Low-dielectric high-Tg resin composition, prepreg sheet and metal laminated plate

Abstract

The invention discloses a low-dielectric high-Tg resin composition, a prepreg sheet and a metal laminated plate. The resin composition comprises a resin system, a halogen-free flame retardant, a coupling agent and an inorganic filling material. The resin system includes a low dielectric resin, a cross-linking agent, and a polyindane resin added in specific weight percentages, and the low dielectric resin is formed from a monomer composition including styrene, divinyl benzene, and ethylene. Therefore, the resin composition with low dielectric constant and high Tg has a glass transition temperature of not less than 200 DEG C, a dielectric constant (Dk) at a frequency of 10 GHz after curing is in a range of 3.0 to 3.2, and a dielectric loss factor (Df) is less than 0.0013. On the basis, the invention also discloses a pre-impregnated sheet and a metal laminated plate applying the low-dielectric high-Tg resin composition.

Description

Technical Field

[0001] The present invention relates to a resin composition and its applications, in particular to a resin composition with low dielectric constant and high Tg, and a prepreg sheet and a metal laminate made of this resin composition. Background Art

[0002] 5G communication can achieve faster and lower-latency transmission effects through the characteristics of high frequency and short wavelength. Currently, in the application fields of 5G, the most concerned characteristics are nothing but the dielectric constant and dissipation factor of materials. Low-dielectric-characteristic materials can reduce signal loss and heat generation in the application scenarios of 5G high-frequency signal transmission. Therefore, the industry is actively developing low-dielectric-characteristic materials that meet the application requirements.

[0003] Among resin materials, polytetrafluoroethylene (PTFE) and polyphenylene ether (PPO / PPE) have attracted particular attention due to their low dielectric constant and dissipation factor. Among them, polytetrafluoroethylene not only has poor processability, but also has poor adhesion to copper foil, which is not conducive to manufacturing circuit boards with high layer counts or high-density interconnect designs. The processability of polyphenylene ether is much better than that of polytetrafluoroethylene materials, and it has become one of the main options to replace polytetrafluoroethylene. Currently, the developed low-dielectric-characteristic materials with polyphenylene ether as the main component (main framework) have been adopted by many copper-clad laminate (CCL) manufacturers.

[0004] High-speed products such as high-end server products pay more attention to the dielectric loss of the board material. However, it is difficult to reduce the dissipation factor of the low-dielectric-characteristic materials with polyphenylene ether as the main component (main framework) to a lower level, and gradually it cannot meet the application requirements. Although the dissipation factor can be reduced by using polyphenylene ether in combination with different types of low-dielectric resins, it is also easy to cause a decrease in the glass transition temperature (Tg), so it is restricted in applications.

[0005] Therefore, developing a low-dielectric-characteristic material with low dielectric constant, low dissipation factor and high glass transition temperature has become an urgent goal for those skilled in the art to develop. Summary of the Invention

[0006] One of the purposes of the present invention is to provide a resin composition with low dielectric constant and high Tg in view of the deficiencies of the prior art. After curing, it can be applied to the board material, which is beneficial to the high-frequency and high-speed signal transmission and long-term reliability of the board material. The present invention also discloses a prepreg sheet and a metal laminate using the above-mentioned resin composition with low dielectric constant and high Tg.

[0007] To achieve the above-mentioned invention object, one of the technical solutions adopted by the present invention is to provide a resin composition with low dielectric constant and high Tg, which includes a resin system of component (A), a halogen-free flame retardant of component (B), a coupling agent of component (C), and an inorganic filler of component (D). Based on the total weight of the resin system, the resin system contains 10% to 40% by weight of a low dielectric resin, 5% to 20% by weight of a crosslinking agent, and 10% to 70% by weight of a polyindene resin. The low dielectric resin is formed from a monomer composition containing styrene, divinylbenzene, and ethylene. In the resin composition with low dielectric constant and high Tg, with respect to 100 parts by weight of the resin system, the dosage of the halogen-free flame retardant is 20 phr to 45 phr, the dosage of the coupling agent is 0.05 phr to 1 phr, and the dosage of the inorganic filler is 80 phr to 120 phr. In addition, the glass transition temperature of the resin composition with low dielectric constant and high Tg is not less than 200 °C, and the dielectric constant (Dk) of the resin composition with low dielectric constant and high Tg after curing at a frequency of 10 GHz is in the range of 3.0 to 3.2, and the dielectric loss factor (Df) is less than 0.0013.

