Cyclic olefin resin composition, resin material, method for producing the same, and use thereof

Abstract

This invention provides a cyclic olefin resin composition, a resin material, a method for producing the same, and its use. [Solution] The present invention discloses the use of a cyclic olefin resin composition M1 in the manufacture of a substrate material for high-frequency and high-speed information transmission devices, wherein the cyclic olefin resin composition M1 comprises component A and component B, wherein component A is a cyclic olefin, and component B is a ruthenium alkylidene compound represented by formula I and / or formula II or a salt thereof, and the molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:(7500~60000). The resin material manufactured using the cyclic olefin resin composition of the present invention exhibits low dielectric loss (D) under high-frequency conditions (frequency ≥ 1 GHz). f <0.001) and low dielectric constant (D k It has a <2.5) and excellent heat resistance. JPEG2026116846000069.jpg42169

Description

[Technical Field]

[0001] This application claims priority to Chinese Patent Application No. 202411987665.6, filed on 31 December 2024. This application incorporates the entire contents of the aforementioned Chinese Patent Application.

[0002] This invention relates to a cyclic olefin resin composition, a resin material, a method for producing the same, and its use. [Background technology]

[0003] Currently, technologies in the fields of AI and 5G high-frequency communication are developing rapidly, with numerous new applications and needs emerging one after another, and the market size continuing to expand. The rapid development of high-frequency and high-speed information transmission technologies has led to increasingly faster and more multi-functional information processing in communication products, significantly improving information processing efficiency. The development of high-frequency and high-speed information transmission technologies demands that new materials in this field possess lower dielectric constants, lower dielectric loss, and superior heat resistance in high-frequency environments. Therefore, the development of polymer materials with low dielectric constants, low dielectric loss, and excellent heat resistance has become a key focus in the field of materials research in recent years.

[0004] Currently, a new generation of high-performance basic materials with polymer structures containing only C and H elements, such as hydrocarbon resins, are rapidly developing in the field of high-frequency and high-speed information transmission. Compared to conventional materials, such materials exhibit extremely excellent low dielectric constant (D) in high-frequency application scenarios (frequency ≥ 1 GHz). k ) and low dielectric loss (D f ) Characteristics (D k <3.0, D f These materials exhibit a <0.003) and their processability far surpasses that of fluoropolymers (such as PTFE and PVDF).

[0005] With the development of related fields, higher demands are now being raised for substrate materials for the new generation of high-frequency and high-speed information transmission: Under high-frequency conditions (frequency ≥ 1 GHz), the dielectric constant D of the material is required. k <2.6, Df <0.001, and considering the usage environment of the material, the heat distortion temperature of the related material is required to be 105 °C or higher. This index poses a major challenge to current common materials. CN113736211B and CN112646322B disclose a polydicyclopentadiene / epoxy resin composite material used in the field of high-frequency copper foil substrates. The composite material manufactured by this technical solution has a dielectric constant D k > 2.5 and a dielectric loss D f > 0.01 under the condition of 1 GHz, and this technical solution cannot meet the performance requirements in the current high-frequency information transmission field.

[0006] CN111969319A discloses a method for manufacturing a polydicyclopentadiene material using a two-component resin system, which is applied to a radio signal transmission device in the 5G field as a low dielectric constant and low loss material. However, in the disclosed technical solution, the dielectric constant D of polydicyclopentadiene obtained at a test frequency of 1 MHz k reaches 2.78, and the dielectric loss D f already reaches 2.1×10 -3 . The dielectric properties of the polydicyclopentadiene material manufactured by this technical solution cannot fully meet the material performance requirements in the current high-frequency application field above 1 GHz.

[0007] CN117734286B discloses a high-temperature resistant and low dielectric hydrocarbon resin used in the field of copper foil substrates and its manufacturing method. The dielectric constant D of the material obtained by this technical solution k > 2.8, and it cannot meet the requirements of high-performance high-frequency applications.

[0008] CN117756971A discloses a method for manufacturing a low dielectric hydrocarbon resin using divinylbenzene as a monomer. The dielectric loss D of the polymer obtained by this technical solution f is in the range of 0.003 to 0.0045 and cannot fully meet the requirements in the current high-frequency communication field.

[0009] In its specification, CN111138755A states that polypropylene material is a typical low dielectric material, and its dielectric constant D k The dielectric loss D is in the range of 2.0 to 2.6. f The report points out that this value is 0.001 (60Hz), and since the dielectric loss of the material increases rapidly in high-frequency environments (above 1GHz), this performance index is insufficient to meet the application requirements of high-performance high-frequency materials.

[0010] Based on the above, the high-frequency information transmission materials reported in the prior art have the following defects: (1) The dielectric properties of materials obtained by compounding epoxy and cyclic olefin resins, particularly the dielectric loss under high-frequency conditions, are excessive; (2) Polydicyclopentadiene materials manufactured by conventional methods still have high high-frequency dielectric loss indices; (3) Low dielectric hydrocarbon resins exhibit dielectric properties slightly above the preferred value in a test environment of 1 GHz or higher; (4) Unmodified polypropylene material has high high-frequency dielectric loss and a low thermal distortion temperature. [Overview of the project]

[0011] The technical problem that the present invention aims to solve is to provide a cyclic olefin resin composition, a method for producing the same, and its use, in response to the drawbacks of conventional high-frequency information transmission materials, which have high dielectric constant, large dielectric loss, and poor heat resistance under high-frequency conditions. The resin material produced using the cyclic olefin resin composition of the present invention exhibits low dielectric loss (D) under high-frequency conditions (frequency ≥ 1 GHz). f <0.001) and low dielectric constant (D k It exhibits a temperature of <2.5) and has excellent heat resistance.

[0012] The present invention solves the aforementioned technical problems through the following technical solutions.

[0013] The present invention provides the use of a cyclic olefin resin composition M1 in the manufacture of a substrate for high-frequency and high-speed information transmission devices, wherein the cyclic olefin resin composition M1 comprises component A and component B, wherein component A is a cyclic olefin, and component B is a ruthenium alkylidene compound represented by formula I and / or formula II or a salt thereof, and the molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:(7500~60000).

[0014] [ka]

[0015] Here, R 11 and R 12 Each is independent of C4-C 18 Alkyl alkyl group, or R 1-1 C4-C replaced by 18 It is an alkyl group; R 1-1 is C6-C 10 It is an aryl group; R 21 , R 22 and R 23 Each is independent of C6-C 18 It is characterized by being an alkyl group.

[0016] In one aspect of the present invention, the high-frequency, high-speed information transmission device substrate material has a dielectric loss < 0.001 under the condition of frequency ≥ 1 GHz (e.g., 1 to 12 GHz, and more specifically, 10 GHz), for example, a dielectric loss of 0.00067, 0.00069, 0.00071, 0.00072, 0.00073, 0.00075, 0.00077, 0.00078, 0.00079, 0.00085, 0.00086, 0.00087, 0.00088, 0.00089, 0.0009, or 0.00091.

[0017] In one aspect of the present invention, the high-frequency, high-speed information transmission device substrate material has a dielectric constant < 2.5 under conditions where the frequency is 1 GHz or higher (e.g., 1 to 12 GHz, and even more e.g., 10 GHz), for example, the dielectric constant being 2.23, 2.26, 2.27, 2.28, 2.29, 2.30, 2.31, or 2.32.

[0018] In one aspect of the present invention, the glass transition temperature of the high-frequency / high-speed information transmission device substrate material is ≥ 135°C, for example, 138°C, 149°C, 152°C, 155°C, 157°C, 160°C, 162°C, 164°C, 165°C, 166°C, 175°C, 177°C, 186°C, 189°C, or 190°C.

[0019] In one aspect of the present invention, the thermal distortion temperature of the high-frequency / high-speed information transmission device substrate material is 110°C or higher, for example, 115°C, 117°C, 119°C, 122°C, 126°C, 127°C, 134°C, 137°C, 142°C, 144°C, 147°C, 158°C, or 167°C.

[0020] In one aspect of the present invention, the molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:(7500~50000), for example, 1:7500, 1:9500, 1:10000, 1:15000, or 1:50000.

[0021] In one embodiment of the present invention, the mass percentage of component A in the cyclic olefin resin composition M1 is 80% or more and less than 100%.

[0022] In one aspect of the present invention, component A is a single type of cyclic olefin or a mixture of multiple types of cyclic olefins, wherein the cyclic olefin contains only two elements, C and H, and it contains one or more R A It may also be replaced with each R A These are independently F, C1-C 18 Alkyl alkyl group, C2-C 18 Alkenyl group, C6-C 10 Aryl group, carbon chain length C2-C18 The alkoxy group, -C(=O)OC2-C 18 Or -OC(=O)C2-C 18 That is the case.

[0023] In one aspect of the present invention, component A is a single type of cyclic olefin or a mixture of multiple types of cyclic olefins, and component A comprises at least a cyclic olefin S1, the cyclic olefin S1 comprises only two elements, C and H, and has the following structural fragment:

[0024] [ka]

[0025] The structural fragment is bonded to the rest of the molecule via carbon atoms indicated by "*", and the cyclic olefin S1 comprises one or more R A It may also be replaced with each R A These are independently F, C1-C 18 Alkyl alkyl group, C2-C 18 Alkenyl group, C6-C 10 Aryl group, C2-C 18 Alkoxy group, -C(=O)OC2-C 18 Or -OC(=O)C2-C 18 Therefore, as can be understood, if component A is a single type of cyclic olefin, then the cyclic olefin is the cyclic olefin S1.

[0026] In one embodiment of the present invention, component A is tetracyclododecene, cyclopentadiene polymer, 5-ethylidene-2-norbornene, cyclohexene, cycloheptene, cyclooctene, and formula A-1

[0027] [ka]

[0028] One or more cyclic olefins having the structure shown in formula A-1 are selected, where m is 0, 1 or 2, and R A1 , R A2 , R A3 and R A4 These are H, F, and C1-C, respectively, independently. 18 Alkyl, C2-C 18 Alkenyl, C6-C 10 Aryl, C2-C 18 Alkoxy, -C(=O)OC2-C 18 Or -OC(=O)C2-C 18 The cyclopentadiene polymer is selected from, for example, one or more of dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, and dihydrodicyclopentadiene, and the dihydrodicyclopentadiene is, for example,

[0029] [ka]

[0030] That is the case.

[0031] In one embodiment of the present invention, component A is tetracyclododecene.

[0032] In one embodiment of the present invention, component A is dihydrodicyclopentadiene.

[0033] In one aspect of the present invention, the mass percentage of dicyclopentadiene in component A is 70% to 100%, for example, 79%, 80%, 90%, or 98%.

[0034] In one embodiment of the present invention, the mass percentage of tricyclopentadiene in component A is 0% to 30%, for example, 10%, 15%, or 20%.

[0035] In one embodiment of the present invention, component A comprises 70% to 100% by mass of dicyclopentadiene and 0% to 30% by mass of tricyclopentadiene.

[0036] In one embodiment of the present invention, component A consists of dicyclopentadiene in a mass percentage of 85% to 95% and tricyclopentadiene in a mass percentage of 5% to 15%.

[0037] In one embodiment of the present invention, component A consists of 90% to 100% by mass of dicyclopentadiene and 0% to 10% by mass of 5-ethylidene-2-norbornene.

[0038] In one embodiment of the present invention, component A comprises 70% to 90% by mass of dicyclopentadiene, 10% to 30% by mass of tricyclopentadiene, and 0% to 5% by mass of tetracyclopentadiene.

[0039] In one embodiment of the present invention, component A comprises 70% to 90% by mass of dicyclopentadiene, 10% to 20% by mass of tricyclopentadiene, 0% to 10% by mass of dihydrodicyclopentadiene, and 0% to 5% by mass of cyclohexene.

[0040] In one embodiment of the present invention, component A is one of the following: Solution 1: Component A consists of 90% dicyclopentadiene by mass and 10% tricyclopentadiene by mass; Solution 2: Component A consists of 98% by mass dicyclopentadiene and 2% by mass 5-ethylidene-2-norbornene; Solution 3: Component A consists of 79% by mass dicyclopentadiene, 20% by mass tricyclopentadiene, and 1% by mass tetracyclopentadiene; Solution 4: Component A consists of 80% by mass dicyclopentadiene, 15% by mass tricyclopentadiene, 4.5% by mass dihydrodicyclopentadiene, and 0.5% by mass cyclohexene.

[0041] In one embodiment of the present invention, in a ruthenium alkylidene compound represented by formula I, R 11 and R 12 So, the above C4-C 18 Alkyl and R 1-1 C4-C replaced by 18 C4-C alkyl group 18 Each alkyl group is independently C4-C 18 These are linear alkyl groups, for example -(CH2)3CH3, -(CH2)5CH3, -(CH2)9CH3, -(CH2) 13 CH3, or -(CH2) 17 It is CH3.

[0042] In one embodiment of the present invention, in a ruthenium alkylidene compound represented by formula I, R 1-1 In the above C6-C 10 The aryl group is either a phenyl group or a naphthyl group, for example, a phenyl group.

