Resin material for halogen-free high-Tg low-dielectric-loss copper-clad plate and preparation process

Abstract

The invention discloses a resin material for a halogen-free high-Tg low-dielectric-loss copper-clad plate and a preparation process, and belongs to the technical field of copper-clad plate production, the resin material comprises the following raw materials by weight: 80-120 parts of modified resin, 30-45 parts of 4-aminophenoxy phthalonitrile, 22-40 parts of polymer nanoparticles, 15-30 parts of a three-dimensional ceramic network filler, 10-20 parts of a curing agent, and 50-100 parts of a solvent. Wherein the modified resin is obtained by modifying mixed resin of linear novolac epoxy resin and bismaleimide resin by taking naringenin, terephthaloyl chloride and 3-((2-hydroxyethyl) amino) propyl alcohol as modifiers. The copper-clad plate prepared by the method has the advantages of high glass transition temperature Tg, high thermal stratification time T288, high copper foil peel strength PS, low dielectric constant Dk and low dielectric loss Df. The glass-transition temperature Tg can reach 250 DEG C or above, the dielectric loss can reach 0.004 or below, and meanwhile, the halogen-free flame-retardant cable material has the halogen-free flame-retardant characteristic and better comprehensive performance.

Description

Technical Field

[0001] The invention relates to the technical field of copper clad laminate production, and in particular to a resin material for a halogen-free copper clad laminate with high Tg and low dielectric loss and a preparation process thereof. Background Art

[0002] In order to increase the transmission speed of communication signals, reduce signal transmission losses, and ensure the speed and quality of 5G communications, the dielectric loss (Df) of the interlayer dielectric material used in the copper clad laminate should be reduced as much as possible, and the glass transition temperature (Tg) should be increased. At the same time, in order to improve environmental protection effects, halogen-free requirements should be met.

[0003] CN105415778B discloses a halogen-free high-frequency and high-speed copper-clad laminate and a preparation method thereof, which is made of adhesive, glass fiber cloth and copper foil, with a glass transition temperature Tg≥150°C, a dielectric constant Dk≦3.9, and a dielectric loss Df≦0.009.

[0004] It can be seen that its glass transition temperature cannot reach above 250°C, and the dielectric loss cannot reach below 0.004. Therefore, it is still difficult for this resin material to simultaneously meet multiple requirements such as high glass transition temperature, low dielectric constant and halogen-free.

[0005] Based on this, the present invention designs a halogen-free, high-Tg, low-dielectric-loss resin material for copper-clad laminates and a preparation process to solve the above problems. Summary of the invention

[0006] In view of the above-mentioned shortcomings of the prior art, the present invention provides a halogen-free, high-Tg, low-dielectric-loss resin material for copper-clad laminates and a preparation process thereof.

[0007] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0008] A resin material for a halogen-free, high-Tg, low-dielectric-loss copper-clad laminate comprises the following raw materials in parts by weight: 80 to 120 parts of a modified resin, 30 to 45 parts of 4-aminophenoxyphthalonitrile, 22 to 40 parts of polymer nanospheres, 15 to 30 parts of a three-dimensional ceramic network filler, 10 to 20 parts of a curing agent, and 50 to 100 parts of a solvent;

[0009] The modified resin is obtained by using naringenin, terephthaloyl chloride and 3-((2-hydroxyethyl)amino)propanol as modifiers to modify a mixed resin of a linear phenolic epoxy resin and a bismaleimide resin; the mass ratio of naringenin, terephthaloyl chloride and 3-((2-hydroxyethyl)amino)propanol is 8.3-13.7:10.8-12.5:7-9.3.

[0010] Furthermore, the preparation method of the modified resin is:

[0011] Mixing 40 to 60 parts of novolac epoxy resin and 40 to 60 parts of bismaleimide resin to obtain a mixed resin;

[0012] 10.8-12.5 parts of terephthaloyl chloride and 7-9.3 parts of 3-((2-hydroxyethyl)amino)propanol are mixed to undergo esterification and cyclization to obtain a cyclic prepolymer;

[0013] 8.3-13.7 parts of naringenin are added dropwise to the cyclic prepolymer, and stirred mechanically at a high speed of 1800-2500 r / min for 15-35 minutes to obtain a modifier;

[0014] The modifier is mixed with the mixed resin, and mechanically stirred at a speed of 500 to 800 r / min for 25 to 45 minutes to obtain a modified resin.