[0008] In an embodiment of the present invention, the number average molecular weight of the polyindene resin is in the range of 300 g / mol to 1000 g / mol.

[0009] In an embodiment of the present invention, the polyindene resin contains two or more reactive functional groups among acrylic groups, styryl groups, and maleimide groups.

[0010] In an embodiment of the present invention, the number average molecular weight of the low dielectric resin is in the range of 4500 g / mol to 6500 g / mol.

[0011] In an embodiment of the present invention, based on 100 mol% of all monomer units of the low dielectric resin, the content of styrene units is in the range of 10% to 40%, the content of divinylbenzene units is in the range of 10% to 40%, and the content of ethylene units is in the range of 10% to 20%.

[0012] In an embodiment of the present invention, the inorganic filler is silica prepared by a synthetic method, and its average particle size D50 is in the range of 2.0 μm to 3.0 μm.

[0013] In an embodiment of the present invention, the specific gravity of the silica is 2.0 g / cm 3 to 2.5 g / cm 3 .

[0014] In an embodiment of the present invention, the halogen-free flame retardant is a compound having the structure shown in the following formula (I):

[0015]

[0016] Among them, R1 represents a covalent bond, -CH2-,

[0017] Among them, R2, R3, R4, and R5 are each independently H, an alkyl group, or

[0018] In an embodiment of the present invention, the crosslinking agent is selected from the group consisting of: triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethallyl isocyanurate (TMAIC), diallyl phthalate, divinylbenzene, and 1,2,4-triallyl trimellitate.

[0019] Another object of the present invention is to provide a prepreg sheet, which is obtained by coating or impregnating a reinforcing material with the low dielectric high-Tg resin composition as described above.

[0020] Another object of the present invention is to provide a metal laminate, which is obtained by laminating the prepreg sheet as described above with a metal layer, or by coating the low dielectric high-Tg resin composition as described above on a metal layer.

[0021] Generally speaking, the low dielectric high-Tg resin composition provided by the present invention, by virtue of "the resin system contains 10% to 40% by weight of a low dielectric resin, 5% to 20% by weight of a crosslinking agent, and 10% to 70% by weight of a polyindane resin based on the total weight of the resin system" and "the low dielectric resin is formed from a monomer composition containing styrene, divinylbenzene, and ethylene", can achieve excellent high-frequency low dielectric properties (Low Dk / Low Df), especially Df < 0.0013, to maintain a stable low transmission loss for a long time, and can maintain the glass transition temperature (Tg) above 200 °C, thereby improving the sheet properties required in practical applications such as water absorption, heat resistance, and peeling strength.

[0022] To further understand the features and technical content of the present invention, please refer to the following detailed description and drawings of the present invention. However, the provided drawings are only for reference and illustration, and are not used to limit the present invention. Description of the Drawings

[0023] Figure 1 and Figure 2 Schematic diagram of manufacturing a prepreg using the resin composition with low dielectric constant and high Tg that can improve processability according to the present invention.

[0024] Figures 3 to 5 Schematic diagram of manufacturing a metal laminate using the resin composition with low dielectric constant and high Tg that can improve processability according to the present invention. Detailed implementation manners

[0025] The following are implementation manners of the present invention regarding "resin composition with low dielectric constant and high Tg that can improve processability, prepreg, and metal laminate" disclosed through specific specific examples. Those skilled in the art can understand the advantages and effects of the present invention from the content disclosed in this specification. The present invention can be implemented or applied through other different specific examples, and various details in this specification can also be modified and changed based on different viewpoints and applications without departing from the concept of the present invention. Additionally, the drawings of the present invention are only for simple schematic illustration and are not drawn according to actual dimensions, stated in advance. The following implementation manners will further detail the related technical content of the present invention, but the disclosed content is not used to limit the protection scope of the present invention.

[0026] Unless otherwise defined, the terms used herein have the same meaning as commonly understood by those skilled in the art. The materials involved in each example are commercially available or prepared according to existing technologies if not otherwise specified. The operations or instruments involved in each example are conventional operations or instruments in the art if not otherwise specified.

