materials by weight:

[0122] Preparation Example 4 prepared 92g of hyperbranched modified prepolymer resin, 25g of inorganic filler, 0.32g of silane coupling agent, 18g of crosslinking agent, 1g of initiator, 0.15g of dibutyltin dilaurate, 0.9g of antioxidant, and 66g of toluene;

[0123] The inorganic filler is prepared by mixing flake boron nitride with a particle size of 10~20μm, flake boron nitride with a particle size of 1~2μm, and spherical boron nitride with a particle size of 1~3μm in a mass ratio of 4:2:3.

[0124] The crosslinking agent was prepared by mixing divinylbenzene and hexamethylene diisocyanate trimer in a mass ratio of 2:1;

[0125] The initiator is dicumyl peroxide;

[0126] The antioxidant is prepared by mixing antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

[0127] The preparation method of the hydrocarbon resin composition for prepreg in this embodiment includes the following specific steps:

[0128] S1: Add inorganic filler, silane coupling agent and 1 / 3 part of toluene to a high-speed disperser and disperse at 1500 rpm for 30 min. Then transfer to a grinder and grind and disperse for 1 h to obtain inorganic filler slurry.

[0129] S2: Add the hyperbranched modified prepolymer resin and 2 / 3 part of toluene to the reactor, and stir at 500 rpm for 1.5 h at 45°C to obtain a resin solution.

[0130] S3: Slowly add the inorganic filler slurry to the resin solution, maintain the temperature, increase the speed to 1200 rpm and stir continuously for 40 min; maintain the temperature, decrease the speed to 400 rpm, add dibutyltin dilaurate and stir for 15 min; maintain the speed, raise the temperature to 50℃, add the crosslinking agent and stir for 10 min; maintain the speed, lower the temperature to 40℃, add the antioxidant and stir for 15 min; lower the temperature to 30℃, decrease the speed to 300 rpm, add the initiator and continue stirring for 2 h; degas under vacuum, filter with a 200~300 mesh filter to obtain a hydrocarbon resin composition for semi-cured sheets.

[0131] Comparative Example 1

[0132] The difference from Example 1 is that this comparative example uses an equal amount of 10-20 μm sheet-like boron nitride as an inorganic filler.

[0133] Comparative Example 2

[0134] The difference from Example 1 is that this comparative example uses an equal amount of 1~3μm spherical boron nitride as an inorganic filler.

[0135] Comparative Example 3

[0136] The difference from Example 1 is that this comparative example uses an equal amount of unmodified aromatic copolymer polybutadiene resin from Preparation Example 1 instead of the hyperbranched prepolymer resin.

[0137] Comparative Example 4

[0138] The difference from Example 1 is that the hyperbranched modified prepolymer resin in this comparative example was not modified with anhydride, but was directly prepared using hydroxyl-terminated hyperbranched polyester.

[0139] Related performance tests

[0140] Glass fibers were placed in a glue tank and impregnated with the resin compositions prepared in Examples 1-5 and Comparative Examples 1-4. The impregnated glass fiber cloth was baked at 155°C for 1 minute to obtain a semi-cured sheet. Five semi-cured sheets were coated with high-ductility electrolytic copper foil on both sides and hot-pressed into copper-clad laminates using a hot press.

[0141] The peel strength was tested according to the IPC-TM-650 2.4 standard, with a total of 6 tests on both sides of the copper clad laminate, and the average value was taken. The dielectric constant and dielectric loss of the sample were tested according to the IPC-TM-650 2.5 standard, and the average value of the two results was taken.

[0142] Table 1 Test Results

[0143]

[0144] As shown in Table 1, Examples 1-5 all maintain excellent low dielectric constant (Dk≤2.98), low loss (Df≤0.0018) and high peel strength (≥2.59N / mm), meeting the requirements of prepreg and copper clad laminate.

[0145] Comparing Comparative Examples 1 and 2 with Example 1, it can be seen that the peel strength and dielectric properties of the single filler are significantly worse than those of Example 1. This indicates that the boron nitride compounding schemes with different particle sizes and morphologies of the present invention can effectively improve the interfacial bonding force between the filler and the resin (improving peel strength), while constructing a dense and uniform dielectric network and reducing the dielectric constant and dielectric loss.