[0015] Furthermore, the preparation method of the polymer nanospheres is: 18 to 22 parts of 2-methylene-4-phenyl-1,3-dioxolane and 10 to 12 parts of γ-aminopropyltriethoxysilane are mechanically stirred at a speed of 600 to 800 r / min, 10 to 14 parts of styrene containing 5 to 7% by mass of divinylbenzene are added dropwise, the reaction is stirred at 80 to 95° C. for 5 to 7 hours, and the nanospheres are dried and granulated at a low temperature (<50° C.) to obtain nanospheres.

[0016] Furthermore, the preparation method of the three-dimensional ceramic network filler is: mix 2 to 3 parts of Al(NO3)3·9H2O, 4 to 5 parts of Na2CO3·10H2O, 10 to 11 parts of mullite powder and 10 to 20 parts of anhydrous ethanol, then add 4 to 6 parts of tetrabutyl titanate, stir and react at 45 to 66°C for 1 to 3 hours to obtain a precursor solution; spread the precursor solution on dust-free paper, first dry it to obtain a template, and then calcine the template at 500 to 700°C to form a template with a three-dimensional network morphology, and then crush and sieve the template to 200 to 300 mesh.

[0017] Furthermore, the curing agent is a curing agent obtained by mixing isocyanate and trimethylolpropane trimethacrylate in a ratio of 1:1.

[0018] Furthermore, the solvent is acetone, ethyl acetate or dimethylformamide.

[0019] Furthermore, the preparation method of the resin composition is: firstly place the modified resin, polymer nanospheres, three-dimensional ceramic network filler and solvent at 55-65° C. and stir and mix for 1-2 hours, then add 4-aminophenoxyphthalonitrile and curing agent, and stir evenly.

[0020] Furthermore, the resin composition is uniformly coated on the glass fiber cloth and baked at 105-125° C. for 35-55 seconds to obtain a prepreg; the prepreg and copper foil are stacked and pressed to prepare a halogen-free high Tg low dielectric loss copper clad laminate.

[0021] Furthermore, the amount of the resin composition is 25-45% of the total mass of the prepreg; the pressure is 100-550 psi; and the pressing time is 100-125 minutes.

[0022] A preparation process of a halogen-free, high-Tg, low-dielectric-loss resin material for copper-clad laminates, comprising the following steps:

[0023] 1. Preparation of modified resin

[0024] The invention adopts naringenin, terephthaloyl chloride and 3-((2-hydroxyethyl)amino)propanol as modifiers to modify the mixed resin of linear phenolic epoxy resin and bismaleimide resin; the mass ratio of naringenin, terephthaloyl chloride and 3-((2-hydroxyethyl)amino)propanol is 8.3-13.7:10.8-12.5:7-9.3;

[0025] 2. Preparation of polymer nanospheres: 18 to 22 parts of 2-methylene-4-phenyl-1,3-dioxolane and 10 to 12 parts of γ-aminopropyltriethoxysilane are mechanically stirred at 600 to 800 r / min, 10 to 14 parts of styrene containing 5 to 7% by mass of divinylbenzene are added dropwise, stirred and reacted at 80 to 95°C for 5 to 7 hours, dried at low temperature, and granulated to obtain nanospheres;

[0026] 3. Preparation of three-dimensional ceramic network filler: 2-3 parts of Al(NO3)3·9H2O, 4-5 parts of Na2CO3·10H2O, 10-11 parts of mullite powder and 10-20 parts of anhydrous ethanol are mixed, and then 4-6 parts of tetrabutyl titanate are added, and the mixture is stirred and reacted at 45-66°C for 1-3 hours to obtain a precursor solution; the precursor solution is spread on dust-free paper, and first dried to obtain a template, and then the template is calcined at 500-700°C to form a template with a three-dimensional network morphology, and then the template is crushed and sieved to 200-300 mesh;

[0027] 4. Preparation of Resin Composition

[0028] First, the modified resin, polymer nano-microspheres, three-dimensional ceramic network filler and solvent are placed at 55-65° C. and stirred for 1-2 hours, and then 4-aminophenoxyphthalonitrile and a curing agent are added and stirred evenly.