[0043] In one embodiment of the present invention, in a ruthenium alkylidene compound represented by formula I, R 11 and R 12 Each is independently C4-C 18 C4-C substituted with an alkyl group or one phenyl group 18 It is an alkyl group.

[0044] In one embodiment of the present invention, the ruthenium alkylidene compound represented by formula I is selected from one or more of the following compounds:

[0045] [ka]

[0046] for example

[0047] [ka]

[0048] That is the case.

[0049] In one embodiment of the present invention, in the ruthenium alkylidene compound represented by formula II, R 21 , R 22 and R 23 So, the above C6-C 18 Each alkyl group is independently C6-C 10 It is an alkyl group, preferably a C6 alkyl group, a C8 alkyl group or C 10 It is an alkyl group.

[0050] In one embodiment of the present invention, the ruthenium alkylidene compound represented by formula II is selected from one or more of the following compounds:

[0051] [ka]

[0052] for example

[0053] [ka]

[0054] That is the case.

[0055] In one embodiment of the present invention, component B is a ruthenium alkylidene compound represented by formula I.

[0056] In one embodiment of the present invention, component B is a ruthenium alkylidene compound represented by formula II.

[0057] In one aspect of the present invention, component B consists of a ruthenium alkylidene compound represented by formula I and a ruthenium alkylidene compound represented by formula II, for example

[0058] [ka]

[0059] That is the case.

[0060] In one aspect of the present invention, component B is a ruthenium alkylidene compound represented by formula I and a ruthenium alkylidene compound represented by formula II, where the molar ratio of the ruthenium alkylidene compound represented by formula I to the ruthenium alkylidene compound represented by formula II is 1:(1.5~5), for example, 1:2.

[0061] In one aspect of the present invention, the cyclic olefin resin composition M1 further comprises component C, which is selected from one or more solid paraffins, liquid paraffins, and chlorinated paraffins having a chlorine content of 5 wt% to 65 wt%, for example, liquid paraffin, chlorinated paraffin having a chlorine content of 5 wt% to 65 wt%, or a mixture of liquid paraffin and chlorinated paraffin having a chlorine content of 5 wt% to 65 wt%, wherein the mass ratio of the liquid paraffin to the chlorinated paraffin having a chlorine content of 5 wt% to 65 wt% is, for example, (10 to 20):1, for example, 11:1; Preferably, the ratio of the total mass of component C and component B to the mass of component A is 1:(15-200), for example 1:(15-55), and more specifically 1:(20-50).

[0062] In one embodiment of the present invention, the cyclic olefin resin composition M1 further comprises component C, wherein component C is liquid paraffin and / or chlorinated paraffin having a chlorine content of 5 wt% to 65 wt%, and the mass ratio of component C to component B is (15 to 70):1, for example 21:1, or 28:1, or 64:1.

[0063] In one embodiment of the present invention, the cyclic olefin resin composition M1 further comprises component C, wherein component C is liquid paraffin, and the mass ratio of component C to component B is (60-70):1, for example, 64:1.

[0064] In one aspect of the present invention, the cyclic olefin resin composition M1 further comprises component C, wherein component C is a paraffin chloride with a chlorine content of 5 wt% to 65 wt%, and the mass ratio of component C to component B is (15 to 35):1, for example, 21:1 or 28:1.

[0065] In one aspect of the present invention, the cyclic olefin resin composition M1 further comprises component C, which is a mixture of liquid paraffin and chlorinated paraffin having a chlorine content of 5 wt% to 65 wt%, wherein the mass ratio of the liquid paraffin to the chlorinated paraffin having a chlorine content of 5 wt% to 65 wt% is, for example, (10 to 20):1, or for example, 11:1; and the mass ratio of component C to component B is (60 to 70):1, or for example, 64:1.

[0066] Preferably, in any one of the above embodiments, the paraffin chloride having a chlorine content of 5 wt% to 65 wt% is a paraffin chloride having a chlorine content of 5 wt% to 52 wt%.

[0067] In one aspect of the present invention, the cyclic olefin resin composition M1 further comprises component D, wherein component D is a thermoplastic resin with a carbon chain length of C 12 The above linear or branched olefins, with a carbon chain length of C 12 Selected from one or more of the linear or branched alkanes, solid paraffins, and mineral oils; the thermoplastic resin, linear olefin, and linear alkane contain only two elements, C and H; Preferably, the thermoplastic resin is selected from one or more of ethylene propylene rubber (EP), ethylene propylene diene terpolymer (EPDM), thermoplastic elastomer (POE), liquid butyl rubber (LBR), styrene butadiene rubber (SBR), hydrogenated styrene butadiene rubber (SEBS), and styrene butadiene styrene block copolymer (SBS); Preferably, the thermoplastic resin is given an additive, the additive being an organophosphorus compound and / or an antioxidant, the organophosphorus compound being selected from, for example, one or more of triphenylphosphine, tricyclohexylphosphine, trioctylphosphine, and tributylphosphine, and the antioxidant being preferably a hindered phenol antioxidant, selected from, for example, one or more of antioxidant 264 (CAS No. 128-37-0), antioxidant 1010 (CAS No. 6683-19-8), and antioxidant 168 (CAS No. 31570-04-4); preferably, the mass percentage of the additive is 0 to 0.5 wt%, for example, 0 to 0.3 wt%, based on the total mass of components A and D; Preferably, the carbon chain length C 12 The linear or branched alkanes described above are n-pentadecanes; Preferably, the mass percentage of component D is 0 to 20 wt%, and more preferably 0 to 10 wt%, based on the total mass of component A and component D.

[0068] In one embodiment of the present invention, the cyclic olefin resin composition M1 comprises component A in any one of the above embodiments and component B in any one of the above embodiments.

[0069] In one embodiment of the present invention, the cyclic olefin resin composition M1 comprises component A in any one embodiment described above, component B in any one embodiment described above, and component C in any one embodiment described above.

[0070] In one embodiment of the present invention, the cyclic olefin resin composition M1 comprises component A in any one embodiment described above, component B in any one embodiment described above, and component D in any one embodiment described above.

[0071] In one embodiment of the present invention, the cyclic olefin resin composition M1 comprises component A in any one embodiment described above, component B in any one embodiment described above, component C in any one embodiment described above, and component D in any one embodiment described above.

[0072] In one embodiment of the present invention, the cyclic olefin resin composition M1 comprises one of the following components: Plan C1: Component A and Component B, The aforementioned component A consists of dicyclopentadiene and tricyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 90%, and the mass percentage of tricyclopentadiene in component A is 10%; The aforementioned component B is

[0073] [ka]

[0074] And, The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; Plan C2: Component A and Component B, The aforementioned component A is tetracyclododecene; The aforementioned component B is

[0075] [ka]

[0076] And, The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:15000; Plan C3: Component A and Component B, The aforementioned component A is dihydrodicyclopentadiene; The aforementioned component B is

[0077] [ka]

[0078] And, The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:15000; Plan C4: Component A, Component B and Component C, The aforementioned component A consists of dicyclopentadiene and 5-ethylidene-2-norbornene, where the mass percentage of dicyclopentadiene in component A is 98%, and the mass percentage of 5-ethylidene-2-norbornene in component A is 2%; The aforementioned component B is

[0079] [ka]

[0080] and; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; The aforementioned component C is liquid paraffin; The total mass ratio of component C and component B to the mass of component A is 1:20; Plan C5: Component A, Component B and Component C, The aforementioned component A consists of dicyclopentadiene and tricyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 90%, and the mass percentage of tricyclopentadiene in component A is 10%; The aforementioned component B is

[0081] [ka]

[0082] and; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; The aforementioned component C is paraffin chloride with a chlorine content of 5%; The total mass ratio of component C and component B to the mass of component A is 1:50; Plan C6: Component A, Component B and Component C, The aforementioned component A consists of dicyclopentadiene and tricyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 90%, and the mass percentage of tricyclopentadiene in component A is 10%; The aforementioned component B is

[0083] [ka]

[0084] and; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; The aforementioned component C is paraffin chloride with a chlorine content of 5%; The total mass ratio of component C and component B to the mass of component A is 1:50; Plan C7: Component A and Component B, The aforementioned component A consists of dicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 79%, the mass percentage of tricyclopentadiene in component A is 20%, and the mass percentage of tetracyclopentadiene in component A is 1%; The aforementioned component B is

[0085] [ka]

[0086] and; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; Plan C8: Component A, Component B and Component C, The aforementioned component A consists of dicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 79%, the mass percentage of tricyclopentadiene in component A is 20%, and the mass percentage of tetracyclopentadiene in component A is 1%; The aforementioned component B is

[0087] [ka]

[0088] and; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; The aforementioned component C is liquid paraffin; The total mass ratio of component C and component B to the mass of component A is 1:200; Plan C9: Component A and Component B, The aforementioned component A consists of dicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 79%, the mass percentage of tricyclopentadiene in component A is 20%, and the mass percentage of tetracyclopentadiene in component A is 1%; The aforementioned component B is

[0089] [ka]

[0090] and; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; Plan C10: Component A and Component B, The aforementioned component A consists of dicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 79%, the mass percentage of tricyclopentadiene in component A is 20%, and the mass percentage of tetracyclopentadiene in component A is 1%; The aforementioned component B is

[0091] [ka]

[0092] and; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:50000; Plan C11: Component A, Component B and Component C, Component A consists of dicyclopentadiene, tricyclopentadiene, dihydrodicyclopentadiene, and cyclohexene, where the mass percentage of dicyclopentadiene in component A is 80%, the mass percentage of tricyclopentadiene in component A is 15%, the mass percentage of dihydrodicyclopentadiene in component A is 4.5%, and the mass percentage of cyclohexene in component A is 0.5%; The aforementioned component B is

[0093] [ka]

[0094] and; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:9500; The aforementioned component C consists of liquid paraffin and chlorinated paraffin with a chlorine content of 52 wt%, where the mass ratio of liquid paraffin to chlorinated paraffin with a chlorine content of 52 wt% is 11:1; The total mass ratio of component C and component B to the mass of component A is 1:20; Plan C12: Component A and Component B, The aforementioned component A consists of dicyclopentadiene and tricyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 90%, and the mass percentage of tricyclopentadiene in component A is 10%; The aforementioned component B is

[0095] [ka]

[0096] It consists of, and here,

[0097] [ka]

[0098] The molar ratio is 1:2; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; Plan C13: Component A and Component B, The aforementioned component A consists of dicyclopentadiene and tricyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 90%, and the mass percentage of tricyclopentadiene in component A is 10%; The aforementioned component B is

[0099] [ka]

[0100] and; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:7500; Plan C14: Component A, Component B, and Component D The aforementioned component A consists of dicyclopentadiene and tricyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 90%, and the mass percentage of tricyclopentadiene in component A is 10%; The aforementioned component B is

[0101] [ka]

[0102] and; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; The aforementioned component D is a mixture of n-pentadecane, EPDM, SBS, and mineral oil; Based on the total mass of components A and D, the mass percentage of n-pentadecane is 4-5%, and the mass percentages of EPDM, SBS, and mineral oil are independently 2-3%; Plan C15: Component A, Component B, and Component D The aforementioned component A consists of dicyclopentadiene and tricyclopentadiene, with dicyclopentadiene accounting for 90% of the mass of component A and tricyclopentadiene accounting for 10% of the mass of component A; The aforementioned component B is

[0103] [ka]

[0104] and; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; The aforementioned component D is a mixture of n-pentadecane, hexadecene, EPDM, SEBS, POE, and mineral oil; Based on the total mass of components A and D, the mass percentage of n-pentadecane is 2-4%, the mass percentage of hexadecene is 0.3-1%, the mass percentage of EPDM is 2-3%, the mass percentage of SEBS is 0.3-1%, the mass percentage of POE is 0.5-1.2%, and the mass percentage of mineral oil is independently 2-3%. Plan C16: Component A, Component B, and Component D Component A consists of dicyclopentadiene and tricyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 90%, and the mass percentage of tricyclopentadiene in component A is 10%; The aforementioned component B is

[0105] [ka]

[0106] and; The aforementioned component D is a mixture of antioxidant 264, triphenylphosphine, n-pentadecane, EPDM, SEBS, and POE; Based on the total mass of components A and D, the mass percentage of antioxidant 264 is 0.1-0.2%, the mass percentage of triphenylphosphine is 0.02-0.1%, the mass percentage of n-pentadecane is 4-5%, the mass percentage of EPDM is 1-2%, the mass percentage of SEBS is 1-2%, and the mass percentage of POE is 1-2%.

[0107] In one aspect of the present invention, the substrate material for the high-frequency / high-speed information transmission device is a copper foil substrate.

[0108] The present invention further provides a cyclic olefin resin composition M1 according to any one of the above-described embodiments, characterized in that the mass percentage of component A in the cyclic olefin resin composition M1 is 80% or more and less than 100%.

