Benzocyclobutene resin, resin composition and use thereof

Abstract

The present invention relates to a benzocyclobutene resin, a resin composition, and uses thereof. The benzocyclobutene resin comprises at least one structural unit A and at least one structural unit B, where structural unit A has a structure represented by Formula I and structural unit B has a structure represented by Formula II. The benzocyclobutene resin has an all-hydrocarbon structure and has a sufficiently low dielectric constant Dk and dielectric dissipation factor Df. The benzocyclobutene resin also has a high glass transition temperature, low water absorption, good heat resistance and moist heat resistance, excellent dielectric properties, high modulus, and mechanical properties. Furthermore, the benzocyclobutene resin also has good processability, fully meeting the performance requirements for resin materials in high-performance PCBs.

Description

[Technical Field]

[0001] The present invention relates to the technical field of communication materials, in particular to benzocyclobutene resins, resin compositions and uses thereof. [Background technology]

[0002] With the progress of society and the development of science and technology, people's demands for communication network speeds are increasing. The currently developing 6G technology uses terahertz (THz) or submillimeter wave bands, and its transmission capacity is 100 times higher than that of 5G. The higher the communication frequency, the higher the requirements for printed circuit boards (PCBs), mainly including lower dielectric loss tangent Df, lower dielectric constant Dk, higher reliability, higher heat resistance, and lower coefficient of thermal expansion CTE.

[0003] PCBs are typically made by processing copper-clad boards through various processes, and their performance and quality depend largely on the properties and manufacturing level of the copper-clad board. Because copper-clad boards contain copper foil, reinforcing materials, and resin materials, research and development is needed to develop resins with excellent dielectric properties, i.e., low dielectric constants and dielectric dissipation factors. Meanwhile, in recent years, there has been a noticeable trend toward smaller, higher-density mounting methods for electronic devices for communication, consumer electronics, and industrial applications. This has led to the need for printed wiring boards to be pressure-bonded multiple times to form high-density, multi-layer printed wiring boards. The copper-clad boards used as raw materials for multi-layer printed wiring boards must have higher heat resistance, better dimensional stability, and a lower thermal expansion coefficient.

[0004] For many years, the industry has been researching thermosetting polyphenylene ether resins, bismaleimide resins, hydrocarbon resins, and other materials with good dielectric properties. Currently, mass-produced PCBs primarily use thermosetting resins based on a vinyl-terminated polyphenylene ether-based composite with triallyl isocyanurate (TAIC). While these resins offer excellent mechanical and heat resistance, the polar groups in TAIC mean that their Dk and Df do not meet the requirements of next-generation communication technologies. To further improve dielectric properties, researchers have focused on developing new low-dielectric materials. Research has shown that reducing the polarizability of molecules within a material and increasing porosity are effective ways to achieve low dielectric constant. For example, polypropylene and polystyrene have low Dk and Df. However, their heat resistance falls far short of the requirements for PCBs.

[0005] The fabrication process for integrated circuits requires temperatures above 400°C, and subsequent processing steps require even higher temperatures. Copper interconnects can be produced by electroplating or chemical reduction and can be completed at temperatures below 250°C. However, to ensure the copper deposition is dense and porosity-free, annealing must be performed at 400–450°C, requiring materials with excellent heat resistance and a high glass transition temperature. While polyimides and polybenzoxazines can meet the required heat resistance, there is an urgent need to design and develop new high-temperature resin materials with an all-hydrocarbon structure to achieve lower Dk and Df. Dow Chemical Company has previously released a phenylethynyl-containing all-hydrocarbon SiLK resin, which has an extremely low dielectric constant (Dk of 2.65) and a high glass transition temperature of 490°C. However, the synthesis cost of such materials is high and their mechanical performance falls short of the required level. Benzocyclobutene is another all-hydrocarbon thermosetting resin. Its excellent heat resistance, mechanical properties, extremely low dielectric loss, extremely low dielectric constant, and low cost make it a promising next-generation high-performance electronic material for advanced microelectronics applications. Benzocyclobutene has a low boiling point of approximately 150°C and is a highly volatile liquid. It is typically prepared and used as a derivative. Benzocyclobutene can react with vinyl groups at high temperatures to form cyclohexane structures, or dimerize to cyclooctane structures at higher temperatures, achieving high heat resistance. Benzocyclobutene derivatives are also low molecular weight and typically contain two or more benzocyclobutene functional groups, allowing further polymerization at high temperatures. For example, siloxane-containing dibenzocyclobutenes can be obtained by the Heck coupling reaction of 4-bromobenzocyclobutene with tetramethyldivinyldisiloxane, or etherification of 4-bromobenzocyclobutene with resorcinol under cuprous chloride catalysis to produce bisbenzocyclobutene derivatives containing phenyl ether and naphthoic acid structures. The above-mentioned materials have extremely high heat resistance and mechanical properties, but since they contain siloxane or phenol groups rather than an all-hydrocarbon structure, it is difficult to obtain low dielectric constants.Prior art has also disclosed the Suzuki coupling reaction of 4-bromobenzocyclobutene and benzenediboronic acid to produce all-hydrocarbon derivatives, but the high cost of benzenediboronic acid and the residual polar boronic acid or boronic acid end groups reduce the dielectric properties, sacrificing the original dielectric advantages of the benzocyclobutene structure. Researchers have also attempted to produce all-hydrocarbon derivatives by Heck coupling reaction using divinylbenzene and benzocyclobutene, but divinylbenzene undergoes radical polymerization at room temperature, which is prone to producing by-products and makes mass production difficult.