[0029] In order to better achieve the purpose of the present invention, the present invention also provides a

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] The present invention introduces a cyclic prepolymer obtained by esterification and ring-forming reaction of terephthaloyl chloride and 3-((2-hydroxyethyl)amino)propanol, which is beneficial to improving the network crosslinking density, dielectric properties, flame retardant properties and heat resistance of the resin composition system, and shows the improvement of glass transition temperature Tg, thermal delamination time T288, and copper foil peeling strength PS; by introducing polymer nano-microspheres, it is beneficial to fill the polymer nano-microspheres into the gaps of the three-dimensional ceramic network filler, and then by compounding with modified resins and other raw materials, the network crosslinking density of the resin composition system can be further enhanced, which is beneficial to reducing the dielectric constant Dk and dielectric loss Df. The copper clad laminate finally prepared has a high glass transition temperature Tg, a high thermal delamination time T288, a high copper foil peeling strength PS, a low dielectric constant Dk and a low dielectric loss Df. The glass transition temperature Tg can reach above 250°C, the dielectric loss can reach below 0.004, and it has halogen-free flame retardant properties and better comprehensive performance. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0033] Example 1

[0034] In some embodiments, the resin composition for a halogen-free, high Tg, low dielectric loss copper clad laminate is prepared by the following method:

[0035] 1.1. Preparation of modified resin: 40 parts of linear phenolic epoxy resin and 60 parts of bismaleimide resin are mixed to obtain a mixed resin; 10.8 parts of terephthaloyl chloride and 9.3 parts of 3-((2-hydroxyethyl)amino)propanol are mixed, and esterification and cyclization reaction are carried out to obtain a cyclic prepolymer; 8.3 parts of naringenin are added dropwise to the cyclic prepolymer, and the mixture is mechanically stirred at 2500 r / min for 15 minutes to obtain a modifier; the modifier is mixed with the mixed resin, and mechanically stirred at 800 r / min for 25 minutes to obtain a modified resin;

[0036] The modified resin uses naringenin, terephthaloyl chloride and 3-((2-hydroxyethyl)amino)propanol as modifiers to modify the mixed resin of linear phenolic epoxy resin and bismaleimide resin;

[0037] 1.2. Preparation of polymer nanospheres: 18 parts of 2-methylene-4-phenyl-1,3-dioxolane and 12 parts of γ-aminopropyltriethoxysilane were mechanically stirred at 600 r / min, 10 parts of styrene containing 7% by mass of divinylbenzene were added dropwise, stirred and reacted at 95° C. for 5 h, dried at low temperature (<50° C.), and granulated to obtain nanospheres;

[0038] 1.3. Preparation of three-dimensional ceramic network filler: 2 parts of Al(NO3)3·9H2O, 4 parts of Na2CO3·10H2O, 10 parts of mullite powder and 10 parts of anhydrous ethanol were mixed, and then 4 parts of tetrabutyl titanate were added, and the mixture was stirred and reacted at 45°C for 3 hours to obtain a precursor solution; the precursor solution was spread on dust-free paper, and the template was first dried to obtain a template, and then the template was calcined at 500°C for 4 hours to form a template with a three-dimensional network morphology, and then the template was crushed and sieved to 300 mesh;

[0039] 1.4. Prepare a resin composition: first place 80 parts of modified resin, 40 parts of polymer nanospheres, 15 parts of three-dimensional ceramic network fillers and 100 parts of solvent at 55° C. and stir for 2 hours, then add 30 parts of 4-aminophenoxyphthalonitrile and 20 parts of curing agent and stir evenly.

[0040] The curing agent is a curing agent obtained by mixing isocyanate and trimethylolpropane trimethacrylate in a ratio of 1:1; and the solvent is acetone.