[0109] The present invention further provides a cyclic olefin resin composition M2 characterized by comprising component A in any one of the above-described embodiments and component B in any one of the above-described embodiments.

[0110] The present invention further provides a cyclic olefin resin composition M3 characterized by comprising component A in any one of the above-described embodiments, component B in any one of the above-described embodiments, and component C in any one of the above-described embodiments.

[0111] The present invention further provides a cyclic olefin resin composition M4 characterized by comprising component A in any one of the above-described embodiments, component B in any one of the above-described embodiments, and component D in any one of the above-described solutions.

[0112] The present invention further provides a cyclic olefin resin composition M5 characterized by comprising component A in any one of the above-described solutions, component B in any one of the above-described solutions, component C in any one of the above-described embodiments, and component D in any one of the above-described embodiments.

[0113] In the present invention, "Component A in any of the above-described modes" means that the type, content, or other characteristics of component A are as described in any of the above-described modes, and is not limited to merely the type of component A being as described in any of the above-described plans.

[0114] "Component B in any of the above-described modes" means that the type, content, or other characteristics of component B are as described in any of the above-described modes, and is not limited to merely the type of component B being as described in any of the above-described modes.

[0115] "Component C in any of the above-described modes" means that the type and content or other characteristics of component C are as described in any of the above-described modes, and is not limited to merely the type of component C being as described in any of the above-described plans.

[0116] "Component D in any of the above-described modes" means that the type, content, or other characteristics of component D are as described in any of the above-described modes, and is not limited to merely the type of component D being as described in any of the above-described plans.

[0117] The present invention further provides a cyclic olefin resin material characterized by being manufactured using a cyclic olefin resin composition M1, M2, M3, M4, or M5 described in any one of the above embodiments as a raw material.

[0118] In one aspect of the present invention, the cyclic olefin resin material has a dielectric loss of <0.001 under the condition of a frequency ≥ 1 GHz (e.g., 1 to 12 GHz, and even more e.g., 10 GHz), for example, the dielectric loss being 0.00067, 0.00069, 0.00071, 0.00072, 0.00073, 0.00075, 0.00077, 0.00078, 0.00079, 0.00085, 0.00086, 0.00087, 0.00088, 0.00089, 0.0009, or 0.00091.

[0119] In one aspect of the present invention, the cyclic olefin resin material has a dielectric constant < 2.5 under conditions of frequency ≥ 1 GHz (e.g., 1 to 12 GHz, and more specifically, 10 GHz), for example, a dielectric constant of 2.23, 2.26, 2.27, 2.28, 2.29, 2.30, 2.31, or 2.32.

[0120] In one aspect of the present invention, the glass transition temperature of the cyclic olefin resin material is ≥135°C, for example, 138°C, 149°C, 152°C, 155°C, 157°C, 160°C, 162°C, 164°C, 165°C, 166°C, 175°C, 177°C, 186°C, 189°C, or 190°C.

[0121] In one aspect of the present invention, the heat distortion temperature of the cyclic olefin resin material is ≥ 110°C, for example, 115°C, 117°C, 119°C, 122°C, 126°C, 127°C, 134°C, 137°C, 142°C, 144°C, 147°C, 158°C, or 167°C.

[0122] The cyclic olefin resin material can be manufactured using conventional liquid molding processes in the art, such as reaction injection molding (RIM), resin transfer molding (RTM), and vacuum-assisted resin infusion (VARI). In the reaction injection molding (RIM), resin transfer molding (RTM), and vacuum-assisted resin infusion (VARI) processes, the molding temperature is 40 to 145°C, for example 40°C, 45°C, 60°C, 70°C, 80°C, or 140°C, preferably 40 to 90°C. The curing time is 1 to 120 minutes, for example 3.5 minutes, 5 minutes, 10 minutes, 20 minutes, 25 minutes, or 30 minutes, preferably 2 to 60 minutes.

[0123] The ROMP polymerization used in the cyclic olefin resin material of the present invention is a front polymerase technique, which is essentially completed within a few seconds once the reaction starts, and the start time is typically 15 to 90 seconds (adjustable). After the front polymerase is complete, the subsequent heat retention process mainly improves the degree of polymerization or the degree of crosslinking of the material to some extent. Therefore, generally, once the start is completed in the range of 40 to 145°C, the minimum performance indicators required by the present invention are already met.

[0124] The present invention also provides a method for producing a cyclic olefin resin material, characterized by comprising the steps of: using a cyclic olefin resin composition M1, M2, M3, M4, or M5 described in any one of the above embodiments as a raw material, mixing the components of the resin composition, and curing and molding the mixture by a liquid molding process, wherein the curing and molding temperature is 40 to 145°C and the curing and molding time is 1 to 120 minutes.

[0125] In one embodiment of the present invention, the curing temperature is 40°C, 45°C, 60°C, 70°C, 80°C, or 140°C.

[0126] In one embodiment of the present invention, the curing time is 2 to 60 minutes, for example 3 to 30 minutes, and more specifically 3.5 minutes, 5 minutes, 10 minutes, 20 minutes, 25 minutes, or 30 minutes.

[0127] In one aspect of the present invention, the liquid molding process is a reaction injection molding (RIM) process, a resin transfer molding (RTM) process, or a vacuum-assisted resin injection molding (VARI) process.

[0128] In one embodiment of the present invention, the liquid molding process is a resin transfer molding (RTM) process, which includes the step of adding a mixture of the components of the cyclic olefin resin composition M1, M2, M3, M4, or M5 to a mold and curing and molding it.

[0129] In one aspect of the present invention, the liquid molding process is a reaction injection molding (RIM) process, the raw material is the cyclic olefin resin composition M3, and the process includes adding a mixture of the components of the cyclic olefin resin composition M3 to a mold and curing it.

[0130] Preferably, the mixture of the components of the cyclic olefin resin composition M3 is obtained by mixing the components of the cyclic olefin resin composition M3 at a pressure of 1 to 3 MPa (for example, 2 MPa). Preferably, the mixture of the components of the cyclic olefin resin composition M3 is added to the mold within 4 to 6 seconds (for example, 5 seconds).

[0131] In one aspect of the present invention, the liquid molding process is a vacuum-assisted resin injection molding (VARI) process, which includes adding a mixture of the components of the cyclic olefin resin composition M1, M2, M3, M4, or M5 to a mold and curing it.

[0132] In one aspect of the present invention, in the reaction injection molding (RIM) process, resin transfer molding (RTM) process, or vacuum-assisted resin injection molding (VARI) process, the mixture is a mixture of component A in each resin composition and other components in each resin composition, wherein component A can be subjected to a preliminary treatment after being stirred at 60°C to 125°C for 4 to 12 hours and then cooled to room temperature.

[0133] In one embodiment of the present invention, the temperature of the mold in the reaction injection molding (RIM), resin transfer molding (RTM), or vacuum forming (VARI) process is 40 to 145°C.

[0134] Preferably, in the reaction injection molding (RIM) process or resin transfer molding (RTM) process, the mold has a mold temperature of 40 to 145°C (e.g., 60 to 140°C) on one side and a mold temperature of 40 to 145°C (e.g., 40 to 140°C) on the other side.

[0135] More preferably, in the reaction injection molding (RIM) process or resin transfer molding (RTM) process, the temperature of the mold is one of the following: Solution 1: One side mold temperature 70°C, other side mold temperature 40°C; Option 2: One side mold temperature 80°C, other side mold temperature 45°C; Option 3: One side mold temperature 140°C, the other side mold temperature 140°C; Option 4: One mold temperature is 60°C, and the other mold temperature is 40°C.

[0136] In one embodiment of the present invention, the reaction injection molding (RIM) process, resin transfer molding (RTM) process, or vacuum-assisted resin injection molding (VARI) process further includes a post-curing step, wherein the temperature of the post-curing step is 60 to 145°C (e.g., 140°C) and the post-curing time is 0 to 60 minutes (e.g., 20 minutes).

[0137] The present invention also provides a cyclic olefin resin material obtained by a method for producing a cyclic olefin resin material described in any one of the above embodiments.

[0138] In one aspect of the present invention, the cyclic olefin resin material has a dielectric loss < 0.001 under the condition of a frequency ≥ 1 GHz (e.g., 1 to 12 GHz, and more specifically, 10 GHz), where the dielectric loss is, for example, 0.00067, 0.00069, 0.00071, 0.00072, 0.00073, 0.00075, 0.00077, 0.00078, 0.00079, 0.00085, 0.00086, 0.00087, 0.00088, 0.00089, 0.0009, or 0.00091.

[0139] In one aspect of the present invention, the cyclic olefin resin material has a dielectric constant < 2.5 under conditions of frequency ≥ 1 GHz (e.g., 1 to 12 GHz, and more specifically, 10 GHz), for example, a dielectric constant of 2.23, 2.26, 2.27, 2.28, 2.29, 2.30, 2.31, or 2.32.

[0140] In one aspect of the present invention, the glass transition temperature of the cyclic olefin resin material is ≥135°C, for example, 138°C, 149°C, 152°C, 155°C, 157°C, 160°C, 162°C, 164°C, 165°C, 166°C, 175°C, 177°C, 186°C, 189°C, or 190°C.

[0141] In one aspect of the present invention, the heat distortion temperature of the cyclic olefin resin material is ≥ 110°C, for example, 115°C, 117°C, 119°C, 122°C, 126°C, 127°C, 134°C, 137°C, 142°C, 144°C, 147°C, 158°C, or 167°C.

[0142] The present invention also provides a method for reducing the dielectric constant and / or dielectric loss of a cyclic olefin resin material, characterized in that, during the production of the cyclic olefin resin material, component B described in any one of the above embodiments is introduced into component A described in any one of the above embodiments, and the molar ratio of Ru in component B to the cyclic olefin monomer of component A is set to 1:(7500~60000).

[0143] Preferably, the raw material for the cyclic olefin resin material is the cyclic olefin resin composition M1, M2, M3, M4, or M5 described in any one of the above embodiments.

[0144] Preferably, the method for producing the cyclic olefin resin material is the method for producing the cyclic olefin resin material described in any one of the above embodiments.

[0145] In one aspect of the present invention, the molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:(7500~50000), for example, 1:7500, 1:9500, 1:10000, 1:15000, or 1:50000.

[0146] The present invention also provides a semi-cured sheet comprising a cyclic olefin resin material as described in any one of the above embodiments.

[0147] The present invention also provides a copper foil substrate comprising a semi-cured sheet as described in any one of the above embodiments.

[0148] The present invention also provides a printed circuit board including a copper foil substrate as described in any one of the above embodiments.

[0149] Within the bounds of common sense in the relevant technical field, each preferred embodiment of the present invention can be obtained by arbitrarily combining the above preferred conditions.

[0150] All reagents and raw materials used in this invention can be obtained commercially.

[0151] The positive and progressive effects of this invention are as follows: (1) A cyclic olefin resin material produced using the cyclic olefin resin composition of the present invention as a raw material exhibits significantly lower dielectric loss and dielectric constant in a high-frequency environment (1 to 12 GHz, e.g., 10 GHz) compared with a cyclic olefin resin material produced using a conventional catalyst. k <2.5, D f The coefficient is <0.001, and the obtained material exhibits excellent heat resistance, with a heat distortion temperature (HDT) of ≥ 110°C and a glass transition temperature (Tg) of ≥ 135°C.

[0152] (2) The cyclic olefin resin system disclosed in the present invention is compatible with multiple liquid molding processes (RIM, RTM, VARI), has high molding efficiency, and low energy consumption. [Modes for carrying out the invention]

[0153] The present invention will be further described below through examples, but this does not limit the present invention to the scope of the examples described. In the following examples, experimental methods for which specific conditions are not specified will follow conventional methods and conditions or be selected based on the product description.

[0154] In the following examples, the dielectric properties (including dielectric constant and dielectric loss) of the molding material are tested in accordance with ASTM D2520.

[0155] The heat distortion temperature (HDT) is measured according to the method specified in GB / T 1634.2-2019; the Tg value is determined by measuring the storage modulus of the material during a programmed heating process with a heating rate of 10 K / min, using dynamic thermodynamic analysis (DMA) testing in double suspension mode, with a test temperature range of 30 to 200°C.

[0156] In the following examples, when relating to the molar ratio of elemental to Ru, the elemental refers to all elemental cyclic olefins contained in the feedstock.

[0157] Example 1: Example of a thermosetting material (DCPD-TCPD + formula IV catalyst + RTM) Preparation of cyclic olefin composition: 900 g of dicyclopentadiene and 100 g of tricyclopentadiene (TCPD,

[0158] [ka]

[0159] After mixing the ingredients, the mixture was heated to 60°C under a nitrogen atmosphere, stirred for 4 hours, cooled to room temperature, and then set aside.