[0006] Therefore, the development of a resin material that combines excellent dielectric properties, heat resistance, mechanical performance, and processability, and that can be easily mass-produced, is an issue that must be resolved as soon as possible in this field. Summary of the Invention [Problem to be solved by the invention]

[0007] In response to the shortcomings of the prior art, the present invention aims to provide a benzocyclobutene resin, a resin composition and its use, which has an all-hydrocarbon structure, a sufficiently low dielectric constant and dielectric dissipation factor, and excellent heat resistance, moist heat resistance, mechanical properties, stability and processability. The manufacturing method is simple and mass production is easy, fully meeting the performance requirements for resin materials for high-performance PCBs. [Means for solving the problem]

[0008] In order to achieve the object of the present invention, the present invention provides the following technical solutions.

[0009] In aspect 1, the present invention provides a method for producing a pharmaceutical composition comprising: at least one structural unit A and at least one structural unit B, wherein said structural unit A has a structure shown in formula I: [ka] In Formula I, R1 is an ethenylene group and / or an ethylene group; The structural unit B has a structure shown in formula II, [ka] In formula II, R2 is a vinyl group, an ethyl group, and / or a phenyl group. Benzocyclobutene resins are provided.

[0010] In the benzocyclobutene resin according to the present invention, the side chain of the structural unit A contains a benzocyclobutyl group structure, and the structural unit B is one or a combination of at least two of polybutadiene, hydrogenated polybutadiene, and polystyrene structures. The benzocyclobutene resin has an all-hydrocarbon structure and exhibits a low dielectric constant Dk and a low dielectric dissipation factor Df. Furthermore, the molecular structure contains highly reactive alkenyl groups, resulting in high crosslinking efficiency during thermosetting reactions. The benzocyclobutene resin has a high glass transition temperature, low water absorption, good thermal stability and moist heat resistance, excellent dielectric properties, high modulus, and mechanical properties, and also has good processability, fully meeting the performance requirements for resin materials in high-performance PCBs.

[0011] Preferably, the structural unit A in the benzocyclobutene resin is 5% or more in mole percent, for example, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%, or a specific point value between the above points; for the sake of space and clarity, the present invention does not comprehensively list specific point values ​​included in the above range, and 30% or more is more preferable, and 30 to 60% is even more preferable.

[0012] Preferably, the benzocyclobutene resin contains a structural unit A1, which has a structure represented by formula IA, contains an ethenylene group that is easily reactive in the molecular structure, and has high crosslinking efficiency in the thermosetting reaction. [ka]

[0013] Preferably, the benzocyclobutene resin comprises a building block A2 having the structure shown in formula IB. [ka]

[0014] Preferably, the structural unit A2 is obtained by hydrogenating the structural unit A1, has a molecular structure containing a saturated carbon chain, and has low dielectric loss.

[0015] Preferably, the structural unit B in the benzocyclobutene resin is 15 to 90% by mole, and may be, for example, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, or 85%, or a specific point value between the above points; for the sake of space and clarity, the present invention does not comprehensively list specific point values ​​included in the above range.

[0016] In a preferred technical solution of the present invention, the structural unit A in the benzocyclobutene resin is 5 to 80% by mole, more preferably 30 to 60%, and the structural unit B is 15 to 90% by mole, more preferably 30 to 70%, thereby providing the benzocyclobutene resin with excellent dielectric properties, heat resistance, modulus, and mechanical properties, as well as high thermosetting crosslinking activity and crosslink density. If the structural unit A mole percentage is too low, the heat resistance of the benzocyclobutene resin decreases. If the structural unit A mole percentage is too high, synthesis becomes more difficult and production costs increase, while the degree of crosslinking curing of the benzocyclobutene resin decreases, resulting in poor dielectric properties.

[0017] Preferably, the benzocyclobutene resin contains a structural unit B1, which has a structure represented by formula IIA, contains a reactive vinyl group in its molecular structure, and has high crosslinking efficiency in a thermosetting reaction. [ka]

[0018] Preferably, the benzocyclobutene resin comprises a structural unit B2, and the structural unit B2 has a structure represented by formula IIB. [ka]

[0019] Preferably, the structural unit B2 is obtained by hydrogenating the structural unit B1, contains saturated alkyl structural units, and has low dielectric loss.

[0020] Preferably, the benzocyclobutene resin contains a structural unit B3, and the structural unit B3 has a structure represented by formula IIC, contains a phenyl group in its side chain, and has good compatibility with other resins. [ka]

[0021] Preferably, the benzocyclobutene resin may contain only the structural unit B1 (unhydrogenated), may contain both the structural unit B1 and the structural unit B2 structure (partially hydrogenated), may contain only the structural unit B2 (fully hydrogenated), may contain both the structural unit B1 and the structural unit B3 structure (unhydrogenated), may contain both the structural unit B1, the structural unit B2, and the structural unit B3 structure (partially hydrogenated), or may contain both the structural unit B2 and the structural unit B3 structure (fully hydrogenated).

[0022] Preferably, the benzocyclobutene resin further comprises a structural unit C, and the structural unit C has a structure represented by Formula IIIA and / or Formula IIIB. [ka] [ka]

[0023] The benzocyclobutene resin according to the present invention has a polymer segment structure and includes at least one (preferably, multiple) structural unit A, at least one (preferably, multiple) structural unit B, and a preferred structural unit C. The present invention does not limit the order in which the structural units are linked, and any chemically possible linking order / linking method is included within the scope of the present invention.