[0041] When preparing a halogen-free high Tg low dielectric loss copper clad laminate, the resin composition is evenly coated on a glass fiber cloth and baked at 105° C. for 55 seconds to obtain a prepreg; preferably, the amount of the resin composition accounts for 25% of the total mass of the prepreg; the prepreg and the copper foil are stacked and pressed; the pressing parameters are: the pressure is 100 psi; the pressing time is 125 minutes.

[0042] Example 2

[0043] In some embodiments, the resin composition for a halogen-free, high Tg, low dielectric loss copper clad laminate is prepared by the following method:

[0044] 1.1. Preparation of modified resin: 60 parts of linear phenolic epoxy resin and 40 parts of bismaleimide resin are mixed to obtain a mixed resin; 12.5 parts of terephthaloyl chloride and 7 parts of 3-((2-hydroxyethyl)amino)propanol are mixed, and esterification and cyclization reaction are carried out to obtain a cyclic prepolymer; 13.7 parts of naringenin are added dropwise to the cyclic prepolymer, and the mixture is mechanically stirred at 1800 r / min for 35 minutes to obtain a modifier; the modifier is mixed with the mixed resin, and mechanically stirred at 500 r / min for 45 minutes to obtain a modified resin;

[0045] The modified resin uses naringenin, terephthaloyl chloride and 3-((2-hydroxyethyl)amino)propanol as modifiers to modify the mixed resin of linear phenolic epoxy resin and bismaleimide resin;

[0046] 1.2. Preparation of polymer nanospheres: 22 parts of 2-methylene-4-phenyl-1,3-dioxolane and 10 parts of γ-aminopropyltriethoxysilane were mechanically stirred at 800 r / min, 14 parts of styrene containing 5% by mass of divinylbenzene were added dropwise, stirred and reacted at 80° C. for 7 h, dried at low temperature (<50° C.), and granulated to obtain nanospheres;

[0047] 1.3. Preparation of three-dimensional ceramic network filler: 3 parts of Al(NO3)3·9H2O, 5 parts of Na2CO3·10H2O, 11 parts of mullite powder and 20 parts of anhydrous ethanol were mixed, and then 6 parts of tetrabutyl titanate were added, and the mixture was stirred and reacted at 66°C for 1 hour to obtain a precursor solution; the precursor solution was spread on dust-free paper, and the template was first dried to obtain a template, and then the template was calcined at 700°C for 5 hours to form a template with a three-dimensional network morphology, and then the template was crushed and sieved to 200 mesh;

[0048] 1.4. Prepare a resin composition: first place 120 parts of modified resin, 22 parts of polymer nanospheres, 30 parts of three-dimensional ceramic network fillers and 50 parts of solvent at 65° C. and stir for 1 hour, then add 45 parts of 4-aminophenoxyphthalonitrile and 10 parts of curing agent and stir evenly.

[0049] The curing agent is a curing agent obtained by mixing isocyanate and trimethylolpropane trimethacrylate in a ratio of 1:1; and the solvent is ethyl acetate.

[0050] When preparing a halogen-free high Tg low dielectric loss copper clad laminate, the resin composition is evenly coated on a glass fiber cloth and baked at 125° C. for 35 seconds to obtain a prepreg; preferably, the amount of the resin composition accounts for 45% of the total mass of the prepreg; the prepreg and copper foil are stacked and pressed; pressing parameters: pressure is 550 psi; pressing time is 100 minutes.

[0051] Example 3

[0052] In some embodiments, the resin composition for a halogen-free, high Tg, low dielectric loss copper clad laminate is prepared by the following method:

[0053] 1.1. Preparation of modified resin: 50 parts of linear phenolic epoxy resin and 50 parts of bismaleimide resin are mixed to obtain a mixed resin; 11.5 parts of terephthaloyl chloride and 8 parts of 3-((2-hydroxyethyl)amino)propanol are mixed, esterification and cyclization reaction are carried out to obtain a cyclic prepolymer; 10.5 parts of naringenin are added dropwise to the cyclic prepolymer, and the mixture is mechanically stirred at 2000 r / min for 25 minutes to obtain a modifier; the modifier is mixed with the mixed resin, and mechanically stirred at 700 r / min for 35 minutes to obtain a modified resin;