[0027] Existing low dielectric constant materials mainly have a polyphenylene ether resin as the main framework and it is difficult to reduce the loss factor to a lower level. Although a new low dielectric constant resin, polydivinylbenzene (PDVB), can be used in combination to reduce the loss factor, it also reduces the glass transition temperature (Tg) at the same time, thus being limited in practical applications. Therefore, the present invention proposes a new concept: using a low dielectric constant resin containing styrene, divinylbenzene, and ethylene monomer units in combination with a polyindene resin to maintain a sufficient glass transition temperature (Tg) while satisfying the low dielectric loss characteristics.

[0028] Specifically, an embodiment of the present invention provides a resin composition with low dielectric constant and high Tg embodying the above invention concept, including a resin system of component (A), a halogen-free flame retardant of component (B), a coupling agent of component (C), and an inorganic filler of component (D). Hereinafter, various components will be described in detail.

[0029] Resin system of component (A)

[0030] The resin system constituting the resin composition with low dielectric constant and high Tg of the present invention, based on the total weight of the resin system, comprises: 10% to 40% by weight of a low dielectric resin, 5% to 20% by weight of a crosslinking agent, and 10% to 70% by weight of a polyindane resin.

[0031] In an embodiment of the present invention, the low dielectric resin is essentially a copolymer containing olefin-based monomers, which is formed from a monomer composition comprising styrene, divinylbenzene, and ethylene. Among them, divinylbenzene, as a monomer unit in the low dielectric resin, can play a role in increasing the glass transition temperature (Tg); ethylene, as a monomer unit in the low dielectric resin, can play a role in reducing the dissipation factor (Df); and styrene, as a monomer unit in the low dielectric resin, can play a role in maintaining good heat resistance.

[0032] Preferably, based on 100 mol% of all monomer units of the low dielectric resin, the content of styrene units is in the range of 10% to 40%, the content of divinylbenzene units is in the range of 10% to 40%, and the content of ethylene units is in the range of 10% to 20%. Therefore, the low dielectric properties and glass transition temperature of the applied sheet can be taken into account.

[0033] In actual application, relative to the total weight of the resin system being 100% by weight, the content of the low dielectric resin can be 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, or 40% by weight. Additionally, the number average molecular weight of the low dielectric resin can be in the range of 4500 g / mol to 6000 g / mol.

[0034] In an embodiment of the present invention, the polyindane resin can cooperate with the above-mentioned low dielectric resin to maintain the glass transition temperature (Tg) above 200°C while reducing the dissipation factor (Df). It is worth noting that the polyindane resin can be used as a modifier to improve the processability, stability, thermal properties, viscoelasticity, rheology, adhesion, and / or mechanical properties of the resin composition. For example, compared with the traditional resin composition with a polyphenylene ether resin as the main framework, the resin composition of the present invention with a polyindane resin as the main framework can bring improved tear strength to the applied sheet.

[0035] Preferably, the polyindane resin contains two or more reactive functional groups among acrylic groups, styryl groups, and maleimide groups, which is beneficial to form a three-dimensional network structure and achieve the required physical and chemical properties (such as high glass transition temperature, low water absorption, and good heat resistance).

[0036] In actual application, relative to the total weight of the resin system being 100% by weight, the content of the polyindane resin can be 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, or 70% by weight. The main molecular chain of the polyindane resin can contain more than 90% of indane repeating units. In addition, the number-average molecular weight of the polyindane resin is in the range of 300 g / mol to 1000 g / mol. And the polyindane resin can be partially or completely hydrogenated to regulate the aromaticity, which is beneficial to improving the compatibility performance.

[0037] In the embodiments of the present invention, the crosslinking agent is a component having an unsaturated functional group containing a double bond or a triple bond and capable of undergoing a crosslinking reaction to form a three-dimensional network structure, such as but not limited to a monofunctional crosslinking agent (having only one unsaturated functional group in the molecule) or a polyfunctional crosslinking agent (having two or more unsaturated functional groups in the molecule). The type of the crosslinking agent is not particularly limited, and preferably it has good compatibility with the above-mentioned resin components.

[0038] Specifically, as the crosslinking agent of the resin system of component (A), it can be selected from the group consisting of: 1,3,5-triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethallyl isocyanurate (TMAIC), diallyl phthalate, 1,2,4-triallyltrimellitate, and divinylbenzene. The above-mentioned crosslinking agents can be used alone or in combination.

[0039] Relative to the total weight of the resin system being 100% by weight, the content of the crosslinking agent can be 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, or 30% by weight.