[0024] Preferably, the structural unit C in the benzocyclobutene resin is 40% or less by mole, such as 0, 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, or 40%, or any specific value between the above values. For the sake of space and clarity, the present invention does not exhaustively list specific values ​​within the above range, but rather, 30% or less is more preferred, 20% or less is even more preferred, and 10% or less is most preferred. This increases the degree of cure of the benzocyclobutene resin and allows it to have a higher glass transition temperature.

[0025] Preferably, the number average molecular weight of the benzocyclobutene resin is 1,000 to 20,000, such as 2,000, 5,000, 8,000, 10,000, 12,000, 15,000, or 18,000, and may be any specific value between the above values. For the sake of space and clarity, the present invention does not exhaustively list the specific values ​​included in the range.

[0026] Illustratively, the method for producing the benzocyclobutene resin comprises the steps of: [ka] and a benzocyclobutene resin is obtained by coupling reaction of the benzocyclobutene resin with the benzocyclobutene resin. [ka] wherein Hal is a halogen and may be, for example, Cl, Br or I.

[0027] Preferably, Hal is Br, i.e., the starting material is 4-bromobenzocyclobutene. [ka] is.

[0028] Preferably, the coupling reaction is carried out in the presence of a palladium catalyst system.

[0029] Preferably, the palladium catalyst system comprises a palladium catalyst and an organophosphine ligand.

[0030] Preferably, the palladium catalyst is palladium acetate and the organophosphine ligand is tris(o-methylphenyl)phosphine.

[0031] Preferably, the coupling reaction is carried out in the presence of an acid binding agent.

[0032] Preferably, the acid binding agent comprises an organic base, more preferably triethylamine.

[0033] Preferably, the coupling reaction is carried out under an inert atmosphere, which includes one of a nitrogen atmosphere, an argon atmosphere, and a helium atmosphere.

[0034] Preferably, the temperature of the coupling reaction is 60 to 100°C, such as 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, or 95°C, and may be any specific point value between the above points, and for the sake of space and clarity, the present invention does not exhaustively list any specific point values ​​included in the above range.

[0035] Preferably, the duration of the coupling reaction is 5 to 36 hours, such as 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 24 hours, 28 hours, 32 hours, or 34 hours, and may be any specific time point between the above-mentioned time points. For the sake of space and clarity, the present invention does not exhaustively list the specific time points included in the above range.

[0036] Illustratively, the method for producing the benzocyclobutene resin comprises the steps of: [ka] and a coupling reaction of Hal with a styrene structural unit B, where Hal is a halogen (e.g., Cl, Br, or I), to obtain the benzocyclobutene resin. R1 in the structural unit A is an ethenylene group, and R2 in the structural unit B is a vinyl group and a phenyl group, i.e., the benzocyclobutene resin simultaneously contains a polybutadiene structural unit (structural unit B1) and a styrene structural unit (structural unit B3), and further contains a preferred structural unit C.

[0037] In a preferred technical solution of the present invention, the benzocyclobutene resin is prepared by coupling polybutadiene or butadiene-styrene copolymer with halobenzocyclobutene. Its chemical properties are stable, and it does not require the addition of a polymerization inhibitor for storage. Furthermore, the preparation process is simple, the yield is high, there are few side reactions, and it is easy to mass-produce.

[0038] Preferably, the preparation of the benzocyclobutene resin further comprises a preferred hydrogenation step, which can be carried out before and / or after the coupling reaction, and may be complete (i.e., hydrogenating all C=C groups in the main chain and branched chains of the benzocyclobutene resin, preferably after the coupling reaction) or partial (before or after the coupling reaction). The hydrogenation reaction completely or partially hydrogenates the C=C double bonds derived from a C-H resin (e.g., polybutadiene and / or styrene-butadiene copolymer) to form saturated carbon chains, thereby further optimizing the dielectric properties of the benzocyclobutene resin.

[0039] In a second aspect, the present invention provides a resin composition, wherein a resin of the resin composition includes the benzocyclobutene resin according to the first aspect.

[0040] Preferably, the content of the benzocyclobutene resin in the resin is 5 to 100% by mass, and may be, for example, 8%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%, or a specific value between the above-mentioned values. For the sake of space and clarity, the present invention does not exhaustively list specific values ​​included in the above range.

[0041] Preferably, the resin further comprises an unsaturated group-containing thermosetting component.

[0042] In the present invention, the resin in the resin composition may be a benzocyclobutene resin used alone or in combination with a thermosetting component containing another unsaturated group (a group with a C=C double bond), and can be used as a base material for next-generation communication devices.

[0043] Preferably, the content of the unsaturated group-containing thermosetting component in the resin is 95% or less by mass, and may be, for example, 0, 5, 10, 20, 30, 40, 50, 60, 70, 80, or 90%, as well as specific values ​​between the above-mentioned values. For the sake of space and clarity, the present invention does not exhaustively list specific values ​​within the above ranges.

[0044] Preferably, the unsaturated group comprises at least one of a vinyl group, a vinylphenyl group, a vinylbenzyl group, an allyl group, a (meth)acrylate group, or an isopropenyl group.

[0045] In the present invention, the (meth)acrylate group includes an acrylate group and / or a methacrylate group.

[0046] In the present invention, the unsaturated group-containing thermosetting component may be an unsaturated group-containing resin (polymer) and / or an unsaturated group-containing low molecular weight compound.

