TW201319113A - Thermosetting resin composition and laminate and circuit board using the same - Google Patents

Abstract

The present invention provides a benzoxazine resin comprising a structure of naphthalene ring, diphenyl or anthracene, and also provides a resin composition, a laminate and a circuit board comprising the benzoxazine resin. By the resin composition containing a benzoxazine resin having a special structure, this invention can have the characters of low dielectric constant, low dielectric loss, high rigidity and high thermal resistance, and also can use the resin composition to prepare a semi-cured prepreg or a resin film for achieving the purpose of being applied in laminate and circuit board.

Description

Thermosetting resin composition and laminated board and circuit board using same

The present invention relates to a benzoxazine resin, and more particularly to a benzoxazine resin for use in laminates and circuit boards.

In response to the world's environmental trends and green regulations, Halogen-free is the current environmental trend of the global electronics industry. Countries around the world and related electronics manufacturers have successively developed mass production schedules for halogen-free electronic products for their electronic products. After the implementation of the Restriction of Hazardous Substances (RoHS), substances including lead, cadmium, mercury, hexavalent chromium, polybrominated biphenyls and polybrominated diphenyl ethers have not been used in the manufacture of electronic products or Its components. Printed Circuit Board (PCB) is the basis of electronic motor products. Halogen-free is the first key control object for printed circuit boards. International organizations have strict requirements on the halogen content of printed circuit boards, including the International Electrotechnical Commission (IEC). The 61249-2-21 specification requires that the bromine and chloride content must be less than 900 ppm and the total halogen content must be less than 1500 ppm; the Japanese Electronic Circuit Industry Association (JPCA) regulates the bromide and chloride content limits. 900 ppm; Greenpeace’s greening policy, which is currently being promoted, requires all manufacturers to completely eliminate the PVC and brominated flame retardants in their electronic products to meet the lead-free and halogen-free green electronics. Therefore, the halogen-free material has become a key development project for the current industry.

The new generation of electronic products tend to be light and thin, and suitable for high-frequency transmission, so the wiring of the circuit board is becoming higher density, and the material selection of the circuit board is moving toward more stringent requirements. The high-frequency electronic components are bonded to the circuit board. In order to maintain the transmission rate and maintain the integrity of the transmission signal, the substrate material of the circuit board must have a lower dielectric constant (Dk) and a dielectric loss (also referred to as a loss factor). Dissipation factor, Df). At the same time, in order to maintain the normal operation of electronic components in high temperature and high humidity environments, the circuit board must also have the characteristics of heat resistance, flame retardancy and low water absorption. Since epoxy resin is excellent in adhesiveness, heat resistance, and moldability, it is widely used for a copper-clad laminate or a sealing material for an electronic component and a motor machine. From the viewpoint of safety against fire, the material is required to have flame retardancy. Generally, the flame retardant epoxy resin is used in combination with a flame retardant to achieve a flame retardant effect, for example, in an epoxy resin. The introduction of a halogen, especially bromine, imparts flame retardancy and increases the reactivity of the epoxy group.

However, recent electronic products tend to be lightweight, miniaturized, and circuit miniaturized. Under such requirements, a relatively large halide is not preferable in terms of weight reduction. In addition, after a long period of use at a high temperature, the dissociation of the halide may occur, and the fine wiring may be corroded. In addition, the used electronic components after use will produce harmful compounds such as halides after burning, and are not friendly to the environment. In order to replace the above-mentioned halide flame retardant, it has been studied to use a phosphorus compound as a flame retardant, for example, a phosphate ester (Republic of China Patent Publication No. I238846) or red phosphorus (Republic of China Patent Publication No. 322507) in an epoxy resin composition. . However, phosphate esters will cause acid hydrolysis due to hydrolysis reaction, which will affect their migration resistance. However, red phosphorus has high flame retardancy, but it is referred to as dangerous goods in fire protection law, because it will be in high temperature and humid environment. A trace amount of phosphine gas occurs.