[0054] The modified resin uses naringenin, terephthaloyl chloride and 3-((2-hydroxyethyl)amino)propanol as modifiers to modify the mixed resin of linear phenolic epoxy resin and bismaleimide resin;

[0055] 1.2. Preparation of polymer nanospheres: 20 parts of 2-methylene-4-phenyl-1,3-dioxolane and 11 parts of γ-aminopropyltriethoxysilane were mechanically stirred at 700 r / min, 12 parts of styrene containing 6% by mass of divinylbenzene were added dropwise, stirred and reacted at 85°C for 6 hours, dried at low temperature (<50°C), and granulated to obtain nanospheres;

[0056] 1.3. Preparation of three-dimensional ceramic network filler: 2.5 parts of Al(NO3)3·9H2O, 4.5 parts of Na2CO3·10H2O, 10.5 parts of mullite powder and 16 parts of anhydrous ethanol were mixed, and then 5 parts of tetrabutyl titanate were added, and the mixture was stirred and reacted at 46°C for 2 hours to obtain a precursor solution; the precursor solution was spread on dust-free paper, and the template was first dried to obtain a template, and then the template was calcined at 600°C for 4.5 hours to form a template with a three-dimensional network morphology, and then the template was crushed and sieved to 250 mesh;

[0057] 1.4. Prepare a resin composition: first place 100 parts of modified resin, 30 parts of polymer nanospheres, 20 parts of three-dimensional ceramic network fillers and 70 parts of solvent at 58°C and stir for 1.6 hours, then add 35 parts of 4-aminophenoxyphthalonitrile and 15 parts of curing agent and stir evenly.

[0058] The curing agent is a curing agent obtained by mixing isocyanate and trimethylolpropane trimethacrylate in a ratio of 1:1; and the solvent is dimethylformamide.

[0059] When preparing a halogen-free high Tg low dielectric loss copper clad laminate, the resin composition is evenly coated on a glass fiber cloth and baked at 115° C. for 45 seconds to obtain a prepreg; preferably, the amount of the resin composition accounts for 35% of the total mass of the prepreg; the prepreg and copper foil are stacked and pressed; pressing parameters: pressure is 250 psi; pressing time is 115 minutes.

[0060] Comparative Example 1

[0061] The difference from Example 3 is that the polymer nanospheres are removed from the raw materials.

[0062] In some embodiments, the resin composition for a halogen-free, high Tg, low dielectric loss copper clad laminate is prepared by the following method:

[0063] 1.1. Preparation of modified resin: 50 parts of linear phenolic epoxy resin and 50 parts of bismaleimide resin are mixed to obtain a mixed resin; 11.5 parts of terephthaloyl chloride and 8 parts of 3-((2-hydroxyethyl)amino)propanol are mixed, esterification and cyclization reaction are carried out to obtain a cyclic prepolymer; 10.5 parts of naringenin are added dropwise to the cyclic prepolymer, and the mixture is mechanically stirred at 2000 r / min for 25 minutes to obtain a modifier; the modifier is mixed with the mixed resin, and mechanically stirred at 700 r / min for 35 minutes to obtain a modified resin;

[0064] The modified resin uses naringenin, terephthaloyl chloride and 3-((2-hydroxyethyl)amino)propanol as modifiers to modify the mixed resin of linear phenolic epoxy resin and bismaleimide resin;

[0065] 1.2. Preparation of three-dimensional ceramic network filler: 2.5 parts of Al(NO3)3·9H2O, 4.5 parts of Na2CO3·10H2O, 10.5 parts of mullite powder and 16 parts of anhydrous ethanol were mixed, and then 5 parts of tetrabutyl titanate were added, and the mixture was stirred and reacted at 46°C for 2 hours to obtain a precursor solution; the precursor solution was spread on dust-free paper, and the template was first dried to obtain a template, and then the template was calcined at 600°C for 4.5 hours to form a template with a three-dimensional network morphology, and then the template was crushed and sieved to 250 mesh;

[0066] 1.3. Prepare a resin composition: first place 100 parts of modified resin, 20 parts of three-dimensional ceramic network filler and 70 parts of solvent at 58° C. and stir for 1.6 hours, then add 35 parts of 4-aminophenoxyphthalonitrile and 15 parts of curing agent and stir evenly.