[0040] In the embodiments of the present invention, the resin system of component (A) can further contain a polyphenylene ether resin as needed, and the terminal of its main molecular chain contains an unsaturated functional group, such as but not limited to a hydroxyl group, a vinyl group, a styryl group, a vinylbenzyl group, an allyl group, an acryloyl group, a methacrylate group, an epoxy group, and a maleimide group. The unsaturated functional group refers to a group capable of undergoing an addition polymerization reaction with other components having unsaturated functional groups, and the addition polymerization reaction can be initiated by light or heat in the presence of a polymerization initiator.

[0041] Specifically, the polyphenylene ether resin of the resin system as component (A) can be selected from the group consisting of: polyphenylene ether resins containing terminal hydroxyl groups, polyphenylene ether resins containing terminal vinyl groups, polyphenylene ether resins containing terminal styryl groups, polyphenylene ether resins containing terminal vinylbenzyl groups, polyphenylene ether resins containing terminal allyl groups, polyphenylene ether resins containing terminal acryloyl groups, polyphenylene ether resins containing terminal methacrylate groups, polyphenylene ether resins containing terminal epoxy groups, and polyphenylene ether resins containing terminal maleimide groups. The above-mentioned polyphenylene ether resins can be used alone or in combination.

[0042] Relative to 100% by weight of the total weight of the resin system, the content of the polyphenylene ether resin can be 20% to 60% by weight. It is worth noting that in the presence of the polyindene resin, the content of the polyphenylene ether resin in the resin system can be significantly reduced, even reduced to 0% (completely not added).

[0043] The weight-average molecular weight of the polyphenylene ether resin can be in the range of 1000 g / mol to 20000 g / mol, preferably in the range of 1000 g / mol to 10000 g / mol. If the molecular weight of the polyphenylene ether resin is too large, the fluidity and solvent solubility of the polyphenylene ether resin may become poor. If the molecular weight of the polyphenylene ether resin is too small, the electrical properties and thermal stability of the resin composition may be impaired.

[0044] In actual application, two different polyphenylene ether resins can be used in combination in the resin system of component (A), such as but not limited to: a polyphenylene ether resin with a bismaleimide group at the end of the molecular main chain and a polyphenylene ether resin with a hydroxyl group, styryl group, methacrylate group or epoxy group at the end of the molecular main chain. Alternatively, three different polyphenylene ether resins can be used in combination in the resin system of component (A), such as but not limited to: a polyphenylene ether resin with a bismaleimide group at the end of the molecular main chain, a polyphenylene ether resin with a styryl group at the end of the molecular main chain, and a polyphenylene ether resin with a methacrylate group at the end of the molecular main chain.

[0045] The preparation method of the above-mentioned polyphenylene ether resin with unsaturated functional groups is not the key technical point of the present invention, and can be obtained or completed by those skilled in the art based on the content disclosed in this specification and the general knowledge they possess.

[0046] Halogen-free flame retardant of component (B)

[0047] The halogen-free flame retardant that constitutes the resin composition with low dielectric constant and high Tg of the present invention can adopt a phosphorus-containing flame retardant, which is used to improve the flame retardancy of the prepared electronic materials and meet the requirements of halogen-free environmental protection. In practical applications, the phosphorus-containing flame retardant can be selected from the group consisting of the following: phosphate esters, phosphazenes, phosphine oxides, ammonium polyphosphate, melamine polyphosphate, melamine phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). The above-mentioned halogen-free flame retardants can be used alone or in combination. However, the present invention is not limited to the above examples.

[0048] Examples of the halogen-free flame retardant of phosphate esters include: triphenyl phosphate (TPP), tetraphenyl resorcinol bis(diphenylphosphate) (RDP), bisphenol A bis(diphenylphosphate) (BDP), Resorcinol bis(di-2,6-xylyl phosphate) (RXP).

[0049] Examples of the halogen-free flame retardant of phosphazenes include cyclic phosphazene compounds and linear phosphazene compounds.

[0050] Examples of the halogen-free flame retardant of phosphine oxides include: tris(4-methoxyphenyl)phosphine oxide, diphenylphosphine oxide, triphenylphosphine oxide, and the phosphine oxide shown by the following formula (I) (the product with the model number PQ-60 of Jin Yi Chemical Industry). It is worth mentioning that the phosphine oxide with the structure of formula (I) can bring the effect of improving the low dielectric constant characteristics to the resin composition in addition to the known flame retardant characteristics, which is beneficial to the application in the high-frequency field.