[0160] Liquid ruthenium catalyst: 0.69 g of liquid ruthenium alkylidene catalyst represented by formula IV (Mw = 939.19 g / mol);

[0161] [ka]

[0162] Molding of high-frequency low-dielectric materials: Molding was performed using the RTM process. Before starting molding, the molds were preheated, with one mold temperature set to 70°C and the other to 40°C. 1000g of cyclic olefin composition and 0.69g of liquid ruthenium catalyst were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (molar ratio of elemental ruthenium to Ru = 10000:1). The cyclic olefin resin mixture was injected into a 1.5mm thick mold using an injection pump, cured for 5 minutes, and then demolded to obtain molded test specimens.

[0163] Performance test of molding material: The obtained material had an HDT of 134°C and a Tg of 162°C. The material measured under a test frequency of 10 GHz was D k =2.28, D f The result was 0.00071.

[0164] Example 2.1: Example of a thermoplastic material (DMON + Formula IV catalyst + RTM) Cyclic olefin composition: 1000g tetracyclododecene (formula V); Liquid ruthenium catalyst: 0.39 g of liquid ruthenium alkylidene catalyst represented by formula IV;

[0165] [ka]

[0166] Molding of high-frequency low-dielectric materials: Molding was performed using the RTM process. Before starting molding, the molds were preheated, with one mold temperature set to 70°C and the other to 40°C. 1000g of cyclic olefin composition and 0.39g of liquid ruthenium catalyst were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 15000:1). The cyclic olefin resin mixture was injected into a 1.5mm thick mold cavity using an injection pump, solidified for 5 minutes, and then demolded to obtain molded test specimens.

[0167] Performance test of molding material: The obtained material had an HDT of 142°C and a Tg of 190°C. The material measured under a test frequency of 10 GHz was D k =2.29, D f The value was 0.00075.

[0168] Example 2.2: Example of a thermoplastic material (dihydrodicyclopentadiene + formula IV catalyst + RTM) Cyclic olefin composition: 1000g dihydrodicyclopentadiene (formula VI); Liquid ruthenium catalyst: 0.47 g of liquid ruthenium alkylidene catalyst represented by formula IV;

[0169] [ka]

[0170] Molding of high-frequency low-dielectric material: Molding was carried out using the RTM process. Before the start of molding, the mold was preheated, and the temperature of one mold was set at 70 °C and the other at 40 °C. 1000 g of cyclic olefin composition and 0.47 g of liquid ruthenium catalyst were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (molar ratio of monomer:Ru = 15000:1). Then, it was injected into a 1.5 mm-thick cavity using an injection pump, cured for 5 minutes, and demolded to obtain a molded test piece.

[0171] Performance test of the molding material: The HDT of the obtained material was 117 °C and the Tg was 152 °C. The material measured under the condition of a test frequency of 10 GHz had D k = 2.29 and D f = 0.00077.

[0172] Example 3: RIM process molding 1 (DCPD-ENB + type VII catalyst - paraffin) Production of cyclic olefin composition RIM-A mixture: 980 g of dicyclopentadiene and 20 g of 5-ethylidene-2-norbornene were uniformly mixed to produce a uniform liquid composition; Production of liquid ruthenium catalyst composition RIM-B mixture: 0.77 g of ruthenium alkylidene catalyst (Mw: 1017.3 g / mol) represented by formula VII and 49.23 g of liquid paraffin were uniformly mixed to produce a homogeneous liquid ruthenium catalyst composition. [

[0173]

Chemical formula

[0174] Molding of high-frequency low-dielectric material: Molding was carried out using the RIM process. Before the start of molding, the mold was preheated, and the temperature of one mold was set at 70 °C and the other at 40 °C. The RIM-A mixture and the RIM-B mixture were mixed at a mass ratio of 20:1 and injected (molar ratio of monomer:Ru 10000:1), the injection pressure was 2.0 MPa, a 1.5 mm-thick mold cavity was filled within 5 seconds, and after a curing time of 3.5 minutes, it was demolded to obtain a molded sample.

[0175] [Performance Test of Molding Material: The HDT of the obtained material was 119°C and the Tg was 155°C. The material measured under the condition of a test frequency of 10 GHz had D k = 2.23 and D f = 0.00079.

[0176] Example 4.1: RIM Process Molding 2 (DCPD - TCPD + Type IV Catalyst - Chlorinated Paraffin) Production of Cyclic Olefin Composition RIM - A Mixture: After mixing 900 g of dicyclopentadiene and 100 g of tricyclopentadiene (TCPD), it was heated to 60°C under a nitrogen atmosphere, stirred for 4 hours, cooled to room temperature, and then prepared.

[0177] Liquid Ruthenium Catalyst Composition RIM - B Mixture: 0.69 g of the liquid ruthenium alkylidene catalyst represented by Formula IV was completely stirred and dissolved in 19.31 g of chlorinated paraffin with a chlorine content of 5%.

[0178] Molding of High - Frequency Low - Dielectric Material: Molding was carried out using the RIM process. Before the start of molding, the mold was preheated, and one mold temperature was set to 70°C and the other to 40°C. The RIM - A mixture and the RIM - B mixture were mixed at a mass ratio of 50:1 and injected (monomer: Ru molar ratio 10000:1). The injection pressure was 2.0 MPa, and a 1.5 - mm - thick mold cavity was filled within 5 seconds. After a curing time of 5 minutes, the mold was removed to obtain a molded sample.

[0179] Performance Test of Molding Material: The HDT of the obtained material was 122°C and the Tg was 157°C. The material measured under the condition of a test frequency of 10 GHz had D[[ID=2​​​​​​​​​

[0181] Liquid ruthenium catalyst composition RIM-B mixture: 0.91 g of liquid ruthenium alkylidene catalyst represented by formula VIII was completely dissolved with stirring in 19.09 g of paraffin chloride with a chlorine content of 5%.

[0182] [ka]

[0183] High-frequency low-dielectric material molding: Molding was performed using the RIM process. Before starting molding, the molds were preheated, with one mold temperature set to 70°C and the other to 40°C. RIM-A mixture and RIM-B mixture were mixed in a mass ratio of 50:1 and injected (monomer:Ru molar ratio 10000:1) at an injection pressure of 2.0 MPa, filling a 1.5 mm thick mold cavity within 5 seconds. After a curing time of 5 minutes, the mold was demolded to obtain the molded sample.

[0184] Performance test of molding material: The obtained material had an HDT of 126°C and a Tg of 160°C. The material measured under a test frequency of 10 GHz was D k =2.30, D f The result was 0.00086.

[0185] Example 5.1: VARI process molding (DCPD-TCPD-TeCPD + formula IV catalyst) Preparation of cyclic olefin composition: 790 g dicyclopentadiene, 200 g tricyclopentadiene (TCPD), and 10 g tetracyclopentadiene (TeCPD)

[0186] [ka]

[0187] After mixing the ingredients, the mixture was heated to 125°C under a nitrogen atmosphere, stirred for 12 hours, cooled to room temperature, and then set aside. Liquid ruthenium catalyst: 0.66 g of liquid ruthenium alkylidene catalyst represented by formula IV; Molding of high-frequency low-dielectric materials: Molding was performed using the VARI process. Before starting molding, the mold was preheated to a mold temperature of 70°C. Next, the mold cavity was subjected to a vacuum of -0.09 MPaG, and the pressure was maintained at the same level during the injection process. 1000 g of cyclic olefin composition and 0.66 g of liquid ruthenium catalyst were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 10000:1). The cyclic olefin resin mixture was then injected into a 1.5 mm thick mold using an injection pump. Once the resin mixture filled the mold, the vacuum valve was quickly turned off, and after solidification for 5 minutes, the mold was demolded to obtain a molded test specimen.

[0188] Performance test of molding material: The obtained material had an HDT of 147°C and a Tg of 177°C. The material measured under a test frequency of 10 GHz was D k =2.26, D f The result was 0.00067. Example 5.2: VARI process molding (DCPD-TCPD-TeCPD + Formula VII catalyst-liquid paraffin) Preparation of cyclic olefin composition: 790 g of dicyclopentadiene, 200 g of tricyclopentadiene (TCPD), and 10 g of tetracyclopentadiene (TeCPD) were mixed, heated to 125°C under a nitrogen atmosphere, stirred for 12 hours, cooled to room temperature, and then set aside; Liquid ruthenium catalyst composition: 0.71 g of ruthenium alkylidene catalyst represented by formula VII was dissolved in 4.29 g of liquid paraffin; Molding of high-frequency low-dielectric materials: Molding was performed using the VARI process. Before starting molding, the mold was preheated to a temperature of 70°C. Next, the mold cavity was evacuated to -0.09 MPaG, and the pressure was maintained at the same level during the injection process. 1000 g of cyclic olefin composition and 5 g of liquid ruthenium catalyst composition were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio = 10000:1). This mixture was injected into a 1.5 mm thick mold using an injection pump. Once the resin mixture filled the mold, the vacuum valve was quickly turned off, and after solidification for 5 minutes, the mold was demolded to obtain a molded test specimen.

[0189] Performance Test of Molding Material: The HDT of the obtained material was 144°C and the Tg was 175°C. The material measured under the condition of a test frequency of 10 GHz had D k = 2.29 and D f = 0.00072.

[0190] Example 5.3: Molding by VARI Process (DCPD - TCPD - TeCPD + Type IX Catalyst) Manufacture of Cyclic Olefin Composition: After mixing 790 g of dicyclopentadiene, 200 g of tricyclopentadiene (TCPD), and 10 g of tetracyclopentadiene (TeCPD), it was heated to 125°C under a nitrogen atmosphere, stirred for 12 hours, and then cooled to room temperature for preparation.

[0191] Liquid Ruthenium Catalyst: 0.72 g of liquid ruthenium alkylidene catalyst represented by Formula IX.

[0192] <遂

Chemical Formula

[0193] Molding of High - Frequency Low - Dielectric Material: Molding was carried out using the VARI process. Before the start of molding, the mold was pre - heated and the mold temperature was set at 70°C. Next, the mold cavity was set to a vacuum state of - 0.09 MPaG, and the pressure was maintained at the same level during the injection process. After thoroughly mixing and dissolving 1000 g of cyclic olefin composition and 0.72 g of liquid ruthenium catalyst, a cyclic olefin resin mixture (molar ratio of monomer:Ru was 10000:1) was obtained. The cyclic olefin resin mixture was injected into a mold with a thickness of 1.5 mm using an injection pump. When the resin mixture filled the mold, the vacuum valve was quickly turned off, and after curing for 5 minutes, it was demolded to obtain a molded test piece.

[0194] <00逕逕0986>Performance Test of Molding Material: The HDT of the obtained material was 144°C and the Tg was 175°C. The material measured under the condition of a test frequency of 10 GHz had D k = 2.28 and D f = 0.00069.

[0195] It should be noted that there are some tags like <遂 which seem to be incorrect or incomplete in the original text. This translation is done based on the best understanding of the provided content.Example 6: Monomer:Ru = 50000:1 (low amount of catalyst used) Preparation of cyclic olefin composition: 790 g of dicyclopentadiene, 200 g of tricyclopentadiene (TCPD), and 10 g of tetracyclopentadiene (TeCPD) were mixed, heated to 125°C under a nitrogen atmosphere, stirred for 12 hours, and then cooled to room temperature to set aside.

[0196] Liquid ruthenium catalyst: 0.132 g of liquid ruthenium alkylidene catalyst represented by formula IV; Molding of high-frequency low-dielectric materials: Molding was performed using the VARI process. Before starting molding, the molds were preheated, with one mold temperature set to 80°C and the other to 45°C. Next, the mold cavity was evacuated to -0.09 MPaG, and the pressure was maintained at the same level during the injection process. 1000 g of cyclic olefin composition and 0.132 g of liquid ruthenium catalyst were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio = 50000:1). The cyclic olefin resin mixture was injected into a 1.5 mm thick mold using an injection pump. Once the resin mixture filled the mold, the vacuum valve was quickly turned off, and after solidification for 30 minutes, the mold was demolded to obtain a molded test specimen.

[0197] Performance test of molding material: The obtained material had an HDT of 115°C and a Tg of 138°C. The material measured under a test frequency of 10 GHz was D k =2.27, D f The value was 0.00085.

[0198] Example 7: Stepwise high-temperature solidification (70 / 40°C for 5 minutes + 140°C for 20 minutes) Preparation of cyclic olefin composition: 790 g of dicyclopentadiene, 200 g of tricyclopentadiene (TCPD), and 10 g of tetracyclopentadiene (TeCPD) were mixed, heated to 125°C under a nitrogen atmosphere, stirred for 12 hours, and then cooled to room temperature to set aside.

[0199] Liquid ruthenium catalyst: 0.66 g of liquid ruthenium alkylidene catalyst represented by formula IV; Molding of high-frequency low-dielectric materials: Molding was performed using the VARI process. Before starting molding, the mold was preheated, with one mold temperature set to 70°C and the other to 40°C. Next, the mold cavity was evacuated to -0.09 MPaG, and the pressure was maintained at the same level during the injection process. 1000 g of cyclic olefin composition and 0.66 g of liquid ruthenium catalyst were thoroughly mixed and dissolved to prepare a cyclic olefin resin mixture (monomer:Ru molar ratio = 10000:1). The cyclic olefin resin mixture was injected into a 1.5 mm thick mold using an injection pump and allowed to solidify for 5 minutes. Once the resin mixture filled the mold, the vacuum valve was quickly turned off, and the temperature on both sides of the mold was rapidly increased to 140°C. Solidification was continued for another 20 minutes, and after the temperature dropped below 80°C, the mold was demolded to obtain the test specimen.