[0047] Preferably, the unsaturated group-containing thermosetting component includes one or a combination of at least two of polybutadiene, styrene-butadiene copolymer, styrene-butadiene-styrene triblock copolymer, unsaturated polyphenylene ether resin, maleimide compound, vinyl aromatic polymer, vinyl alicyclic polymer, allyl compound, and polyfunctional vinyl compound.

[0048] In the present invention, the thermosetting components, polybutadiene, styrene-butadiene copolymer, and styrene-butadiene-styrene triblock copolymer, all contain a crosslinkable active group C=C, and are 1,2-vinyl groups based on butadiene monomers. [ka] may be.

[0049] Preferably, the unsaturated polyphenylene ether resin comprises a polyphenylene ether resin capped with an unsaturated group, which may be any one of a vinylbenzyl group, a vinylphenyl group, an acrylate group, or a methacrylate group.

[0050] Preferably, the allyl group compound includes any one or a combination of at least two of triallyl isocyanurate (TAIC), trimethallyl isocyanurate (TMAIC), triallyl cyanurate (TAC), triallyl polyisocyanurate, triallyl cyanurate, and diallyl phthalate.

[0051] Preferably, the polyfunctional vinyl compound includes any one or a combination of at least two of trimethylacrylic acid, divinylbenzene, a polyfunctional acrylate, and P,P'-divinyl-1,2-diphenylethane (BVPE).

[0052] Preferably, the resin further includes a thermoplastic resin.

[0053] Preferably, the content of the thermoplastic resin in the resin is 80% or less by mass, and may be, for example, 0, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70% or 75%, as well as specific values ​​between the above-mentioned values. For the sake of space and clarity, the present invention does not exhaustively list specific values ​​included in the above ranges.

[0054] Preferably, the thermoplastic resin comprises a hydrogenated styrene-butadiene block copolymer (SEBS) and / or a thermoplastic polyphenylene ether (PPO).

[0055] Preferably, the hydrogenated styrene-butadiene block copolymer comprises unmodified SEBS and / or modified SEBS.

[0056] Preferably, the modified SEBS includes one or a combination of at least two of maleic anhydride-modified SEBS, epoxy-modified SEBS, amine-modified SEBS, and carboxyl-modified SEBS.

[0057] Preferably, the resin composition further contains an initiator.

[0058] Preferably, the mass of the initiator is 0.1 to 3 parts, for example, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, or 2.8 parts, relative to 100 parts of the total mass of the benzocyclobutene resin and the preferred unsaturated group-containing thermosetting component in the resin, and may be any specific value between the above-mentioned values. For reasons of space and clarity, the present invention does not exhaustively list specific values ​​included in the above ranges.

[0059] Preferably, the initiator includes any one or a combination of at least two of an organic peroxide, an azo-based initiator, and a carbon-based radical initiator.

[0060] Preferably, the initiator includes any one or a combination of at least two of t-butylisopropylphenyl peroxide, dicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne, 1,1-bis(t-butylperoxy)-3,3,5-dimethylcyclohexane, 2,3-dimethyl-2,3-diphenylbutane, and poly-1,4-diisopropylbenzene.

[0061] Preferably, the resin composition further contains a filler.

[0062] Preferably, in the resin composition, the mass of the resin is 100 parts, and the mass of the filler is 5 to 400 parts, for example, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 120 parts, 150 parts, 180 parts, 200 parts, 220 parts, 250 parts, 280 parts, 300 parts, 320 parts, 350 parts or 380 parts, and specific point values ​​between the above point values ​​may also be used. For the sake of space and simplicity, the present invention does not comprehensively list specific point values ​​included in the above range, and 5 to 200 parts is more preferable, and 5 to 150 parts is even more preferable.

[0063] Preferably, the filler is an inorganic filler and / or an organic filler, more preferably an inorganic filler.

[0064] Preferably, the inorganic filler includes any one or a combination of at least two of non-metal oxides, metal oxides, metal hydroxides, metal nitrides, non-metal nitrides, inorganic hydrates, inorganic salts, metal hydrates, and inorganic phosphorus.

[0065] Preferably, the inorganic filler includes one or a combination of at least two of silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, and mica.

[0066] Preferably, the silica may be any one of fused silica, crystalline silica, spherical silica, and hollow silica, or a combination of at least two of them.

[0067] Preferably, the organic filler comprises one or a combination of at least two of polyphenylene ether filler (powder and / or microspheres), polytetrafluoroethylene filler (powder), polyether ether ketone filler, polyphenylene sulfide filler, and polyether sulfone filler (powder).

[0068] Preferably, the median diameter (D50 ) is 0.01 to 50 μm, and may be, for example, 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, or a specific point value between the above point values. For reasons of space and simplicity, the present invention does not comprehensively list specific point values ​​included in the above range, and 0.01 to 20 μm is more preferable, and 0.01 to 10 μm is even more preferable.

[0069] Illustratively, the particle size of the filler is measured with a Malvern Mastersizer MS3000.

[0070] Preferably, the filler comprises a surface-treated filler.

[0071] Preferably, the surface treatment agent for the surface treatment includes one or a combination of at least two of a silane coupling agent, a silicone oligomer, and a titanate coupling agent.

[0072] Preferably, the mass of the surface treatment agent is 0.1 to 5 parts, for example, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, or 4.5 parts, and may be a specific point value between the above points. For reasons of space and simplicity, the present invention does not comprehensively list specific point values ​​included in the above range, and 0.5 to 3 parts is more preferable, and 0.75 to 2 parts is even more preferable.