[0051]

[0052] Among them, R1 represents a covalent bond, -CH2-,

[0053] wherein, R2, R3, R4, and R5 are each independently H, an alkyl group, or

[0054] Regarding the resin system of component (A) in 100 parts by weight, the amount of the halogen-free flame retardant of component (B) is 20 phr to 45 phr, such as but not limited to 20 phr, 25 phr, 30 phr, 35 phr, 40 phr, or 45 phr. If the amount of the halogen-free flame retardant is less than the above range, the electronic materials prepared from the resin composition cannot achieve the required flame retardant performance. If the amount of the halogen-free flame retardant is greater than the above range, it may negatively affect the electrical properties and practical required characteristics such as water absorption and tear strength.

[0055] The coupling agent of component (C)

[0056] The coupling agent constituting the low dielectric high Tg resin composition of the present invention can be at least one of a silane compound and a siloxane compound, and is used to increase the interfacial adhesion strength between the resin and a reinforcing material such as a fiber cloth, and to improve the compatibility between the resin and a reinforcing material such as a fiber cloth and an inorganic powder material.

[0057] Examples of the silane compound include amino silane, vinyl silane, acrylic silane, and epoxy silane. Examples of the siloxane compound include amino siloxane, vinyl siloxane, acrylic siloxane, and epoxy siloxane.

[0058] Regarding the resin system of component (A) in 100 parts by weight, the amount of the coupling agent of component (D) can be 0.05 phr to 1 phr, preferably 0.3 phr to 0.7 phr.

[0059] In some embodiments, regarding the resin system of component (A) in 100 parts by weight, the amount of the coupling agent of component (D) can be 0.05 phr, 0.1 phr, 0.2 phr, 0.3 phr, 0.4 phr, 0.5 phr, 0.6 phr, 0.7 phr, 0.8 phr, 0.9 phr, or 1 phr.

[0060] The inorganic filler of component (D)

[0061] The inorganic filler constituting the resin composition with low dielectric constant and high Tg of the present invention can be selected from the group consisting of: silica, alumina, zinc oxide, titanium oxide, magnesium oxide, antimony oxide, beryllium oxide, aluminum nitride, boron nitride, calcium carbonate, potassium titanate, glass fiber, barium titanate, barium sulfate, aluminum hydroxide, and magnesium hydroxide. The above inorganic fillers can be used alone or in combination. Therefore, not only can the dielectric constant and dielectric loss be maintained at a lower level, but also the mechanical strength, thermal conductivity, heat resistance and other properties of the resin composition can be improved. However, the present invention is not limited to the above examples.

[0062] Preferably, the inorganic filler of component (E) is spherical silica, which can be prepared by a synthetic method. In addition, the specific gravity of spherical silica is 2.0 g / cm 3 to 2.5 g / cm 3 , and the average particle size D50 is in the range of 2.0 μm to 3.0 μm; the specific gravity of spherical silica is preferably 2.2 g / cm 3 . In addition, spherical silica can be surface-modified with at least one functional group in acrylic group or vinyl group to have good compatibility with the resin system of component (A), so that it can be added to the resin composition in a larger amount without damaging the properties required in practical applications.

[0063] Relative to 100 parts by weight of the resin system, the amount of the inorganic filler of component (E) is 80 phr to 120 phr, preferably 90 phr to 110 phr.

[0064] In some embodiments, relative to 100 parts by weight of the resin system of component (A), the amount of the inorganic filler of component (E) can be 80 phr, 85 phr, 90 phr, 95 phr, 100 phr, 105 phr, 110 phr, 115 phr or 120 phr.

[0065] Pre-impregnated sheet and metal laminate

[0066] Please refer to Figure 1 and Figure 2 , the present invention also provides a pre-impregnated sheet 1 (prepreg) and a metal laminate using the above resin composition with low dielectric constant and high Tg. Specifically, the pre-impregnated sheet 1 is formed by coating or impregnating a reinforcing material 11 with a resin composition 12 having low dielectric constant and high Tg, so that the resin composition 12 with low dielectric constant and high Tg adheres to the reinforcing material 11 and forms a semi-cured state through high-temperature heating. The reinforcing material 11 is, for example but not limited to, an electronic-grade general-purpose glass fiber cloth.