[0146] Comparing Comparative Examples 3 and 4 with Example 1, it can be seen that hyperbranching modification can improve the reactivity of the prepolymer resin and its compatibility with fillers and other components; anhydride modification can effectively improve the grafting rate of hyperbranched polyester and aromatic copolymer polybutadiene, enhance the bonding ability of prepolymer with inorganic fillers and crosslinking agents, and further optimize the dielectric properties and peel strength of the system.

[0147] The present invention has been described above by way of example. It should be noted that any simple modifications, alterations or other equivalent substitutions that can be made by those skilled in the art without creative effort without departing from the core of the present invention fall within the protection scope of the present invention.

Claims

1. A hydrocarbon resin composition for prepreg, characterized in that, It is prepared from the following parts by weight of raw materials: The composition includes 90-100 parts of hyperbranched modified prepolymer resin, 15-25 parts of inorganic filler, 0.2-0.4 parts of silane coupling agent, 10-20 parts of crosslinking agent, 0.8-1.5 parts of initiator, 0.1-0.3 parts of dibutyltin dilaurate, 0.5-1 part of antioxidant, and 50-80 parts of toluene. The preparation method of hyperbranched modified prepolymer resin includes the following steps: (1) Hydroxyl-terminated hyperbranched polyester, maleic anhydride, p-toluenesulfonic acid and N,N-dimethylformamide are mixed evenly and reacted at 60~90℃ for 3~5h under inert gas protection to obtain anhydride-modified hyperbranched polyester; (2) Aromatic ring copolymer polybutadiene, anhydride-modified hyperbranched polyester, dicumyl peroxide and xylene are mixed evenly and reacted at 110~130℃ for 2~4h under inert gas protection, and then heated to 140~160℃ for 0.5~1h, cooled and filtered to obtain hyperbranched modified prepolymer resin; The preparation method of aromatic ring copolymer polybutadiene includes the following steps: styrene, 1,3-butadiene and maleic anhydride are polymerized in an organic solvent at 75-80℃ in the presence of an inert atmosphere and an initiator at a mass ratio of (25~35):(62~74):(1~3) to obtain aromatic ring copolymer polybutadiene.

2. The hydrocarbon resin composition for prepreg according to claim 1, characterized in that, In step (1), the hydroxyl-terminated hyperbranched polyester has a hydroxyl value of 100~300mgKOH / g and a number-average molecular weight of 2000~3000g / mol.

3. The hydrocarbon resin composition for prepreg according to claim 1, characterized in that, In step (1), the mass ratio of hydroxyl-terminated hyperbranched polyester, maleic anhydride, p-toluenesulfonic acid and N,N-dimethylformamide is (15~25):(2~6):(0.2~0.5):(50~90).

4. The hydrocarbon resin composition for prepreg according to claim 1, characterized in that, In step (2), the mass ratio of aromatic ring copolymer polybutadiene, anhydride-modified hyperbranched polyester, dicumyl peroxide and xylene is 100:(12~20):(0.4~1):(110~180).

5. The hydrocarbon resin composition for prepreg according to claim 1, characterized in that, The inorganic filler is prepared by mixing plate-shaped boron nitride with a particle size of 10-20 μm, plate-shaped boron nitride with a particle size of 1-2 μm, and spherical boron nitride with a particle size of 1-3 μm in a mass ratio of (4-5):(2-3):(3-4).

6. The hydrocarbon resin composition for prepreg according to claim 1, characterized in that, The crosslinking agent is prepared by mixing divinylbenzene and hexamethylene diisocyanate trimer in a mass ratio of (2~4):

1.

7. A method for preparing a hydrocarbon resin composition for a semi-cured sheet according to any one of claims 1-6, characterized in that, Includes the following steps: S1: Mix the inorganic filler, silane coupling agent and 1 / 3 part of toluene evenly to obtain the inorganic filler slurry; S2: Mix the hyperbranched modified prepolymer resin and 2 / 3 part of toluene evenly to obtain a resin solution; S3: Add the inorganic filler slurry to the resin solution and mix evenly. Then add dibutyltin dilaurate, crosslinking agent, and antioxidant in sequence and mix evenly. Add an initiator to react and obtain a hydrocarbon resin composition for semi-cured sheets.

8. The method for preparing a hydrocarbon resin composition for a semi-cured sheet according to claim 7, characterized in that, In step S1, the mixing process is as follows: mix at a speed of 1000~1500 rpm for 15~30 min, and then grind and disperse for 1~2 h; in step S3, the reaction temperature is 30~35℃, and the reaction time is 1~2 h.

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