[0073] Preferably, the resin composition further contains a flame retardant.

[0074] Preferably, in the resin composition, the mass of the flame retardant is 1 to 50 parts, for example, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, or 45 parts, based on 100 parts of the mass of the resin. For the sake of space and clarity, the present invention does not exhaustively list specific values ​​included in the range.

[0075] Preferably, the flame retardant includes one or a combination of at least two of a nitrogen-based flame retardant, a halogen-based flame retardant, a phosphorus-based flame retardant, and a metal hydroxide flame retardant.

[0076] A solvent may be further added to the resin composition. The amount of solvent added can be selected by those skilled in the art according to their experience and process needs, as long as the viscosity of the resin composition is suitable for use, making it easy to immerse, apply, etc. After that, the solvent in the resin composition will be partially or completely volatilized during drying, semi-curing, or full curing.

[0077] The solvent used in the present invention is not particularly limited, and generally includes ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; alcohols such as methanol, ethanol, and butanol; alcohols such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, and butyl carbitol; and nitrogen-containing solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. These solvents may be used alone or in combination. Ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene are preferred.

[0078] The resin composition according to the present invention is produced by the following method, which includes mixing and uniformly dispersing the components of the resin composition to obtain the resin composition.

[0079] In a third aspect, the present invention provides a resin film, wherein a material of the resin film includes the resin composition according to the second aspect.

[0080] Preferably, the resin film is produced by applying the resin composition to a release agent and drying and / or semi-curing the composition.

[0081] In a fourth aspect, the present invention provides a resin-coated copper foil comprising a copper foil layer and a resin layer, the resin layer being made of the resin composition according to the second aspect.

[0082] Preferably, the resin-coated copper foil is produced by applying the resin composition to a copper foil and drying and / or semi-curing the resin composition.

[0083] In a fifth aspect, the present invention provides a prepreg including a reinforcing material and the resin composition according to the second aspect attached to the reinforcing material.

[0084] Preferably, the resin composition is applied to the reinforcing material by dipping and drying.

[0085] Preferably, the raw material of the reinforcing material includes one or a combination of at least two of natural fibers, organic synthetic fibers, organic woven fabrics, and inorganic fibers, such as glass cloth, quartz glass fiber blended fabric, nonwoven fabric, quartz cloth, fiber paper, pulp paper, etc.

[0086] For example, the prepreg can be produced by immersing a reinforcing material in a resin adhesive liquid of the resin composition, and then drying the reinforcing material to obtain the prepreg.

[0087] Preferably, the drying temperature is 100 to 180°C, and may be, for example, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, or 175°C, or a specific point value between the above point values, and for the sake of space and clarity, the present invention does not comprehensively list specific point values ​​included in the above range.

[0088] Preferably, the drying time is 1 to 30 minutes, for example, 2 minutes, 5 minutes, 8 minutes, 10 minutes, 15 minutes, 20 minutes, or 25 minutes, and may be a specific value between the above-mentioned values. For the sake of space and clarity, the present invention does not exhaustively list specific values ​​included in the above range.

[0089] In a sixth aspect, the present invention provides a metal foil-clad sheet comprising at least one of the resin film according to the third aspect, the resin-coated copper foil according to the fourth aspect, and the prepreg according to the fifth aspect.

[0090] Preferably, the metal foil in the metal foil-clad plate is a copper foil, and the metal foil-clad plate is a copper-clad plate.

[0091] For example, the method for manufacturing the metal foil-clad plate includes laminating a metal foil onto one or both sides of a single prepreg and curing the metal foil to obtain the metal foil-clad plate, or stacking at least two prepregs to form a laminate, and then laminating a metal foil onto one or both sides of the laminate and curing the metal foil to obtain the metal foil-clad plate.

[0092] Preferably, the curing is carried out in a press.

[0093] Preferably, the curing temperature is 170 to 280°C, such as 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, or 270°C, and may be any specific point value between the above points, and for the sake of space and clarity, the present invention does not exhaustively list any specific point values ​​included in the above range.

[0094] Preferably, the curing pressure is 20 to 60 kg / cm 2 For example, 25 kg / cm 2 , 30kg / cm 2 , 35kg / cm 2 , 40kg / cm 2 , 45kg / cm 2 ,50kg / cm 2 or 55 kg / cm 2 , and specific point values ​​between the above point values, and for the sake of space and clarity, the present invention does not exhaustively list specific point values ​​within the ranges.

[0095] Preferably, the curing time is 60 to 300 minutes, for example, 80 minutes, 100 minutes, 120 minutes, 150 minutes, 180 minutes, 200 minutes, 220 minutes, 240 minutes, 260 minutes, or 280 minutes, and may be a specific point value between the above points, and for the sake of space and clarity, the present invention does not comprehensively list specific point values ​​included in the above range. [Effects of the Invention]

[0096] Compared with the prior art, the present invention has the following beneficial effects:

[0097] (1) The benzocyclobutene resin of the present invention has an all-hydrocarbon structure due to the design of the structural units, and has a sufficiently low dielectric constant Dk and dielectric dissipation factor Df. At the same time, the benzocyclobutene resin has a high glass transition temperature, low water absorption, good heat resistance and moist heat resistance, excellent dielectric properties, high modulus and mechanical properties, and also has good processability, and can fully meet the various performance requirements for resin materials for high-performance PCBs.