In the circuit board technology of the conventional copper foil substrate (or copper foil laminate), an epoxy resin and a hardener are used as a raw material of a thermosetting resin composition, and a reinforcing material (such as a glass fiber cloth) and the thermosetting resin are used. The heat is combined to form a semipreg, and the prepreg is pressed together with the upper and lower copper foils under high temperature and high pressure. In the prior art, an epoxy resin and a phenol novolac resin hardener having a hydroxyl group (-OH) are generally used as a raw material of a thermosetting resin. The combination of a phenol resin and an epoxy resin causes an epoxy group to form another hydroxyl group after ring opening, and a hydroxyl group. It will increase the dielectric constant and dielectric loss value, and it will easily combine with moisture to increase hygroscopicity.

The Republic of China Patent Publication No. 308566 and No. 460,537 disclose a thermosetting resin composition comprising a dihydrogen oxynaphthalene ring resin such as bisphenol A benzoxazine resin (Bisphenol-A). Benzoxazine, BPA-BZ) or Bisphenol-F Benzoxazine (BPF-BZ), which improves the hardenability of the composition without sacrificing mechanical properties. The Republic of China Patent Publication No. 201114853 discloses a dicyclopenta-diene-dihydrobenzoxazine (DCPD-BZ) which is used in the saturated cyclic structure of the benzoxazine resin. In the thermosetting resin composition, the coefficient of thermal expansion can be effectively reduced, and the dielectric constant and dielectric loss of the substrate can be lowered.

In terms of electrical properties, the main considerations include the dielectric constant of the material and the dielectric loss. In general, since the signal transmission speed of the substrate is inversely proportional to the square root of the dielectric constant of the substrate material, the dielectric constant of the substrate material is generally as small as possible; on the other hand, the smaller the dielectric loss represents the loss of signal transmission. The less the material, the lower the dielectric loss, the better the transmission quality.

Therefore, how to develop materials with low dielectric constant and low dielectric loss and apply them to the manufacture of high-frequency printed circuit boards is a problem that manufacturers of printed circuit board materials are trying to solve at this stage.

In view of the shortcomings of the above-mentioned prior art, the inventor felt that he had not perfected it, exhausted his mind and researched and overcome it, and based on his accumulated experience in the industry for many years, he developed a benzoxazine resin in order to achieve Low dielectric constant, low dielectric loss, high rigidity and high heat resistance.

The main object of the present invention is to provide a benzoxazine resin which can be used in a thermosetting resin group to achieve low dielectric constant, low dielectric loss, high rigidity and high by containing a naphthalene ring, a biphenyl or an anthracene ring structure. The heat resistance can be made into a semi-cured film or a resin film, thereby achieving the purpose of being applied to a laminate board and a circuit board.

To achieve the above object, the present invention provides a benzoxazine resin selected from one of the following compounds:

Wherein n and m are any positive integers, and Y represents a hydrogen group, an aliphatic functional group or an aromatic functional group.

The benzoxazine resin containing a naphthalene ring, a biphenyl or an anthracene ring structure according to the present invention has a functional group of a benzoxazine, which can be used with other cross-linking agents such as phenols or amines. The reaction is bonded, and each has a naphthalene ring, a biphenyl or an anthracene ring structure, which provides high rigidity and high heat resistance of the resin. The benzoxazine resin containing a naphthalene ring, a biphenyl ring and an anthracene ring structure according to the present invention can be applied to the resin industry, such as a common epoxy resin application industry, as an adhesive, an insulating layer material of a metal foil substrate or Semi-cured film, etc.

The benzoxazine resin containing a naphthalene ring structure according to the present invention is synthesized from naphthalene type phenol novolac and three raw materials such as aniline and formaldehyde, and the synthesis method is generally used in the prior art. The method used. Similarly, the benzoxazine resin containing a biphenyl structure and the benzoxazine resin containing an anthracene ring structure are a biphenyl type phenol novolac and an anthracene type containing an anthracene ring, respectively. Phenol novolac), synthesized with three raw materials such as aniline and formaldehyde.