[0200] Performance test of molding material: The obtained material had an HDT of 158°C and a Tg of 189°C. The material measured under a test frequency of 10 GHz was D k =2.26, D f The result was 0.00073.

[0201] Example 8: Storage period test (6 months) Preparation of cyclic olefin composition: 800 g of dicyclopentadiene, 150 g of tricyclopentadiene, 45 g of dihydrodicyclopentadiene, and 5 g of cyclohexene were mixed, heated to 125°C under a nitrogen atmosphere, stirred for 12 hours, and then cooled to room temperature to set aside.

[0202] Preparation of liquid ruthenium catalyst composition: 0.77 g of ruthenium alkylidene catalyst represented by formula VII, 45.23 g of liquid paraffin, and 4 g of chlorinated paraffin with a chlorine content of 52% were thoroughly mixed to form a homogeneous liquid ruthenium catalyst composition.

[0203] Following the manufacturing method described above, two sets of cyclic olefin resin compositions with the same mixing ratio were prepared, and one of these sets was sealed and stored in a cool, dry place for six months.

[0204] Molding of newly manufactured cyclic olefin resin composition material: Molding was performed using the RIM process. Before starting molding, the molds were preheated, with one mold temperature set to 70°C and the other to 40°C. 1000g of cyclic olefin composition and 50g of liquid ruthenium catalyst were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 9500:1). The cyclic olefin resin mixture was injected into a 1.5mm thick mold using an injection pump, solidified for 10 minutes, and then demolded to obtain test specimens.

[0205] Performance test of molding material: The obtained material had an HDT of 127°C and a Tg of 165°C. The material measured under a test frequency of 10 GHz was D k =2.30, D f The result was 0.00089.

[0206] Molding of cyclic olefin resin composition material stored for 6 months: Molding was performed using the RIM process. Before starting molding, the molds were preheated, with one mold temperature set to 70°C and the other to 40°C. 1000g of cyclic olefin composite material and 50g of liquid ruthenium catalyst were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio 9500:1). The cyclic olefin resin mixture was injected into a 1.5mm thick mold using an injection pump, solidified for 10 minutes, and then demolded to obtain a test specimen.

[0207] Performance test of molding material: The obtained material had an HDT of 127°C and a Tg of 164°C. The material measured under a test frequency of 10 GHz was D k =2.30, D f The result was 0.00088.

[0208] Example 9: Initiation system for ruthenium catalyst mixed composition (Formula IV + Formula VII catalyst composition + RTM) Preparation of cyclic olefin composition: 900 g of dicyclopentadiene and 100 g of tricyclopentadiene (TCPD) were mixed, heated to 60°C under a nitrogen atmosphere, stirred for 4 hours, and then cooled to room temperature for pre-treatment.

[0209] Liquid ruthenium catalyst composition: 0.46 g of liquid ruthenium alkylidene catalyst represented by formula IV (Mw = 939.19 g / mol) and 0.25 g of ruthenium alkylidene catalyst represented by formula VII (Mw = 1017.3 g / mol) were uniformly mixed to obtain a liquid ruthenium catalyst composition.

[0210] Molding of high-frequency low-dielectric materials: Molding was performed using the RTM process. Before starting molding, the molds were preheated, with one mold temperature set to 70°C and the other to 40°C. 1000g of cyclic olefin composition and 0.71g of liquid ruthenium catalyst composition were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio = 10000:1). The cyclic olefin resin mixture was injected into a 1.5mm thick mold using an injection pump, solidified for 5 minutes, and then demolded to obtain molded test specimens.

[0211] Performance test of molding material: The obtained material had an HDT of 137°C and a Tg of 166°C. The material measured under a test frequency of 10 GHz was D k =2.29, D f The result was 0.00072.

[0212] Example 10: Upper limit of Ru catalyst usage (7500:1) Preparation of cyclic olefin composition: 900 g of dicyclopentadiene and 100 g of tricyclopentadiene (TCPD) were mixed, heated to 60°C under a nitrogen atmosphere, stirred for 4 hours, and then cooled to room temperature for pre-treatment.

[0213] Liquid ruthenium catalyst: 0.91 g of liquid ruthenium alkylidene catalyst represented by formula IV (Mw = 939.19 g / mol); Molding of high-frequency low-dielectric materials: Molding was performed using the RTM process. Before starting molding, the molds were preheated, with one mold temperature set to 70°C and the other to 40°C. 1000g of cyclic olefin composition and 0.91g of liquid ruthenium catalyst composition were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio = 7500:1). The cyclic olefin resin mixture was injected into a 1.5mm thick mold using an injection pump, solidified for 5 minutes, and then demolded to obtain molded test specimens.

[0214] Performance test of molding material: The obtained material had an HDT of 167°C and a Tg of 186°C. The material measured under a test frequency of 10 GHz was D k =2.30, D f The result was 0.00091.

[0215] Example 11: Example of a thermosetting material (DCPD-TCPD-n-pentadecane + EPDM (containing 50% mineral oil)-SBS + formula IV catalyst + RTM) Preparation of cyclic olefin composition: 900 g of dicyclopentadiene and 100 g of tricyclopentadiene (TCPD,

[0216] [ka]

[0217] The mixture was added to the reactor, and 50 g of Keltan@4890C (EPDM, containing 25 g of mineral oil) and 25 g of Kraton@D1102 (SBS) were dispersed with 50 g of n-pentadecane. The mixture was then poured into the reactor, heated to 110°C under a nitrogen atmosphere, stirred for 8 hours, and cooled to room temperature for pre-cooking. Liquid ruthenium catalyst: 0.69 g of liquid ruthenium alkylidene catalyst represented by formula IV (Mw = 939.19 g / mol);

[0218] [ka]

[0219] Molding of high-frequency low-dielectric materials: Molding was performed using the RTM process. Before starting molding, the molds were preheated, with one mold temperature set to 70°C and the other to 40°C. 1125g of cyclic olefin composition and 0.69g of liquid ruthenium catalyst were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 10000:1). The cyclic olefin resin mixture was injected into a 1.5mm thick mold using an injection pump, solidified for 5 minutes, and then demolded to obtain molded test specimens.

[0220] Performance test of molding material: The obtained material had an HDT of 124°C and a Tg of 151°C. The material measured under a test frequency of 10 GHz was D k =2.31, D f The result was 0.00079.

[0221] Example 12: Example of a thermosetting material (DCPD-TCPD-n-pentadecane-cetocene + EPDM (containing 50% mineral oil)-POE-SEBS + formula IV catalyst + RTM) Preparation of cyclic olefin composition: 900 g of dicyclopentadiene and 100 g of tricyclopentadiene (TCPD,

[0222] [ka]

[0223] The following were mixed and added to the reactor: 50 g of n-pentadecane-cetocene mixture (mass ratio 85 / 15) was used to disperse 50 g of Keltan@4890C (EPDM, containing 25 g of mineral oil), 10 g of Fortify™ C1070D (POE), and 15 g of Kraton@G1651 (SEBS). The mixture was then poured into the reactor, heated to 110°C under a nitrogen atmosphere, stirred for 8 hours, and cooled to room temperature for pre-cooling.

[0224] Liquid ruthenium catalyst: 0.69 g of liquid ruthenium alkylidene catalyst represented by formula IV (Mw = 939.19 g / mol);

[0225] [ka]

[0226] Molding of high-frequency low-dielectric materials: Molding was performed using the RTM process. Before starting molding, the molds were preheated, with one mold temperature set to 70°C and the other to 40°C. 1125g of cyclic olefin composition and 0.69g of liquid ruthenium catalyst were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 10000:1). The cyclic olefin resin mixture was injected into a 1.5mm thick mold using an injection pump, solidified for 5 minutes, and then demolded to obtain molded test specimens.

[0227] Performance test of molding material: The obtained material had an HDT of 122°C and a Tg of 149°C. The material measured under a test frequency of 10 GHz was D k =2.30, D f The result was 0.00078.

[0228] Example 13: Example of a thermosetting material (DCPD-TCPD-n-pentadecane+-POE-SEBS+antioxidant 264+triphenylphosphine+formula IV catalyst+RTM) Preparation of cyclic olefin composition: 900 g dicyclopentadiene, 100 g tricyclopentadiene (TCPD,

[0229] [ka]

[0230] Mix 1.5 g of antioxidant 264 and 0.5 g of triphenylphosphine (TPP) with 50 g of n-pentadecane, disperse 20 g of Nordel™ 6565XFC (EPDM), 15 g of Fortify™ C1070D (POE), and 15 g of Kraton@ G1651 (SEBS) in 50 g of n-pentadecane, pour into the reactor, heat to 110°C under a nitrogen atmosphere, stir for 8 hours, and cool to room temperature for pre-cooking.

[0231] Liquid ruthenium catalyst: 0.69 g of liquid ruthenium alkylidene catalyst represented by formula IV (Mw = 939.19 g / mol);

[0232] [ka]

[0233] Molding of high-frequency low-dielectric materials: Molding was performed using the RTM process. Before starting molding, the molds were preheated, with one mold temperature set to 70°C and the other to 40°C. 1102 g of cyclic olefin composition and 0.69 g of liquid ruthenium catalyst were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio = 10000:1). The cyclic olefin resin mixture was injected into a 1.5 mm thick mold using an injection pump, solidified for 9 minutes, and then demolded to obtain molded test specimens.

[0234] Performance test of molding material: The obtained material had an HDT of 127°C and a Tg of 152°C. The material measured under a test frequency of 10 GHz was D k =2.32, D f The result was 0.0009.

[0235] Example 14: Semi-cured manufacturing process of cyclic olefin resin-glass fiber cloth Preparation of cyclic olefin composition: 790 g of dicyclopentadiene, 200 g of tricyclopentadiene (TCPD), and 10 g of tetracyclopentadiene (TeCPD) were mixed, heated to 125°C under a nitrogen atmosphere, stirred for 12 hours, and then cooled to room temperature to set aside.

[0236] Liquid ruthenium catalyst: 0.132 g of liquid ruthenium alkylidene catalyst represented by formula IV; 1000 g of the manufactured cyclic olefin composition and 0.132 g of liquid ruthenium catalyst were rapidly mixed in a mixer for 15 minutes, with the system temperature controlled to 2-8°C during mixing, and the uniformly mixed resin mixture was placed into an impregnation tank. A glass fiber cloth was impregnated in a resin tank to allow the resin to adhere to the glass fiber cloth. The impregnated glass fiber cloth was then passed through a 100°C heat bridge for 10 seconds and heated to produce a semi-cured cyclic olefin resin-glass fiber cloth semi-cured sheet.

[0237] Example 15: Manufacturing of a copper foil substrate made of cyclic olefin resin Four semi-cured cyclic olefin resin-glass fiber cloth sheets and two 18 μm copper foils were prepared using the method of Example 14 from the same lot. One copper foil, four semi-cured cyclic olefin resin-glass fiber cloth sheets, and one copper foil were laminated in that order, and the substrate was formed by pressure molding under vacuum at 140°C for 1 hour. The four cured cyclic olefin resin-glass fiber cloth sheets formed an insulating layer between the copper foils.

[0238] Dielectric constant D of the insulating layer material of the manufactured copper foil substrate k is 2.8, dielectric loss D f The coefficient of gravity was 0.0025, and the glass transition temperature (Tg) was 152°C.

[0239] Comparative Example 1: Adoption of G2 (The G2 catalyst has extremely low solubility in cyclic olefin resins and is prone to causing explosive polymerization) Preparation of cyclic olefin composition: 90 g of dicyclopentadiene and 10 g of tricyclopentadiene (TCPD) were mixed, heated to 60°C under a nitrogen atmosphere, stirred for 4 hours, and then cooled to room temperature for pre-treatment.

[0240] [ka]

[0241] Specimen Preparation: 0.064 g of Grubbs' second-generation catalyst (formula X) solid was added to a cyclic olefin composition and vigorously stirred at room temperature (800 rpm). After stirring for 1.5 minutes, the catalyst powder did not dissolve, and explosive polymerization with intense heat occurred in a portion of the resin mixture, resulting in agglomeration. The remaining portion did not react, making specimen preparation impossible.

[0242] Comparative Example 2: A G2-dichloromethane solution was used for comparison with Example 1. Preparation of cyclic olefin composition: 900 g of dicyclopentadiene and 100 g of tricyclopentadiene (TCPD) were mixed, heated to 60°C under a nitrogen atmosphere, stirred for 4 hours, and then cooled to room temperature for pre-treatment.

[0243] Preparation of ruthenium catalyst solution: 0.64 g of Grubbs second-generation catalyst was dissolved in 9.36 g of dichloromethane to prepare a G2-DCM solution.