[0098] (2) The benzocyclobutene resin can be produced by the coupling reaction of polybutadiene and halogenobenzocyclobutene. The production process is simple, the yield is high, there are few side reactions, and it is easy to mass-produce. Furthermore, the chemical properties of the benzocyclobutene resin are stable, and there is no need to add a polymerization inhibitor for storage.

[0099] (3) The present invention designs and optimizes the benzocyclobutene resin structure, and the resin composition and metal foil-clad sheet containing it have a Dk of 3.4 or less, a Df of 0.0010 or less at 10 GHz, a glass transition temperature Tg of 200-285°C, a heat resistance of greater than 60 min at 300°C, can pass the PCT 6-hour test, a PCT / 6-hour water absorption of 0.08% or less, and a peel strength of 0.33-0.63 N / mm, and combine excellent dielectric properties, heat resistance, and moist heat resistance, fully meeting the requirements for high-performance PCBs used in next-generation communication technologies. [Brief explanation of the drawings]

[0100] [Figure 1] 1 is an infrared spectrum of the benzocyclobutene resin CH-BCB2 according to Example 1. [Figure 2] 1 is a GPC spectrum of the benzocyclobutene resin CH-BCB2 according to Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0101] The technical solution of the present invention will be further described below by means of specific embodiments. Those skilled in the art should understand that the above examples are only for understanding the present invention and should not be considered as specifically limiting the present invention.

[0102] In the following specific embodiments of the present invention, the specific information of the resin used to prepare the benzocyclobutene resin is as follows:

[0103] B1000: Polybutadiene, a structural unit formed by 1,2-polymerization of butadiene [ka] is 85% by mole, and the structural units formed by 1,4-polymerization [ka] is 15% by mole. Nippon Soda Co., Ltd. B2000: Polybutadiene containing 88% by mole of structural units formed by 1,2-polymerization and 12% by mole of structural units formed by 1,4-polymerization. Nippon Soda Co., Ltd. B3000: Polybutadiene in which 92% by mole of structural units formed by 1,2-polymerization and 8% by mole of structural units formed by 1,4-polymerization. Nippon Soda Co., Ltd. BI3060: A partially hydrogenated polybutadiene resin, in which 60% by mole of structural units formed by 1,2-polymerization are structural units [ka] The proportion of structural units formed by 1,4-polymerization is 32% by mole, and the proportion of structural units formed by 1,4-polymerization is 8% by mole. Nippon Soda Co., Ltd. Ricon 154: Polybutadiene containing 90% by mole of 1,2-polymerized structural units and 10% by mole of 1,4-polymerized structural units. Manufactured by Sartomer Corporation, USA. Ricon 184: a butadiene-styrene copolymer, in which the structural units formed by 1,2-polymerization account for 30% by mole, the structural units formed by 1,4-polymerization account for 48% by mole, and the styrene structural units [ka] The molar percentage is 22%. Sartomer Corporation, USA. Ricon 100: A butadiene-styrene copolymer containing 70% by mole of 1,2-polymerized structural units, 8% by mole of 1,4-polymerized structural units, and 22% by mole of styrene structural units. Manufactured by Sartomer Corporation, USA.

[0104] [Example 1] The benzocyclobutene resin CH-BCB2 is produced by the following method.

[0105] As shown in Table 1, 169.44 g of 4-bromobenzocyclobutene, 100 g of polybutadiene B2000, 16.35 g of tris(o-methylphenyl)phosphine, 7.48 g of palladium acetate, 500 g of triethylamine, and 1000 g of acetonitrile were added to a flask and stirred at 85 °C for 24 h under an argon atmosphere. The mixture was cooled and the solvent was spin-dried. The mixture was rapidly passed through a neutral alumina column and the solvent was spin-dried to obtain a viscous liquid. After dissolving in toluene, four times the amount of toluene was added to methanol, and the mixture was thoroughly shaken and allowed to stand. The toluene layer was then separated. The mixture was then spin-dried and vacuum-dried to obtain the colorless, viscous liquid benzocyclobutene resin CH-BCB2.

[0106] The structure of the benzocyclobutene resin CH-BCB2 was identified using a Fourier transform infrared spectrometer (FTIR, IS10 FT-IR, Thermo Fisher Scientific), and the resulting infrared spectrum is shown in Figure 1. As can be seen from Figure 1, -1 This is the characteristic absorption of benzocyclobutene four-membered ring, which means that CH-BCB2 resin has benzocyclobutene structure. TLC column shows that the raw material has disappeared, which means that benzocyclobutene has been incorporated into polybutadiene.

[0107] Based on the description in GB / T 21863-2008, the molecular weight of the benzocyclobutene resin CH-BCB2 was measured by gel permeation chromatography (GPC) using polystyrene calibration, and the resulting GPC spectrum is shown in Figure 2. The viscosity-average molecular weight of the benzocyclobutene resin CH-BCB2, 3421, shown in Figure 2, is its number-average molecular weight Mn of 2416.