Another object of the present invention is to provide a thermosetting resin composition comprising: (1) the above benzoxazine resin; and (2) a crosslinking agent. The resin composition has high heat resistance and high rigidity.

The crosslinking agent is selected from at least one of the group consisting of a phenol resin, an amine resin, a phenol resin, an acid anhydride resin, a styrene resin, a butadiene resin, a polyamide resin, a polyimide resin, and a poly Ester resin, polyether resin, polyphenylene ether resin, cyanate resin, isocyanate resin, maleic imine resin, bisphenol A benzoxazine resin, bisphenol F benzoxazine resin, brominated resin, Phosphorus resin and nitrogen-containing resin. The crosslinking agent functions to bond with the benzoxazine resin containing a naphthalene ring, a biphenyl or an anthracene ring structure according to the present invention to complete the crosslinking reaction.

The above composition further comprises an epoxy resin and a hardening accelerator.

The epoxy resin is selected from at least one of the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, Bisphenol AD (bisphenol AD) epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F phenolic resin (bisphenol F novolac) epoxy resin, o-cresol ( O-cresol novolac) epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, multifunctional epoxy resin, dicyclopentadiene epoxy Resin, phosphorus-containing epoxy resin, p-xylene epoxy resin, naphthalene epoxy resin, benzopyran epoxy resin, biphenyl novolac Epoxy resin and phenol aralkyl novolac epoxy resin.

The hardening accelerator is selected from at least one of the group consisting of: Lewisine and Lewis acid. The Lewis base may include imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenylimidazole (2). -phenyl-1H-imidazole, 2PI), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP), 4-dimethylaminopyridine (4-dimethylaminopyridine, DMAP) and the like. Lewis acid may include metal salt compounds of manganese, iron, cobalt, nickel, copper and zinc. The main purpose of adding a hardening accelerator is to increase the reaction rate of the resin composition.

The above composition further comprising at least one selected from the group consisting of inorganic fillers, surfactants, toughening agents, flame retardants, organic oxime elastomers, and solvents.

The inorganic filler is not particularly limited, and conventional inorganic fillers for laminated sheets may be used, for example, cerium oxide (a molten state or a non-molten state and a porous state), alumina, magnesia, magnesium hydroxide, Calcium carbonate, aluminum nitride, boron nitride, aluminum hydroxide, aluminum lanthanum carbide, tantalum carbide, sodium carbonate, titanium dioxide, zinc oxide, zirconium oxide, quartz, diamond powder, diamond powder, graphite, magnesium carbonate, potassium titanate , ceramic fiber, mica, boehmite (ALOOH), aluminum hydroxide (Aluminium Trihydrate, ATH, Al(OH)3), zinc molybdate, ammonium molybdate, zinc borate, calcium phosphate, calcined talc, talc, Cerium nitride, molybdenum, segmental kaolin, clay, basic magnesium sulfate whisker, mullite whisker, barium sulfate, magnesium hydroxide whisker, magnesium oxide whisker, calcium oxide whisker, carbon nanotube , nano-sized cerium oxide and its related inorganic powder, or powder particles modified with an organic core outer shell as an insulator. The inorganic filler may be in the form of a sphere, a fiber, a plate, a granule, a sheet or a whisker, and may be optionally pretreated by a surfactant.

The inorganic filler may be a particle powder having a particle diameter of 100 μm or less, and preferably a particle powder having a particle diameter of 1 to 20 μm, preferably a nanometer-sized particle powder having a particle diameter of 1 μm or less; the needle-like inorganic filler may be It is a powder having a diameter of 50 μm or less and a length of 1 to 200 μm. The main purpose of adding the inorganic filler is to increase the thermal conductivity of the resin composition, to improve the thermal expansion property and the mechanical strength, and to increase the rigidity, and it is preferred to uniformly distribute the inorganic filler in the resin composition.