[0244] Material Forming: Forming was performed using the RTM process. Before starting the molding process, the molds were preheated, with one mold temperature set to 70°C and the other to 40°C. 10 g of the prepared ruthenium catalyst solution was dropped into 1000 g of cyclic olefin composition (monomer:Ru molar ratio = 10000:1), and the mixture was uniformly stirred to form a resin composition. This composition was then rapidly injected into a 1.5 mm thick mold using a metering pump, solidified for 5 minutes, and then demolded to obtain a test specimen.

[0245] Performance test of molding material: The obtained material had an HDT of 126°C and a Tg of 161°C. The material measured under a test frequency of 10 GHz was D k =2.38, D f The result was 0.00308.

[0246] Comparative Example 3: A G2-toluene solution was used for comparison with Example 1. Preparation of cyclic olefin composition: 900 g of dicyclopentadiene and 100 g of tricyclopentadiene (TCPD) were mixed, heated to 60°C under a nitrogen atmosphere, stirred for 4 hours, and then cooled to room temperature for pre-treatment.

[0247] Preparation of ruthenium catalyst solution: 0.64 g of Grubbs second-generation catalyst was dissolved in 9.36 g of toluene to form a G2-toluene solution.

[0248] Material Forming: Forming was performed using the RTM process. Before starting the molding process, the molds were preheated, with one mold temperature set to 70°C and the other to 40°C. 10 g of the prepared ruthenium catalyst solution was dropped into 1000 g of cyclic olefin composition (monomer:Ru molar ratio = 10000:1), and the mixture was uniformly stirred to form a resin composition. This composition was then rapidly injected into a 1.5 mm thick mold using a metering pump, solidified for 5 minutes, and then demolded to obtain a test specimen.

[0249] Performance test of molding material: The obtained material had an HDT of 124°C and a Tg of 160°C. The material measured under a test frequency of 10 GHz was D k =2.21, D f The result was 0.00106.

[0250] Comparative Example 4: A Hoveyda-toluene catalyst solution was used for comparison with Example 1. Preparation of cyclic olefin composition: 900 g of dicyclopentadiene and 100 g of tricyclopentadiene (TCPD) were mixed, heated to 60°C under a nitrogen atmosphere, stirred for 4 hours, and then cooled to room temperature for pre-treatment.

[0251] Preparation of ruthenium catalyst solution: 0.46 g of Hoveyda catalyst solid represented by formula XI was weighed and dissolved in 9.54 g of toluene to form XI-toluene solution.

[0252] [ka]

[0253] Material Forming: Forming was performed using the RTM process. Before starting the molding process, the molds were preheated, with one mold temperature set to 70°C and the other to 40°C. 10 g of the prepared ruthenium catalyst solution was dropped into 1000 g of cyclic olefin composition (monomer:Ru molar ratio = 10000:1), and the mixture was uniformly stirred to form a resin composition. This composition was then rapidly injected into a 1.5 mm thick mold using a metering pump, solidified for 5 minutes, and then demolded to obtain a test specimen.

[0254] Performance test of molding material: The obtained material had an HDT of 113°C and a Tg of 149°C. The material measured under a test frequency of 10 GHz was D k =2.22, D f The result was 0.00114. Comparative Example 5: Comparison with Examples 5 and 6 (Monomer residue due to excessively low catalyst concentration) Preparation of cyclic olefin composition: 790 g of dicyclopentadiene, 200 g of tricyclopentadiene (TCPD), and 10 g of tetracyclopentadiene (TeCPD) were mixed, heated to 125°C under a nitrogen atmosphere, stirred for 12 hours, and then cooled to room temperature to set aside.

[0255] Liquid ruthenium catalyst: 0.066 g of liquid ruthenium alkylidene catalyst represented by formula IV; Molding of high-frequency low-dielectric materials: Molding was performed using the VARI process. Before starting molding, the molds were preheated, with one mold temperature set to 80°C and the other to 45°C. Next, the mold cavity was evacuated to -0.09 MPaG, and the pressure was maintained at the same level during the injection process. 1000 g of cyclic olefin composition and 0.066 g of liquid ruthenium catalyst were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio = 80000:1). The cyclic olefin resin mixture was injected into a 1.5 mm thick mold using an injection pump. Once the resin mixture filled the mold, the vacuum valve was quickly turned off, and after solidification for 30 minutes, the mold was demolded to obtain a molded test specimen.

[0256] Performance test of molding material: The Tg of the obtained material was 65°C. The material measured under a test frequency of 10 GHz was D k =2.41, D f The result was 0.00589.

[0257] Comparative Example 6.1: Comparison with Examples 5 and 6 (Catalyst concentration is too high) Preparation of cyclic olefin composition: 790 g of dicyclopentadiene, 200 g of tricyclopentadiene (TCPD), and 10 g of tetracyclopentadiene (TeCPD) were mixed, heated to 125°C under a nitrogen atmosphere, stirred for 12 hours, and then cooled to room temperature to set aside.

[0258] Liquid ruthenium catalyst: 1.32 g of liquid ruthenium alkylidene catalyst represented by formula IV; Molding of high-frequency low-dielectric materials: Molding was performed using the VARI process. Before starting molding, the molds were preheated, with one mold temperature set to 60°C and the other to 40°C. Next, the mold cavity was evacuated to -0.09 MPaG, and the pressure was maintained at the same level during the injection process. 1000 g of cyclic olefin composition and 1.32 g of liquid ruthenium catalyst were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio = 5000:1). The cyclic olefin resin mixture was injected into a 1.5 mm thick mold using an injection pump. Once the resin mixture filled the mold, the vacuum valve was quickly turned off, and after solidification for 30 minutes, the mold was demolded to obtain molded test specimens.

[0259] Performance test of the molding material: The obtained material has a heat distortion temperature (HDT) of 120°C and a glass transition temperature (Tg) of 144°C. The material measured under a test frequency of 10 GHz had a dielectric constant (D k ) = 2.29, dielectric loss (D f ) = 0.00109.

[0260] Comparative Example 6.2: Comparison with Examples 5, 6, and 10 (Catalyst concentration is too high) Preparation of cyclic olefin composition: 790 g of dicyclopentadiene, 200 g of tricyclopentadiene (TCPD), and 10 g of tetracyclopentadiene (TeCPD) were mixed, heated to 125°C under a nitrogen atmosphere, stirred for 12 hours, and then cooled to room temperature to set aside.

[0261] Liquid ruthenium catalyst: 1.02 g of liquid ruthenium alkylidene catalyst represented by formula IV; Molding of high-frequency low-dielectric materials: Molding was performed using the VARI process. Before starting molding, the molds were preheated, with one mold temperature set to 60°C and the other to 40°C. Next, the mold cavity was evacuated to -0.09 MPaG, and the pressure was maintained at the same level during the injection process. 1000 g of cyclic olefin composition and 1.02 g of liquid ruthenium catalyst were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio = 6500:1). The cyclic olefin resin mixture was injected into a 1.5 mm thick mold using an injection pump. Once the resin mixture filled the mold, the vacuum valve was quickly turned off, and after solidification for 30 minutes, the mold was demolded to obtain molded test specimens.

[0262] Performance test of the molding material: The obtained material had a heat distortion temperature (HDT) of 122°C and a glass transition temperature (Tg) of 151°C. The material measured under a test frequency of 10 GHz had a dielectric constant (D k ) = 2.29, dielectric loss (D f ) = 0.00102.

[0263] Comparative Example 7: Comparison with Example 1 (Thermal degradation occurred due to excessively high molding temperature and excessively long molding time). Preparation of cyclic olefin composition: 900 g of dicyclopentadiene and 100 g of tricyclopentadiene (TCPD) were mixed, heated to 60°C under a nitrogen atmosphere, stirred for 4 hours, and then cooled to room temperature for pre-treatment.

[0264] Liquid ruthenium catalyst: 0.69 g of liquid ruthenium alkylidene catalyst represented by formula IV; Material Forming: Forming was performed using the RTM process. 1000g of cyclic olefin composition and 0.69g of liquid ruthenium catalyst were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 10000:1). The cyclic olefin resin mixture was injected into a 1.5mm thick mold using an injection pump, and rapidly heated to a temperature of 160°C in one mold and 130°C in the other, and solidified for 180 minutes. After solidification was complete and the mold temperature dropped to 80°C, the demolded product was obtained.

[0265] Performance test of molding material: The obtained material had an HDT of 147°C and a Tg of 176°C. The material measured under a test frequency of 10 GHz was D k =2.32, D f The result was 0.00264.

[0266] Comparative Example 8: Comparison with Example 1 (Unreacted monomers remain due to excessively low molding temperature) Preparation of cyclic olefin composition: 900 g of dicyclopentadiene and 100 g of tricyclopentadiene (TCPD) were mixed, heated to 60°C under a nitrogen atmosphere, stirred for 4 hours, and then cooled to room temperature for pre-treatment.

[0267] Liquid ruthenium catalyst: 0.69 g of liquid ruthenium alkylidene catalyst represented by formula IV; Material Forming: Forming was performed using the RTM process. Before starting the molding process, the molds were preheated, with one mold temperature set to 35°C and the other to 35°C. 1000g of cyclic olefin composition and 0.69g of liquid ruthenium catalyst were thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio = 10000:1). The cyclic olefin resin mixture was injected into a 1.5mm thick mold using an injection pump, solidified for 120 minutes, and then demolded to obtain a molded test specimen.

[0268] Performance test of molding material: The obtained material had an HDT of 111°C and a Tg of 128°C. The material measured under a test frequency of 10 GHz was D k =2.39, D f The result was 0.00282.

[0269] Comparison explanation: (1) From a comparison of Example 1 and Comparative Example 1, the liquid ruthenium catalyst / catalyst composition in the resin composition disclosed in the present invention has superior solubility in the cyclic olefin composition compared to conventional solid catalysts. From a comparison of Example 1 and Comparative Examples 2-4, the liquid ruthenium catalyst composition disclosed in the present invention has significantly lower D than the material obtained by mixing and solidifying a solution of conventional Grubbs secondary catalyst and Hoveyda catalyst with the disclosed cyclic olefin composition. f Value (Df It showed <0.001).

[0270] (2) From the comparative results of Examples 5 and 6 and Comparative Examples 5 and 6, it was found that when the catalyst content in the cyclic olefin resin composition is too low, the presence of residual monomers after material solidification causes D f If the amount increases rapidly and the catalyst content in the cyclic olefin resin composition is too high, the residual metal ion concentration in the material after solidification increases, D f The value increased so much that it could not meet the related application requirements.

[0271] (3) From a comparison of the results of Example 1 and Comparative Example 7, it was found that after solidifying the cyclic olefin resin composition at high temperature for a long period of time, the heat resistance of the material improved, but the dielectric properties, particularly D f The performance deteriorated significantly, making it impossible to meet the relevant application requirements.

[0272] (4) A comparison of the results of Example 1 and Comparative Example 8 showed that when the solidification temperature of the cyclic olefin resin composition was too low, the dielectric properties of the material could not meet the requirements for the relevant applications even after solidification for a long time.

[0273] (5) The materials obtained by mixing and solidifying any one of the cyclic olefins in Examples 1 to 13 with a liquid ruthenium catalyst / catalyst composition all exhibited remarkably low D at a test frequency of 10 GHz. f Value (<0.001) and D k The value obtained was (<2.5).

Claims

1. The use of cyclic olefin resin composition M1 in the manufacture of base materials for high-frequency and high-speed information transmission devices, The cyclic olefin resin composition M1 comprises component A and component B, wherein component A is a cyclic olefin, and component B is a ruthenium alkylidene compound represented by formula I and / or formula II or a salt thereof, and the molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:(7500 to 60000). 【Chemistry 1】 Here, R １１ and R １２ Each is independent of C ４ -C １８ Alkyl alkyl group, or R １－１ C replaced by ４ -C １８ It is an alkyl group; R １－１ is C ６ -C １０ an aryl group; R ２１ , R ２２ and R ２３ Each is independent of C ６ -C １８ Use of cyclic olefin resin composition M1, characterized by being an alkyl group, in the manufacture of a base material for high-frequency and high-speed information transmission devices.