[0108] [Examples 2 to 7] The benzocyclobutene resin was different from Example 1 in the types and amounts of raw materials used, as shown in Table 1. The process parameters not shown in Table 1 were all the same as those in Example 1. In Table 1, the molar percentages of structural unit A (%), structural unit B (%), and structural unit C (%) are the molar percentages in each benzocyclobutene resin. The percentages of structural unit A (%) and structural unit B (%) are calculated based on the amount of 4-bromo-BCB added and the molar percentage of 1,2-polymerized structural units in the resin raw material. (The 4-bromo-BCB reaction was confirmed by thin-layer chromatography during the manufacturing process, so that 4-bromo-BCB was completely converted to structural unit A. The difference in the molar percentages of the 1,2-polymerized structural units and structural unit A in the resin raw material is the amount of structural unit B (the corresponding resin raw material is polybutadiene). When the resin raw material is a butadiene-styrene copolymer, the content of structural unit B is calculated by adding the molar percentage of the styrene structural unit to the difference in the molar percentages of the 1,2-polymerized structural units and structural unit A in the resin raw material.) The structural unit C originated from the resin raw material (polybutadiene or butadiene-styrene copolymer) and was obtained from a raw material manufacturer.

[0109] [Table 1]

[0110] [Comparative Manufacturing Example 1] Benzocyclobutene resin CH-BCB-D1 was synthesized using the method in Example 1 of prior art CN107501459A, which was obtained by copolymerizing 4-vinylbiphenyl and 4-vinylbenzocyclobutene.

[0111] In the following specific embodiments of the present invention, the materials involved are as follows: (1) Benzocyclobutene resin Benzocyclobutene resins CH-BCB1 to CH-BCB7 according to Examples 1 to 7; CH-BCB-D1 according to Comparative Production Example 1. (2) Unsaturated group-containing thermosetting component Styrene-butadiene copolymer, Ricon 100, Sartomer, USA. (3) Initiator t-Butyl isopropyl phenyl peroxide, BIPB, HUNAN FARIDA TECHNOLOGY CO.,LTD. (4) Filler Silica, HM102YJ, Jiangsu Teruyue. (5) Flame retardants SYTELX 8010, Albemarle, USA.

[0112] [Application example 1] The resin composition included, in parts by weight, 100 parts of a component such as benzocyclobutene resin CH-BCB1.

[0113] The prepreg and copper-clad board containing the resin composition are produced by the following method.

[0114] (1) The resin composition and toluene were mixed in the formulation to prepare an adhesive solution with a solid content of 65%. 1035 L of glass cloth was immersed in the adhesive solution, adjusted to an appropriate thickness, and then baked in an oven at 130°C for 4 minutes to obtain a prepreg.

[0115] (2) Ten sheets of prepreg are stacked, and 18μ HVLP copper foil is placed on both the top and bottom of the stack. The temperature is 210℃ and the pressure is 30kg / cm. 2 The coating was cured for 120 minutes under the above conditions to obtain the copper clad board.

[0116] The copper clad board was subjected to a performance test, and the specific method was as follows.

[0117] (1) Glass transition temperature Tg: Measured with a dynamic mechanical analyzer (DMA) Rheometric RSAIII.

[0118] (2) Dielectric constant Dk and dielectric loss tangent Df: The dielectric constant Dk and dielectric loss tangent Df were measured by the split post dielectric resonator (SPDR) method using a dielectric analyzer HP Agilent E4991A at a frequency of 10 GHz.

[0119] (3) Peel strength PS: Measured according to the IPC-TM-6502.4.8C standard to measure the peel strength between the copper foil and the circuit board after thermal stress.

[0120] (4) Moisture and heat resistance: After PCT / 6 hours and etching to remove the copper foil, the plate was cut into three 100mm x 100mm samples. The plate samples were steamed in an autoclave at 105°C and 103.4 kPa for 360 minutes, then immersed in a tin oven at 288°C to measure the delamination time. If the time was less than 300 seconds, the specific time was recorded. After reaching 5 minutes, the measurement was stopped and the time was recorded as >300 seconds. A circle indicates that the sample did not delaminate within 300 seconds and passed the moist heat resistance test. An error indicates that the sample exhibited delamination within 300 seconds and failed the moist heat resistance test.

[0121] (5) Heat resistance T300: Measured according to the IPC-TM-6502.4.24.1 standard to measure the heat resistance of the material.

[0122] (6) PCT water absorption rate (%) / 6h: The copper foil was removed by etching from the plate, and the plate was cut into three samples of 100mm x 100mm. The plate samples were steamed for 360 minutes at 105°C and 103.4kPa pressure in an autoclave, and the masses before and after PCT were measured. The PCT water absorption rate was calculated as follows: mass change after PCT / mass before PCT x 100%.

[0123] The measurement results are shown in Table 2.

[0124] [Application Examples 2 to 8, Comparative Examples 1 to 2] The resin composition and the prepreg and copper-clad board containing the same differ from Application Example 1 in that the formulation of the resin composition was different, as shown in Tables 2 and 3. Here, the units for the amount of each component used are all "parts," "--" indicates that the component was not added, and the manufacturing methods for the prepreg and copper-clad board and the performance test methods were the same as those of Application Example 1.

[0125] [Table 2] [Table 3]

[0126] In combination with the performance test data described above, the benzocyclobutene resin of the present invention can be used to produce a resin composition and a copper-clad board, and the copper-clad board has a Dk of 2.90 to 3.40, a Df of 0.0005 to 0.0010, a glass transition temperature Tg of 200 to 285°C at 10 GHz, can pass the PCT 6-h test, a PCT water absorption of 0.05 to 0.08%, a heat resistance at 300°C of more than 60 min, and a peel strength of 0.33 to 0.63 N / mm, combining excellent dielectric properties, heat resistance, and moist heat resistance.