The surfactant, or a siloxane coupling agent, may be used without any particular limitation, and specifically, it is selected from the group consisting of vinyl triethoxy decane, vinyl trimethoxy decane, and vinyl. Reference (β-methoxy-ethoxy decane), γ-glycidoxypropyltrimethoxydecane, γ-aminopropyltriethoxydecane, wherein the dispersing agent can be BYK-103, BYK- 901, BYK-161 or BYK-164, etc. The main purpose of adding a surfactant is to improve the uniform dispersibility of the inorganic filler in the resin composition.

The toughening agent is selected from the group consisting of rubber resins, polybutadienes, core-shell polymers and the like. The main purpose of adding a toughening agent is to improve the toughness of the resin composition.

The flame retardant is selected from the group consisting of: a phosphorus-containing flame retardant, a nitrogen-containing flame retardant (such as Melamine Cyanurate), a bromine-containing flame retardant (TBBPA, Tetra-Bromo-Bisphenol A), or a combination thereof, wherein The phosphorus-containing flame retardant may be a phosphate-based phosphorus-containing flame retardant or a DOPO-based phosphorus-containing flame retardant. The former is not cross-linkable with the resin, and may be, for example, Exolit OP 935 (available from Clariant), SPB-100 (optional) Available from Otsuka Chemical Co., Ltd., PX-200 (available from Dabha Chemical); the latter is crosslinkable with the resin and can be, for example, Bisphenol novolac (BPN) substituted by DOPO or its derivatives or Phenol novolac (PN), such as DOPO-bisphenol-A novolac (DOPO-BPAN) or DOPO-phenol novolac (DOPO-PN), but not as limit.

The hybrid type silicone powder is generally a rubber and resin type composite powder, preferably a spherical powder, and the addition of the organic cerium elastomer increases the heat resistance and impact absorption of the thermosetting resin composition of the present invention. . The organic fluorene elastomer is not particularly limited, and any of the organic enamel elastomers used for the laminate may be used, for example, X-52-7030, KMP-605, KMP-602, KMP-601, KMP-600 produced by Shin-Etsu. , KMP-590 and KMP-594 and other products.

The solvent comprises methanol, ethanol, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxy ethyl acetate, B A solvent such as oxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide or propylene glycol methyl ether or a mixed solvent thereof. The main purpose of adding a solvent is to change the solid content of the resin composition and to adjust the viscosity of the resin composition.

Still another object of the present invention is to provide a halogen-free and phosphorus-free resin composition comprising: (1) a naphthalene type epoxy resin; (2) the above benzoxazine resin; (3) a hardening accelerator; and selectivity One of (4) aluminum hydroxide and boehmite or a combination thereof is added.

The halogen-free and non-phosphorus resin composition of the present invention uses aluminum hydroxide or boehmite as a flame retardant, and effectively improves the prior art use of a halogen flame retardant (such as a brominated flame retardant) to release dioxin upon combustion. Harmful substances such as (Dioxin) and the use of phosphorus-containing flame retardants can cause poor chemical resistance. The present invention uses the principle of aluminum hydroxide and boehmite as a flame retardant. In order to utilize high temperature, aluminum hydroxide and boehmite will release crystal water to prevent the flame from continuing to burn. In addition, a naphthalene type epoxy resin (particularly a tetrafunctional naphthalene type epoxy resin), and a benzoxazine resin containing a naphthalene ring, a biphenyl or an anthracene ring structure according to the present invention are used, since a naphthalene ring or a biphenyl group is used. Or high-temperature heat-resistant and flame-resistant structure, with aluminum hydroxide and boehmite, can effectively achieve the V-0 flame resistance of UL-94.

The above composition further comprising at least one selected from the group consisting of inorganic fillers, surfactants, toughening agents, flame retardants, organic oxime elastomers, and solvents.