[0067] Cooperate with Figures 3 to 5As shown, the metal laminate can be obtained by the following methods: laminating the above-mentioned prepreg sheet 1 with at least one metal layer 2 (such as a copper foil layer) and bonding them together by hot pressing, or coating the above-mentioned resin composition 12 with low dielectric constant and high Tg on a metal layer 2 and fully drying and curing it. In the example of laminating the above-mentioned prepreg sheet 1 with at least one metal layer 2 (such as a copper foil layer), a predetermined number of prepreg sheets 1 can be stacked, and a metal layer 2 can be laminated on at least one outer side of the formed laminate 1'.

[0068] In actual application, the metal layer 2 on the outer side of the metal laminate can be patterned by conventional process steps to obtain a printed circuit board.

[0069] Performance evaluation

[0070] Use toluene to form a thermosetting resin varnish from the resin compositions shown in Table 1 and Table 2. Then, using Nanya fiberglass cloth (Nanya Plastics Corporation, product model NE1078) as the reinforcing material, impregnate the above-mentioned thermosetting resin varnish at room temperature, and then dry it at 130°C for several minutes to obtain a prepreg sheet with a resin content of 70% by weight. Then stack 4 prepreg bodies between 2 copper foils with a thickness of 35 μm and perform a hot pressing operation to obtain a copper foil substrate sample with a thickness of 0.4 mm. The above hot pressing operation is to apply a pressure of 25 kg / cm 2 at a temperature of 85°C and hold the temperature for 20 minutes, then heat it to 210°C at a heating rate of 3°C / min, hold the temperature for 120 minutes, and then slowly cool it to 130°C. The obtained copper foil substrate sample is evaluated for performance according to the following.

[0071] Glass transition temperature (°C): Tested with a dynamic mechanical analyzer (DMA).

[0072] Water absorption rate (%): After the sample is heated in a pressure cooker at 2 atm and 120°C for 120 minutes, calculate the weight change before and after heating.

[0073] T288 solder dip resistance: After the sample is heated in a pressure cooker at 2 atm and 120°C for 120 minutes, immerse it in a solder bath at 288°C and record the time when delamination occurs on the sample.

[0074] Dielectric constant (Dk) and dielectric loss (Df): After removing the copper foil from the sample, bake it in an oven at 105°C for 30 minutes, and then use an analyzer (product model E4991A) from Agilent Technologies to test the dielectric constant and dielectric loss at a frequency of 10 GHz.

[0075] Tear strength: Prepare a copper foil substrate sample of 1 cm × 10 cm and analyze the tear strength between the copper foil and the substrate with a universal testing tensile machine.

[0076] In Table 1 or Table 2, the details of each component are as follows:

[0077] Low dielectric resin: Product with the model Poly-DVB from DENKA Company;

[0078] Polyindene resin: Product with the model NE-X-9480 from DIC Corporation of Japan;

[0079] Polyphenylene ether resin: Product with the model MX9000 from SABIC Company;

[0080] BMI resin - 1: Product with the model MIR-3000-70MT from Nippon Kayaku Co., Ltd.;

[0081] BMI resin - 2: Product with the model MIR-5000-60T from Nippon Kayaku Co., Ltd.;

[0082] Crosslinking agent: TAIC from Evonik Company;

[0083] Flame retardant: Product with the model PQ-60 from Jin Yi Chemical Industry Company;

[0084] Synthetic silica: Product with the model EQ2410-SMC from Continental Mitsuki Company; Coupling agent: Product with the model Z-6030 from Dow Corning Company;

[0085] Peroxide: Product with the model Luperox F from ARKEMA Company.

[0086] Table 1

[0087]

[0088]

[0089] Table 2

[0090]

[0091]

[0092] As can be seen from Table 1 and Table 2 above, the resin compositions of Comparative Examples 1 to 3 only added a combination of polyphenylene ether resin and low-dielectric resin, without adding polyindene resin. The Df value of the prepared boards could not be reduced to below 0.0014 or even below 0.0013, that is, the required low-dielectric characteristics (Low Dk / Low Df) were not achieved. Although the resin compositions of Comparative Examples 2 and 3 had a higher Tg for the prepared boards due to the additional addition of BMI resin, their Df values also increased, raising concerns about increased transmission loss. In contrast, the resin compositions of Examples 1 to 3 used a combination of low-dielectric resin and polyindene resin, which could achieve the required lower low-dielectric constant and dielectric loss, maintain the glass transition temperature (Tg) above 200 °C, and not damage the practical properties such as water absorption and heat resistance. In addition, the resin compositions of Examples 1 to 3 could bring improved tear strength to the applied boards due to the use of polyindene resin.