[0127] The resin composition of Comparative Example 1 does not contain the benzocyclobutene resin defined by the present invention, and its structure contains a high content of benzene ring structures, resulting in poor dielectric properties. In the resin composition of Comparative Example 2, butadiene-styrene copolymer (styrene-butadiene resin) and 4-bromobenzocyclobutene were physically mixed in the proportions used in Example 7, and then the same other components as in Application Example 7 were added. However, the benzocyclobutene was not grafted onto the styrene-butadiene resin, and most of the 4-bromobenzocyclobutene volatilized during the pre-curing process, with the remainder being the properties of the styrene-butadiene resin. Therefore, the dielectric properties and heat resistance of Comparative Example 2 were significantly inferior to those of the benzocyclobutene resin and resin composition defined by the present invention.

[0128] The present invention has been described in the above examples with respect to the benzocyclobutene resin, resin composition and use thereof, but the applicant declares that the present invention is not limited to the above process, i.e., it does not mean that the present invention must be carried out depending on the above process. Those skilled in the art should understand that any improvements to the present invention, equivalent substitution of raw materials used in the present invention, addition of auxiliary components, selection of specific forms, etc., are all within the protection scope and disclosure of the present invention.

Claims

1. Contains at least one type of structural unit A and at least one type of structural unit B, The building block A has a structure shown in formula I: 【Chemistry 1】 R １ is an ethenylene group and / or an ethylene group, The building block B has a structure shown in formula II: 【Chemistry 2】 R ２ is a vinyl group, an ethyl group and / or a phenyl group, A benzocyclobutene resin characterized by:

2. the content of the structural unit A in the benzocyclobutene resin is 5% or more, preferably 30% or more, and more preferably 30 to 60% by mole; Preferably, the benzocyclobutene resin comprises a structural unit A1, and the structural unit A1 has a structure represented by formula IA: 【Transformation 3】 Preferably, the structural unit B in the benzocyclobutene resin is 15 to 90% by mole, Preferably, the benzocyclobutene resin comprises a structural unit B1, and the structural unit B1 has a structure represented by formula IIA: 【Chemistry 4】 The benzocyclobutene resin according to claim 1 .

3. The benzocyclobutene resin further includes a structural unit C, and the structural unit C has a structure represented by Formula IIIA and / or Formula IIIB, 【Transformation 5】 【Transformation 6】 Preferably, the structural unit C in the benzocyclobutene resin is 40% or less by mole, more preferably 30% or less, and even more preferably 20% or less. The benzocyclobutene resin according to claim 1 or 2.

4. The number average molecular weight of the benzocyclobutene resin is 1,000 to 20,000. The benzocyclobutene resin according to any one of claims 1 to 3.

5. A resin composition comprising: The resin of the resin composition contains the benzocyclobutene resin according to any one of claims 1 to 4. A resin composition characterized by:

6. The content of the benzocyclobutene resin in the resin is 5 to 100% by mass, Preferably, the resin further comprises an unsaturated group-containing thermosetting component; Preferably, the content of the unsaturated group-containing thermosetting component in the resin is 95% by mass or less, Preferably, the resin composition further comprises an initiator, Preferably, the weight of the initiator is 0.1 to 3 parts per 100 parts of the total weight of the benzocyclobutene resin and the preferred unsaturated group-containing thermosetting component in the resin; Preferably, the initiator comprises one or a combination of at least two of an organic peroxide, an azo-based initiator, and a carbon-based radical initiator; Preferably, the initiator comprises one or a combination of at least two of t-butylisopropylphenyl peroxide, dicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne, 1,1-bis(t-butylperoxy)-3,3,5-dimethylcyclohexane, 2,3-dimethyl-2,3-diphenylbutane, and poly-1,4-diisopropylbenzene; Preferably, the resin composition further contains a filler, Preferably, the mass of the filler in the resin composition is 5 to 400 parts, more preferably 5 to 200 parts, based on 100 parts by mass of the resin; Preferably, the filler is an inorganic filler and / or an organic filler, more preferably an inorganic filler; Preferably, the inorganic filler comprises one or a combination of at least two of silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, and mica; Preferably, the organic filler includes one or a combination of at least two of a polyphenylene ether filler, a polytetrafluoroethylene filler, a polyether ether ketone filler, a polyphenylene sulfide filler, and a polyether sulfone filler; Preferably, the median diameter of the filler is 0.01 to 50 μm, more preferably 0.01 to 20 μm; Preferably, the filler comprises a surface-treated filler; Preferably, the surface treatment agent for the surface treatment includes one or a combination of at least two of a silane coupling agent, a silicone oligomer, and a titanate coupling agent, Preferably, the mass of the surface treatment agent is 0.1 to 5 parts based on 100 parts by mass of the filler to be treated; Preferably, the resin composition further contains a flame retardant, Preferably, the mass of the flame retardant in the resin composition is 1 to 50 parts per 100 parts of the resin. The resin composition according to claim 5 .

7. A resin film, The material of the resin film includes the resin composition according to claim 5 or 6, Preferably, the resin film is produced by applying the resin composition to a release agent and drying and / or semi-curing the composition. A resin film characterized by:

8. The laminated laminated board includes a copper foil layer and a resin layer, and the material of the resin layer includes the resin composition according to claim 5 or 6. A resin-coated copper foil characterized by:

9. A composite material comprising a reinforcing material and the resin composition according to claim 5 or 6 attached to the reinforcing material, Preferably, the resin composition is applied to the reinforcing material by immersion drying. A prepreg characterized by:

10. The resin film according to claim 7, the resin-coated copper foil according to claim 8, and the prepreg according to claim 9 are included. A metal foil-clad plate characterized by:

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