[0067] The curing agent is a curing agent obtained by mixing isocyanate and trimethylolpropane trimethacrylate in a ratio of 1:1; and the solvent is dimethylformamide.

[0068] When preparing the copper clad laminate, the resin composition is evenly coated on the glass fiber cloth and baked at 115°C for 45 seconds to obtain a prepreg; preferably, the amount of the resin composition accounts for 35% of the total mass of the prepreg; the prepreg and the copper foil are stacked and pressed; the pressing parameters are: the pressure is 250psi; the pressing time is 115 minutes.

[0069] Comparative Example 2

[0070] The difference from Example 3 is that 3-((2-hydroxyethyl)amino)propanol is removed from the raw materials, so that terephthaloyl chloride and 3-((2-hydroxyethyl)amino)propanol cannot undergo esterification and cyclization to obtain a cyclic prepolymer.

[0071] In some embodiments, the resin composition for a halogen-free, high Tg, low dielectric loss copper clad laminate is prepared by the following method:

[0072] 1.1. Preparation of modified resin: 50 parts of linear phenolic epoxy resin and 50 parts of bismaleimide resin were mixed to obtain a mixed resin; 10.5 parts of naringenin were added dropwise to 11.5 parts of terephthaloyl chloride, and the mixture was stirred mechanically at 2000 r / min for 25 min to obtain a modifier; the modifier was mixed with the mixed resin, and the mixture was stirred mechanically at 700 r / min for 35 min to obtain a modified resin;

[0073] The modified resin uses naringenin and terephthaloyl chloride as modifiers to modify the mixed resin of linear phenolic epoxy resin and bismaleimide resin;

[0074] 1.2. Preparation of polymer nanospheres: 20 parts of 2-methylene-4-phenyl-1,3-dioxolane and 11 parts of γ-aminopropyltriethoxysilane were mechanically stirred at 700 r / min, 12 parts of styrene containing 6% by mass of divinylbenzene were added dropwise, stirred and reacted at 85°C for 6 hours, dried at low temperature (<50°C), and granulated to obtain nanospheres;

[0075] 1.3. Preparation of three-dimensional ceramic network filler: 2.5 parts of Al(NO3)3·9H2O, 4.5 parts of Na2CO3·10H2O, 10.5 parts of mullite powder and 16 parts of anhydrous ethanol were mixed, and then 5 parts of tetrabutyl titanate were added, and the mixture was stirred and reacted at 46°C for 2 hours to obtain a precursor solution; the precursor solution was spread on dust-free paper, and the template was first dried to obtain a template, and then the template was calcined at 600°C for 4.5 hours to form a template with a three-dimensional network morphology, and then the template was crushed and sieved to 250 mesh;

[0076] 1.4. Prepare a resin composition: first place 100 parts of modified resin, 30 parts of polymer nanospheres, 20 parts of three-dimensional ceramic network fillers and 70 parts of solvent at 58°C and stir for 1.6 hours, then add 35 parts of 4-aminophenoxyphthalonitrile and 15 parts of curing agent and stir evenly.

[0077] The curing agent is a curing agent obtained by mixing isocyanate and trimethylolpropane trimethacrylate in a ratio of 1:1; and the solvent is dimethylformamide.

[0078] When preparing the copper clad laminate, the resin composition is evenly coated on the glass fiber cloth and baked at 115°C for 45 seconds to obtain a prepreg; preferably, the amount of the resin composition accounts for 35% of the total mass of the prepreg; the prepreg and the copper foil are stacked and pressed; the pressing parameters are: the pressure is 250psi; the pressing time is 115 minutes.

[0079] Experimental example

[0080] The following properties of the copper clad laminates prepared in Examples 1-3 and Comparative Examples 1-2 were tested respectively:

[0081] 1) Glass transition temperature Tg;

[0082] 2) Dielectric constant Dk;

[0083] 3) Dielectric loss Df;

[0084] 4) Thermal stratification time T288;

[0085] 5) Flame retardant properties;

[0086] 6) Copper foil peel strength PS;

[0087] 7) Water absorption rate.