2. The use of the cyclic olefin resin composition M1 in the manufacture of a base material for a high-frequency / high-speed information transmission device according to claim 1, characterized in that one or more of the following conditions are met. (1) The substrate material of the high-frequency / high-speed information transmission device has a dielectric loss of <0.001 under the condition of frequency ≥ 1 GHz, for example, a dielectric loss of 0.00067, 0.00069, 0.00071, 0.00072, 0.00073, 0.00075, 0.00077, 0.00078, 0.00079, 0.00085, 0.00086, 0.00087, 0.00088, 0.00089, 0.0009 or 0.00091; the frequency is ≥ 1 GHz, for example, 1 to 12 GHz, and more specifically, 10 GHz; (2) The substrate material of the high-frequency / high-speed information transmission device has a dielectric constant of <2.5 under the condition of frequency ≥ 1 GHz, for example, a dielectric constant of 2.23, 2.26, 2.27, 2.28, 2.29, 2.30, 2.31 or 2.32; the frequency is ≥ 1 GHz, for example, 1 to 12 GHz, and more specifically, 10 GHz; (3) The glass transition temperature of the substrate material of the high-frequency / high-speed information transmission device is ≥ 135°C, for example, 138°C, 149°C, 152°C, 155°C, 157°C, 160°C, 162°C, 164°C, 165°C, 166°C, 175°C, 177°C, 186°C, 189°C, or 190°C; (4) The thermal distortion temperature of the base material of the high-frequency / high-speed information transmission device is ≥ 110°C, for example, 115°C, 117°C, 119°C, 122°C, 126°C, 127°C, 134°C, 137°C, 142°C, 144°C, 147°C, 158°C, or 167°C; (5) In the cyclic olefin resin composition M1, the mass percentage of component A is 80% or more and less than 100%. (6) The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:(7500 to 50000), for example 1:7500, 1:9500, 1:10000, 1:15000, or 1:50000; (7) Component A is a single type of cyclic olefin or a mixture of multiple types of cyclic olefins, the cyclic olefin contains only two elements, C and H, and it contains one or more R Ａ It may be replaced by the above R Ａ F and C are independent. １ -C １８ Alkyl, C ２ -C １８ Alkenil, C ６ -C １０ Aryl, carbon chain length is C ２ -C １８ Alkoxy of -C(=O)OC ２ -C １８ , or -OC(=OC)C ２ -C １８ And; Preferably, component A is a single type of cyclic olefin or a mixture of multiple types of cyclic olefins, component A includes at least a cyclic olefin S1, and the cyclic olefin S1 contains only two elements, C and H, and has the following structural fragment: 【Chemistry 2】 The structural fragment is bonded to the rest of the molecule via carbon atoms indicated by "*", and the cyclic olefin S1 is one or more R Ａ It may be replaced by the above R Ａ F and C are independent. １ -C １８ Alkyl, C ２ -C １８ Alkenil, C ６ -C １０ Ariel, C ２ -C １８ Alkoxy, -C(=O)OC ２ -C １８ , or -OC(=OC)C ２ -C １８ And; More preferably, component A is tetracyclododecene, cyclopentadiene polymer, 5-ethylidene-2-norbornene, cyclohexene, cycloheptene, cyclooctene, and a cyclic olefin having the structure represented by formula A-1. 【Transformation 3】 One or more of the following are selected, and in formula A-1, m is 0, 1, or 2, R Ａ１ , R Ａ２ , R Ａ３ , and R Ａ４ These are H, F, and C, respectively, independently. １ -C １８ Alkyl, C ２ -C １８ Alkenil, C ６ -C １０ Ariel, C ２ -C １８ Alkoxy, -C(=O)OC ２ -C １８ , or -OC(=OC)C ２ -C １８ The cyclopentadiene polymer is selected from, for example, one or more of dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, and dihydrodicyclopentadiene, and the dihydrodicyclopentadiene is, for example 【Chemistry 4】 The condition for being; (8) In the ruthenium alkylidene compound represented by formula I, R １１ and R １２ In the case of C ４ -C １８ Alkyl and R １－１ C replaced by ４ -C １８ C in alkyl ４ -C １８ Each alkyl group is independently C ４ -C １８ It is a linear alkyl group, for example -(CH ２ ) ３ CH ３ ,-(CH ２ ) ５ CH ３ ,-(CH ２ ) ９ CH ３ ,-(CH ２ ) １３ CH ３ , or - (CH ２ ) １７ CH ３ The condition for being; (9) In the ruthenium alkylidene compound represented by formula I, R １－１ In the case of C ６ -C １０ The aryl is either phenyl or naphthyl, for example, phenyl; In the ruthenium alkylidene compound represented by the formula II, R ２１ , R ２２ , and R ２３ , the C ６ -C １８ alkyls are each independently C ６ -C １０ alkyl, preferably C ６ alkyl, C ８ alkyl, or C １０ alkyl; Preferably, the ruthenium alkylidene compound represented by formula II is selected from one or more of the following compounds: 【Transformation 5】 for example 【Transformation 6】 The condition for this to be true.

3. The use of the cyclic olefin resin composition M1 in the manufacture of a base material for a high-frequency / high-speed information transmission device according to claim 1, characterized in that one or more of the following conditions are met. (1) The condition that component A is one of the following: Solution A1: The component A is tetracyclododecene; Plan A2: The component A is dihydrodicyclopentadiene; Plan A3: In component A, the mass percentage of dicyclopentadiene is 70% to 100%, for example, 79%, 80%, 90%, or 98%; Plan A4: In component A, the mass percentage of tricyclopentadiene is 0% to 30%, for example, 10%, 15%, or 20%; (2) In the ruthenium alkylidene compound represented by formula I, R １１ and R １２ Each of them is independent of C ４ -C １８ C substituted with an alkyl group or one phenyl group ４ -C １８ It is an alkyl group; Preferably, the ruthenium alkylidene compound represented by formula I is selected from one or more of the following compounds: 【Transformation 7】 for example 【Transformation 8】 The condition for this to be true.

4. The use of the cyclic olefin resin composition M1 in the manufacture of a base material for a high-frequency / high-speed information transmission device according to claim 1, characterized in that one or more of the following conditions are met. (1) The component A comprises 70% to 100% by mass of dicyclopentadiene and 0% to 30% by mass of tricyclopentadiene; Preferably, component A is one of the following: Plan B1: Component A consists of 85% to 95% by mass of dicyclopentadiene and 5% to 15% by mass of tricyclopentadiene; Plan B2: Component A consists of 90% to 100% by mass of dicyclopentadiene and 0% to 10% by mass of 5-ethylidene-2-norbornene; Plan B3: Component A consists of 70% to 90% by mass of dicyclopentadiene, 10% to 30% by mass of tricyclopentadiene, and 0% to 5% by mass of tetracyclopentadiene; Plan B4: Component A consists of 70% to 90% by mass of dicyclopentadiene, 10% to 20% by mass of tricyclopentadiene, 0% to 10% by mass of dihydrodicyclopentadiene, and 0% to 5% by mass of cyclohexene; More preferably, the condition is that component A is one of the following: Solution 1: Component A consists of 90% by mass dicyclopentadiene and 10% by mass tricyclopentadiene; Solution 2: Component A consists of 98% by mass dicyclopentadiene and 2% by mass 5-ethylidene-2-norbornene; Solution 3: Component A consists of 79% by mass dicyclopentadiene, 20% by mass tricyclopentadiene, and 1% by mass tetracyclopentadiene; Solution 4: The above-mentioned component A consists of 80% by mass dicyclopentadiene, 15% by mass tricyclopentadiene, 4.5% by mass dihydrodicyclopentadiene, and 0.5% by mass cyclohexene; (2) The substrate material of the high-frequency / high-speed information transmission device is a copper foil substrate; (3) The condition that component B is as follows: Solution D1: Component B is a ruthenium alkylidene compound represented by formula I; Solution D2: Component B is a ruthenium alkylidene compound represented by formula II; Solution D3: The component B is a ruthenium alkylidene compound represented by formula I and a ruthenium alkylidene compound represented by formula II, for example 【Chemistry 9】 Here, the molar ratio of the ruthenium alkylidene compound represented by formula I to the ruthenium alkylidene compound represented by formula II is, for example, 1:(1.5-5), and further, for example, 1:

2.

5. The cyclic olefin resin composition M1 further comprises component C and / or component D, Component C is selected from one or more of solid paraffin, liquid paraffin, and chlorinated paraffin having a chlorine content of 5 wt% to 65 wt%, for example, liquid paraffin, chlorinated paraffin having a chlorine content of 5 wt% to 65 wt%, or a mixture of liquid paraffin and chlorinated paraffin having a chlorine content of 5 wt% to 65 wt%, in which the mass ratio of the liquid paraffin to the chlorinated paraffin having a chlorine content of 5 wt% to 65 wt% is, for example, (10 to 20):1, and moreover, for example, 11:1; Component D is a thermoplastic resin, carbon chain length C １２ The above linear or branched olefins, carbon chain length C １２ Selected from one or more of the linear or branched alkanes, solid paraffins, and mineral oils, the thermoplastic resin, the linear olefin, and the linear alkane contain only two elements, C and H; Preferably, the thermoplastic resin is selected from one or more of ethylene propylene rubber (EP), ethylene propylene diene terpolymer (EPDM), thermoplastic elastomer (POE), liquid butyl rubber (LBR), styrene butadiene rubber (SBR), hydrogenated styrene butadiene rubber (SEBS), and styrene butadiene styrene block copolymer (SBS); preferably, an additive is added to the thermoplastic resin, the additive being an organophosphorus compound and / or an antioxidant, the organophosphorus compound being selected from one or more of, for example, triphenylphosphine, tricyclohexylphosphine, trioctylphosphine, and tributylphosphine, the antioxidant is preferably a hindered phenol antioxidant, selected from one or more of, for example, antioxidant 264, antioxidant 1010, and antioxidant 168; preferably, the mass percentage of the additive is 0 to 0.5 wt%, for example, 0 to 0.3 wt%, based on the total mass of components A and D; Preferably, the carbon chain length C １２ The above linear or branched alkanes are n-pentadecanes; Preferably, the total mass ratio of component C and component B to the mass of component A is 1:(15-200), for example 1:(15-55), and more preferably 1:(20-50). Preferably, the use of the cyclic olefin resin composition M1 in the manufacture of a base material for a high-frequency / high-speed information transmission device according to claim 1, characterized in that the mass percentage of component D is 0 to 20 wt%, preferably 0 to 10 wt%, based on the total mass of component A and component D.

6. The use of the cyclic olefin resin composition M1 in the manufacture of a base material for a high-frequency / high-speed information transmission device according to claim 5, characterized in that one or more of the following conditions are met. (1) Component C is liquid paraffin and / or chlorinated paraffin having a chlorine content of 5 wt% to 65 wt%, and the mass ratio of component C to component B is (15 to 70):1, for example 21:1, 28:1, or 64:1; Preferably, component C is one of the following: Solution E1: Component C is liquid paraffin, and the mass ratio of component C to component B is (60-70):1, for example, 64:1; Solution E2: Component C is a paraffin chloride with a chlorine content of 5 wt% to 65 wt%, and the mass ratio of component C to component B is (15 to 35):1, for example, 21:1 or 28:1; Solution E3: The component C is a mixture of liquid paraffin and chlorinated paraffin having a chlorine content of 5 wt% to 65 wt%, the mass ratio of liquid paraffin to chlorinated paraffin having a chlorine content of 5 wt% to 65 wt% in the mixture is (10 to 20):1, for example 11:1, and the mass ratio of component C to component B is (60 to 70):1, for example 64:

1. (2) The paraffin chloride having a chlorine content of 5 wt% to 65 wt% is defined as paraffin chloride having a chlorine content of 5 wt% to 52 wt%.