[0093] Advantages of the Examples

[0094] The low-dielectric high-Tg resin composition provided by the present invention, by virtue of "the resin system comprises 10% to 40% by weight of low-dielectric resin, 5% to 20% by weight of crosslinking agent, and 10% to 70% by weight of polyindene resin based on the total weight of the resin system" and "the low-dielectric resin is formed from a monomer composition comprising styrene, divinylbenzene, and ethylene", can achieve excellent high-frequency low-dielectric characteristics (Low Dk / Low Df), especially Df < 0.0013, to maintain stable low transmission loss for a long time, and can maintain the glass transition temperature (Tg) above 200 °C, thereby improving the practical board properties such as water absorption, heat resistance, and peeling strength.

[0095] The content disclosed above is only the preferred feasible embodiments of the present invention, and does not limit the protection scope of the claims of the present invention. Therefore, all equivalent technical changes made by using the content of the specification and drawings of the present invention are included in the protection scope of the claims of the present invention.

Claims

1. A low dielectric high Tg resin composition, characterized in that: The low dielectric high Tg resin composition comprises: (A) a resin system comprising, based on the total weight of the resin system, 10 wt % to 40 wt % of a low dielectric resin, 5 wt % to 20 wt % of a crosslinking agent, and 10 wt % to 70 wt % of a polyindene resin, wherein the low dielectric resin is formed from a monomer composition comprising styrene, divinylbenzene, and ethylene; (B) Halogen-free flame retardant; (C) a coupling agent; and (D) Inorganic fillers; Wherein, relative to 100 parts by weight of the resin system, the amount of the halogen-free flame retardant is 20 phr to 45 phr, the amount of the coupling agent is 0.05 phr to 1 phr, and the amount of the inorganic filler is 80 phr to 120 phr; Among them, the glass transition temperature of the low-dielectric high-Tg resin composition is not less than 200°C, and the dielectric constant (Dk) of the low-dielectric high-Tg resin composition after curing at a frequency of 10 GHz is in the range of 3.0 to 3.2 and the dielectric loss factor (Df) is less than 0.0013.

2. The low dielectric high Tg resin composition according to claim 1, characterized in that: The number average molecular weight of the polyindane resin is in the range of 300 g / mol to 1000 g / mol.

3. The low dielectric high Tg resin composition according to claim 2, characterized in that: The polyindane resin contains two or more reactive functional groups selected from the group consisting of an acrylic group, a styrene group and a maleimide group.

4. The low dielectric high Tg resin composition according to claim 1, characterized in that: The number average molecular weight of the low dielectric resin is in the range of 4500 g / mol to 6500 g / mol.

5. The low dielectric high Tg resin composition according to claim 4, characterized in that: Based on 100 mol% of all monomer units of the low dielectric resin, the content of styrene units is in the range of 10% to 40%, the content of divinylbenzene units is in the range of 10% to 40%, and the content of ethylene units is in the range of 10% to 20%.

6. The low dielectric high Tg resin composition according to claim 1, characterized in that: The inorganic filler is silicon dioxide prepared by a synthetic method, and the average particle size D50 thereof is in the range of 2.0 μm to 3.0 μm.

7. The low dielectric high Tg resin composition according to claim 6, characterized in that: The specific gravity of the silicon dioxide is 2.0 g / cm 3 Up to 2.5g / cm 3 .

8. The low dielectric high Tg resin composition according to claim 1, characterized in that: The halogen-free flame retardant is a compound having a structure shown in the following formula (I): Wherein, R1 represents a covalent bond, -CH2-, Wherein, R2, R3, R4, R5 are each independently H, alkyl or 9. The low dielectric high Tg resin composition according to claim 1, characterized in that: The crosslinking agent is selected from the group consisting of: 1,3,5-triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethallylisocyanurate (TMAIC), diallyl phthalate, divinylbenzene and 1,2,4-Triallyl trimellitate.

10. A prepreg sheet, characterized in that: The prepreg is prepared by coating or impregnating a reinforcing material with the low dielectric and high Tg resin composition according to claim 1.

11. A metal laminate, characterized in that: The metal laminate is made by laminating the prepreg according to claim 10 with a metal layer, or by coating the low-dielectric and high-Tg resin composition according to claim 1 on a metal layer.

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