[0088] The test results are shown in Table 1.

[0089] Table 1 Comparison of the performance of copper clad laminates prepared in Examples 1-3 and Comparative Examples 1-2

[0090] project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Tg(℃) 248 234 246 203 196 Dk(10GHz) 3.46 3.84 3.53 4.05 3.77 Df(10GHz) 0.0028 0.0037 0.0030 0.0052 0.0042 T288(min) 85 91 75 69 48 Flame retardant properties V-0 V-0 V-0 V-0 V-1 PS(N / cm) 1.15 1.20 1.18 1.01 0.97 Water absorption (%) 0.09 0.08 0.11 0.09 0.10

[0091] It can be seen from Table 1 that the cyclic prepolymer obtained by introducing terephthaloyl chloride and 3-((2-hydroxyethyl)amino)propanol to undergo esterification and cyclization reaction is beneficial to improving the network crosslinking density, dielectric properties, flame retardant properties and heat resistance of the resin composition system, showing the improvement of glass transition temperature Tg, thermal delamination time T288, and copper foil peeling strength PS; by introducing polymer nanospheres, it is beneficial to fill the polymer nanospheres into the gaps of the three-dimensional ceramic network filler, and then by compounding with modified resins and other raw materials, the network crosslinking density of the resin composition system can be further enhanced, which is beneficial to reducing the dielectric constant Dk and dielectric loss Df. The copper clad laminate finally prepared has a high glass transition temperature Tg, a high thermal delamination time T288, a high copper foil peeling strength PS, a low dielectric constant Dk and a low dielectric loss Df. The glass transition temperature Tg can reach above 250°C, the dielectric loss can reach below 0.004, and it has halogen-free flame retardant properties and good comprehensive performance.

[0092] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. Such modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A halogen-free high Tg low dielectric loss copper clad laminate resin material, characterized in that: The invention comprises the following raw materials in parts by weight: 80 to 120 parts of modified resin, 30 to 45 parts of 4-aminophenoxyphthalonitrile, 22 to 40 parts of polymer nano-microspheres, 15 to 30 parts of three-dimensional ceramic network filler, 10 to 20 parts of curing agent, and 50 to 100 parts of solvent; The modified resin is obtained by using naringenin, terephthaloyl chloride and 3-((2-hydroxyethyl)amino)propanol as modifiers to modify a mixed resin of a linear phenolic epoxy resin and a bismaleimide resin; the mass ratio of naringenin, terephthaloyl chloride and 3-((2-hydroxyethyl)amino)propanol is 8.3-13.7:10.8-12.5:7-9.

3.

2. The halogen-free high Tg low dielectric loss copper clad laminate resin material according to claim 1, characterized in that: The preparation method of the modified resin is: Mixing 40 to 60 parts of novolac epoxy resin and 40 to 60 parts of bismaleimide resin to obtain a mixed resin; 10.8-12.5 parts of terephthaloyl chloride and 7-9.3 parts of 3-((2-hydroxyethyl)amino)propanol are mixed to undergo esterification and cyclization to obtain a cyclic prepolymer; 8.3-13.7 parts of naringenin are added dropwise to the cyclic prepolymer, and stirred mechanically at a high speed of 1800-2500 r / min for 15-35 minutes to obtain a modifier; The modifier is mixed with the mixed resin, and mechanically stirred at a speed of 500 to 800 r / min for 25 to 45 minutes to obtain a modified resin.

3. The halogen-free, high Tg, low dielectric loss resin material for copper-clad laminates according to claim 2, characterized in that: The preparation method of the polymer nano-microspheres is as follows: 18 to 22 parts of 2-methylene-4-phenyl-1,3-dioxolane and 10 to 12 parts of γ-aminopropyltriethoxysilane are mechanically stirred at a speed of 600 to 800 r / min, 10 to 14 parts of styrene containing 5 to 7% by mass of divinylbenzene are added dropwise, the reaction is stirred at 80 to 95° C. for 5 to 7 hours, low-temperature drying and granulation are performed to obtain the nano-microspheres.