7. The use of the cyclic olefin resin composition M1 in the manufacture of a base material for a high-frequency / high-speed information transmission device according to claim 1, characterized in that the cyclic olefin resin composition M1 is one of the following: Solution F1: The cyclic olefin resin composition M1 comprises component A as described in any one of claims 1 to 4 and component B as described in any one of claims 1 to 4; Solution F2: The cyclic olefin resin composition M1 comprises component A according to any one of claims 1 to 4, component B according to any one of claims 1 to 4, and component C according to any one of claims 5 to 6; Solution F3: The cyclic olefin resin composition M1 comprises component A according to any one of claims 1 to 4, component B according to any one of claims 1 to 4, and component D according to any one of claims 5 to 6; Proposal F4: The cyclic olefin resin composition M1 comprises component A according to any one of claims 1 to 4, component B according to any one of claims 1 to 4, component C according to any one of claims 5 to 6, and component D according to any one of claims 5 to 6; Preferably, the cyclic olefin resin composition M1 consists of one of the following: Plan C1: Component A and Component B, The aforementioned component A consists of dicyclopentadiene and tricyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 90%, and the mass percentage of tricyclopentadiene in component A is 10%; The aforementioned component B is 【Chemistry 10】 And, The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; Plan C2: Component A and Component B, The aforementioned component A is tetracyclododecene; The aforementioned component B is 【Chemistry 11】 And, The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:15000; Plan C3: Component A and Component B, The aforementioned component A is dihydrodicyclopentadiene; The aforementioned component B is 【Chemistry 12】 And, The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:15000; Plan C4: Component A, Component B and Component C, The aforementioned component A consists of dicyclopentadiene and 5-ethylidene-2-norbornene, where the mass percentage of dicyclopentadiene in component A is 98%, and the mass percentage of 5-ethylidene-2-norbornene in component A is 2%; The aforementioned component B is 【Chemistry 13】 And; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; The aforementioned component C is liquid paraffin; The total mass ratio of component C and component B to the mass of component A is 1:20; Plan C5: Component A, Component B and Component C, The aforementioned component A consists of dicyclopentadiene and tricyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 90%, and the mass percentage of tricyclopentadiene in component A is 10%; The aforementioned component B is 【Chemistry 14】 And; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; The aforementioned component C is paraffin chloride with a chlorine content of 5%; The total mass ratio of component C and component B to the mass of component A is 1:50; Plan C6: Component A, Component B and Component C, The aforementioned component A consists of dicyclopentadiene and tricyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 90%, and the mass percentage of tricyclopentadiene in component A is 10%; The aforementioned component B is 【Chemistry 15】 And; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; The aforementioned component C is paraffin chloride with a chlorine content of 5%; The total mass ratio of component C and component B to the mass of component A is 1:50; Plan C7: Component A and Component B The aforementioned component A consists of dicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 79%, the mass percentage of tricyclopentadiene in component A is 20%, and the mass percentage of tetracyclopentadiene in component A is 1%; The aforementioned component B is 【Chemistry 16】 And; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; Plan C8: Component A, Component B and Component C, The aforementioned component A consists of dicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 79%, the mass percentage of tricyclopentadiene in component A is 20%, and the mass percentage of tetracyclopentadiene in component A is 1%; The aforementioned component B is 【Chemistry 17】 And; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; The aforementioned component C is liquid paraffin; The total mass ratio of component C and component B to the mass of component A is 1:200; Plan C9: Component A and Component B, The aforementioned component A consists of dicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 79%, the mass percentage of tricyclopentadiene in component A is 20%, and the mass percentage of tetracyclopentadiene in component A is 1%; The aforementioned component B is [Chemistry 18] And; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; Plan C10: Component A and Component B, The aforementioned component A consists of dicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 79%, the mass percentage of tricyclopentadiene in component A is 20%, and the mass percentage of tetracyclopentadiene in component A is 1%; The aforementioned component B is 【Chemistry 19】 And; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:50000; Plan C11: Component A, Component B and Component C, The aforementioned component A consists of dicyclopentadiene, tricyclopentadiene, dihydrodicyclopentadiene, and cyclohexene, where the mass percentage of dicyclopentadiene in component A is 80%, the mass percentage of tricyclopentadiene in component A is 15%, the mass percentage of dihydrodicyclopentadiene in component A is 4.5%, and the mass percentage of cyclohexene in component A is 0.5%; The aforementioned component B is 【Chemistry 20】 And; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:9500; The aforementioned component C consists of liquid paraffin and chlorinated paraffin with a chlorine content of 52 wt%, where the mass ratio of liquid paraffin to chlorinated paraffin with a chlorine content of 52 wt% is 11:1; The total mass ratio of component C and component B to the mass of component A is 1:20; Plan C12: Component A and Component B, The aforementioned component A consists of dicyclopentadiene and tricyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 90%, and the mass percentage of tricyclopentadiene in component A is 10%; The aforementioned component B is 【Chemistry 21】 It consists of, and here, 【Chemistry 22】 The molar ratio is 1:2; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; Plan C13: Component A and Component B, The aforementioned component A consists of dicyclopentadiene and tricyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 90%, and the mass percentage of tricyclopentadiene in component A is 10%; The aforementioned component B is 【Chemistry 23】 And; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:7500; Plan C14: Component A, Component B, and Component D The aforementioned component A consists of dicyclopentadiene and tricyclopentadiene, where the mass percentage of dicyclopentadiene in component A is 90%, and the mass percentage of tricyclopentadiene in component A is 10%; The aforementioned component B is 【Chemistry 24】 And; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; The aforementioned component D is a mixture of n-pentadecane, EPDM, SBS, and mineral oil; Based on the total mass of components A and D, the mass percentage of n-pentadecane in component D is 4-5%, and the mass percentages of EPDM, SBS, and mineral oil are independently 2-3%; Plan C15: Component A, Component B, and Component D The aforementioned component A consists of dicyclopentadiene and tricyclopentadiene, with dicyclopentadiene accounting for 90% of the mass of component A and tricyclopentadiene accounting for 10% of the mass of component A; The aforementioned component B is 【Chemistry 25】 And; The molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:10000; The aforementioned component D is a mixture of n-pentadecane, hexadecene, EPDM, SEBS, POE, and mineral oil; Based on the total mass of components A and D, the mass percentage of n-pentadecane is 2-4%, the mass percentage of hexadecene is 0.3-1%, the mass percentage of EPDM is 2-3%, the mass percentage of SEBS is 0.3-1%, the mass percentage of POE is 0.5-1.2%, and the mass percentage of mineral oil is independently 2-3%. Plan C16: Component A, Component B, and Component D Component A consists of dicyclopentadiene and tricyclopentadiene, where dicyclopentadiene accounts for 90% of the mass of component A, and tricyclopentadiene accounts for 10% of the mass of component A; The aforementioned component B is 【Chemistry 26】 And; The aforementioned component D is a mixture of antioxidant 264, triphenylphosphine, n-pentadecane, EPDM, SEBS, and POE; Based on the total mass of components A and D, the mass percentage of antioxidant 264 is 0.1-0.2%, the mass percentage of triphenylphosphine is 0.02-0.1%, the mass percentage of n-pentadecane is 4-5%, the mass percentage of EPDM is 1-2%, the mass percentage of SEBS is 1-2%, and the mass percentage of POE is 1-2%.

8. A cyclic olefin resin composition characterized by being one of the following cyclic olefin resin compositions M1, M2, M3, M4, or M5. Cyclic olefin resin composition M1: The cyclic olefin resin composition M1 according to any one of claims 1 to 7, wherein the mass percentage of component A in the cyclic olefin resin composition M1 is 80% or more and less than 100%; Cyclic olefin resin composition M2: comprising component A according to any one of claims 1 to 4 and component B according to any one of claims 1 to 4; Cyclic olefin resin composition M3: comprising component A according to any one of claims 1 to 4, component B according to any one of claims 1 to 4, and component C according to any one of claims 5 to 6; Cyclic olefin resin composition M4: comprising component A according to any one of claims 1 to 4, component B according to any one of claims 1 to 4, and component D according to any one of claims 5 to 6; Cyclic olefin resin composition M5: comprises component A according to any one of claims 1 to 4, component B according to any one of claims 1 to 4, component C according to any one of claims 5 to 6, and component D according to any one of claims 5 to 6.

9. A cyclic olefin resin material, A cyclic olefin resin composition M1, cyclic olefin resin composition M2, cyclic olefin resin composition M3, cyclic olefin resin composition M4, or cyclic olefin resin composition M5 described in claim 8 is manufactured as a raw material. Preferably, the cyclic olefin resin material is characterized by satisfying one or more of the following conditions. (1) The cyclic olefin resin material has a dielectric loss of <0.001 at a frequency ≥ 1 GHz, for example, a dielectric loss of 0.00067, 0.00069, 0.00071, 0.00072, 0.00073, 0.00075, 0.00077, 0.00078, 0.00079, 0.00085, 0.00086, 0.00087, 0.00088, 0.00089, 0.0009 or 0.00091; the frequency is ≥ 1 GHz, for example, 1 to 12 GHz, and more specifically, 10 GHz; (2) The cyclic olefin resin material has a dielectric constant < 2.5 at a frequency ≥ 1 GHz, for example, a dielectric constant of 2.23, 2.26, 2.27, 2.28, 2.29, 2.30, 2.31 or 2.32; the frequency is ≥ 1 GHz, for example, 1 to 12 GHz, and more specifically, 10 GHz; (3) The glass transition temperature of the cyclic olefin resin material is ≥ 135°C, for example, 138°C, 149°C, 152°C, 155°C, 157°C, 160°C, 162°C, 164°C, 165°C, 166°C, 175°C, 177°C, 186°C, 189°C, or 190°C; (4) The thermal distortion temperature of the cyclic olefin resin material is ≥ 110°C, for example, 115°C, 117°C, 119°C, 122°C, 126°C, 127°C, 134°C, 137°C, 142°C, 144°C, 147°C, 158°C, or 167°C; (5) The cyclic olefin resin material is manufactured using a liquid molding process, such as a reaction injection molding process, a resin transfer molding process, and a vacuum-assisted resin injection molding process, wherein the molding temperature in the reaction injection molding process, the resin transfer molding process, and the vacuum-assisted resin injection molding process may be 40 to 145°C, preferably 40 to 90°C, for example 40°C, 45°C, 60°C, 70°C, 80°C, or 140°C; and the curing time is 1 to 120 minutes, preferably 2 to 60 minutes, for example 3.5 minutes, 5 minutes, 10 minutes, 20 minutes, 25 minutes, or 30 minutes.

10. A method for producing a cyclic olefin resin material, The process includes a step of producing a cyclic olefin resin material by mixing each component of the resin composition using the cyclic olefin resin composition M1, cyclic olefin resin composition M2, cyclic olefin resin composition M3, cyclic olefin resin composition M4, or cyclic olefin resin composition M5 described in claim 8 as raw materials, and curing and molding the resin composition, wherein the curing and molding temperature is 40 to 145°C and the curing and molding time is 1 to 120 minutes; Preferably, the curing temperature is 40°C, 45°C, 60°C, 70°C, 80°C, or 140°C; Preferably, the curing time is 2 to 60 minutes, for example 3 to 30 minutes, and more specifically, for example 3.5 minutes, 5 minutes, 10 minutes, 20 minutes, 25 minutes, or 30 minutes; Preferably, the liquid molding process is a reaction injection molding process, a resin transfer molding process, and a vacuum-assisted resin injection molding process; (1) The liquid molding process is a resin transfer molding process and includes the step of adding a mixture of components of the cyclic olefin resin composition M1, M2, M3, M4, or M5 to a mold and curing it; (2) The liquid molding process is a reaction injection molding process, the raw material is the cyclic olefin resin composition M3, and the process includes adding a mixture of the components of the cyclic olefin resin composition M3 to a mold and curing it; Preferably, the mixture of the components of the cyclic olefin resin composition M3 is obtained by mixing the components of the cyclic olefin resin composition M3 at a pressure of 1 to 3 MPa, for example, 2 MPa; Preferably, the mixture of the components of the cyclic olefin resin composition M3 is added to the mold within 4 to 6 seconds, for example, within 5 seconds; (3) A manufacturing method characterized by satisfying any one of the following conditions: the liquid molding process is a vacuum-assisted resin injection molding process, and the liquid molding process includes adding a mixture of components of the cyclic olefin resin composition M1, M2, M3, M4, or M5 to a mold and curing it.

11. A method for producing a cyclic olefin resin material according to claim 10, characterized in that one or more of the following conditions are met. (1) In the reaction injection molding process, resin transfer molding process or vacuum-assisted resin injection molding process, the mixture is a mixture of component A in each resin composition and other components in each resin composition, wherein component A may be stirred at 60°C to 125°C for 4 to 12 hours, cooled to room temperature, and then subjected to a pretreatment; (2) In the reaction injection molding process, resin transfer molding process or vacuum-assisted resin injection molding process, the temperature of the mold is 40 to 145°C; Preferably, in the reaction injection molding process or resin transfer molding process, the mold temperature on one side of the mold is 40 to 145°C, for example 60 to 140°C, and the mold temperature on the other side is 40 to 145°C, for example 40 to 140°C; More preferably, in the reaction injection molding (RIM) process or resin transfer molding (RTM) process, the temperature of the mold is one of the following: Solution 1: One side mold temperature 70°C, other side mold temperature 40°C; Option 2: One side mold temperature 80°C, other side mold temperature 45°C; Option 3: One side mold temperature 140°C, the other side mold temperature 140°C; Option 4: One side mold temperature 60°C, other side mold temperature 40°C; (3) The reaction injection molding process, resin transfer molding process, or vacuum-assisted resin injection molding process further includes a post-curing step, wherein the temperature of the post-curing step is 60 to 145°C, for example 140°C, and the post-curing time is 0 to 60 minutes, for example 20 minutes.

12. A method for reducing the dielectric constant and / or dielectric loss of a cyclic olefin resin material, In manufacturing the cyclic olefin resin material, component B according to any one of claims 1 to 4 is introduced into component A according to any one of claims 1 to 4, wherein the molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:(7500 to 60000); Preferably, the raw material for the cyclic olefin resin material is the cyclic olefin resin composition M1, M2, M3, M4, or M5 described in claim 8; Preferably, the method for producing the cyclic olefin resin material is the method for producing the cyclic olefin resin material described in any one of claims 10 to 11; A method for reducing the dielectric constant and / or dielectric loss of a cyclic olefin resin material, preferably characterized in that the molar ratio of Ru in component B to the cyclic olefin monomer of component A is 1:(7500 to 50000), for example, 1:7500, 1:9500, 1:10000, 1:15000, or 1:50000.

13. A semi-cured sheet comprising the cyclic olefin resin material described in claim 9.

14. A copper foil substrate comprising the semi-cured sheet described in claim 13.

15. A printed circuit board including a copper foil substrate as described in claim 14.

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