4. The halogen-free high Tg low dielectric loss copper clad laminate resin material according to claim 3, characterized in that: The preparation method of the three-dimensional ceramic network filler is as follows: 2 to 3 parts of Al(NO3)3·9H2O, 4 to 5 parts of Na2CO3·10H2O, 10 to 11 parts of mullite powder and 10 to 20 parts of anhydrous ethanol are mixed, and then 4 to 6 parts of tetrabutyl titanate are added, and the mixture is stirred and reacted at 45 to 66°C for 1 to 3 hours to obtain a precursor solution; the precursor solution is spread on dust-free paper, and first dried to obtain a template, and then the template is calcined at 500 to 700°C to form a template with a three-dimensional network morphology, and then the template is crushed and sieved to 200 to 300 meshes.

5. The halogen-free high Tg low dielectric loss copper clad laminate resin material according to claim 4, characterized in that: The curing agent is a curing agent obtained by mixing isocyanate and trimethylolpropane trimethacrylate in a ratio of 1:

1.

6. The halogen-free high Tg low dielectric loss copper clad laminate resin material according to claim 5, characterized in that: The solvent is acetone, ethyl acetate or dimethylformamide.

7. The halogen-free high Tg low dielectric loss copper clad laminate resin material according to claim 6, characterized in that: The preparation method of the resin composition is: firstly, the modified resin, polymer nano-microspheres, three-dimensional ceramic network filler and solvent are placed at 55-65° C. and stirred for 1-2 hours, and then 4-aminophenoxyphthalonitrile and curing agent are added and stirred evenly.

8. The halogen-free, high Tg, low dielectric loss resin material for copper-clad laminates according to claim 7, characterized in that: The resin composition is uniformly coated on the glass fiber cloth and baked at 105-125° C. for 35-55 seconds to obtain a prepreg; the prepreg and copper foil are stacked and pressed to prepare a halogen-free high Tg low dielectric loss copper clad laminate.

9. The halogen-free, high Tg, low dielectric loss resin material for copper-clad laminates according to claim 8, characterized in that: The amount of the resin composition is 25-45% of the total mass of the prepreg; the pressure is 100-550 psi; and the pressing time is 100-125 minutes.

10. A process for preparing the halogen-free, high Tg, low dielectric loss resin material for copper-clad laminates according to claim 7, characterized in that: The following steps are involved:

1. Preparation of modified resin The invention adopts naringenin, terephthaloyl chloride and 3-((2-hydroxyethyl)amino)propanol as modifiers to modify the mixed resin of linear phenolic epoxy resin and bismaleimide resin; the mass ratio of naringenin, terephthaloyl chloride and 3-((2-hydroxyethyl)amino)propanol is 8.3-13.7:10.8-12.5:7-9.3; 2. Preparation of polymer nanospheres: 18 to 22 parts of 2-methylene-4-phenyl-1,3-dioxolane and 10 to 12 parts of γ-aminopropyltriethoxysilane are mechanically stirred at 600 to 800 r / min, 10 to 14 parts of styrene containing 5 to 7% by mass of divinylbenzene are added dropwise, stirred and reacted at 80 to 95°C for 5 to 7 hours, dried at low temperature, and granulated to obtain nanospheres; 3. Preparation of three-dimensional ceramic network filler: 2-3 parts of Al(NO3)3·9H2O, 4-5 parts of Na2CO3·10H2O, 10-11 parts of mullite powder and 10-20 parts of anhydrous ethanol are mixed, and then 4-6 parts of tetrabutyl titanate are added, and the mixture is stirred and reacted at 45-66°C for 1-3 hours to obtain a precursor solution; the precursor solution is spread on dust-free paper, and first dried to obtain a template, and then the template is calcined at 500-700°C to form a template with a three-dimensional network morphology, and then the template is crushed and sieved to 200-300 mesh; 4. Preparation of Resin Composition First, the modified resin, polymer nano-microspheres, three-dimensional ceramic network filler and solvent are placed at 55-65° C. and stirred for 1-2 hours, and then 4-aminophenoxyphthalonitrile and a curing agent are added and stirred evenly.