Still another object of the present invention is to provide a prepreg film having characteristics of low dielectric constant, low dielectric loss, high rigidity, high heat resistance, and halogen-free. Accordingly, the prepreg film disclosed in the present invention may comprise a reinforcing material and the halogen-free resin composition described above, wherein the halogen-free resin composition is attached to the reinforcing material by impregnation or the like, and is formed by heating at a high temperature. Cured state. Among them, the reinforcing material may be a fiber material, a woven fabric and a non-woven fabric, such as a glass fiber cloth, etc., which may increase the mechanical strength of the prepreg film. In addition, the reinforcing material may be optionally pretreated with a decane coupling agent or a decane coupling agent, such as a glass fiber cloth pretreated with a decane coupling agent. The aforementioned prepreg film can be cured by high temperature heating or heating under high temperature and high pressure to form a cured film or a solid insulating layer. If the halogen-free resin composition contains a solvent, the solvent is volatilized and removed in a high temperature heating process.

Still another object of the present invention is to provide a laminated board having low dielectric constant, low dielectric loss, high rigidity, high heat resistance, and halogen-free characteristics, and is particularly suitable for a circuit board for high-speed and high-frequency signal transmission. . Accordingly, the present invention provides a laminate comprising two or more metal foils and at least one insulating layer. The metal foil may further comprise an alloy of copper and at least one metal such as aluminum, nickel, platinum, silver, gold, etc.; the insulating layer is formed by curing the aforementioned prepreg film under high temperature and high pressure, such as laminating the aforementioned prepreg film. It is formed by pressing between two copper foils under high temperature and high pressure. The laminated board is further processed by a manufacturing process or the like to form a circuit board, and the circuit board is bonded to the electronic component and operated in a severe environment such as high temperature and high humidity without affecting the quality thereof.

Still another object of the present invention is to provide a circuit board comprising the above laminated board, which has low dielectric constant, low dielectric loss, high rigidity, high heat resistance and halogen-free characteristics, and is suitable for high speed and high frequency. Signal transmission. Wherein, the circuit board comprises at least one of the foregoing laminated boards, and the circuit board can be fabricated by a conventional process.

The present invention will be further described in the following examples, in which the present invention may be practiced by those of ordinary skill in the art. It is to be understood that the following examples are merely illustrative of the invention and are not intended to limit the scope of the invention, and that Modifications and variations are possible within the scope of the invention.

In order to fully understand the objects, features and advantages of the present invention, the present invention will be described in detail by the following specific embodiments.

The resin compositions of Examples 2 to 5 are listed in Table 1, and the resin compositions of Comparative Examples 1 to 4 are listed in Table 3.

Example 1 (E1)

A resin composition comprising the following ingredients:

(A) 100 parts by weight of the benzoxazine resin of the formula 1;

(B) 20 parts by weight of phenolic resin (Phenol novolac).

Example 2 (E2)

A resin composition comprising the following ingredients:

(A) 100 parts by weight of dicyclopentadiene epoxy resin (HP-7200);

(B) 75 parts by weight of the benzoxazine resin of the formula 3;

(C) 10 parts by weight of an amino triazine novolac (ATN);

(D) 30 parts by weight of DOPO-BPAN resin flame retardant;

(E) 80 parts by weight of a cerium oxide (Silica) inorganic filler;

(F) 0.3 parts by weight of 2E4MI catalyst;

(G) 20 parts by weight of methyl ethyl ketone (MEK).

Example 3 (E3)

A resin composition comprising the following ingredients:

(A) 50 parts by weight of dicyclopentadiene epoxy resin (HP-7200);

(B) 50 parts by weight of bisphenol A epoxy resin (BE-188E);

(C) 40 parts by weight of bisphenol A benzoxazine resin (BPA-BZ);

(D) 35 parts by weight of a benzoxazine resin of the formula 3;

(E) 25 parts by weight of Styrene-maleic anhydride (SMA);

(F) 30 parts by weight of a phosphazene compound (SPB-100) flame retardant;

(G) 70 parts by weight of a molten cerium oxide (Fused silica) inorganic filler;

(H) 0.35 parts by weight of 2E4MI catalyst;

(I) 20 parts by weight of methyl ethyl ketone (MEK).

Example 4 (E4)

A resin composition comprising the following ingredients:

(A) 100 parts by weight of bisphenol A cyanate resin (BA-230S);

(B) 40 parts by weight of the benzoxazine resin of the formula 5;

(C) 30 parts by weight of a polyphenylene ether resin (PPO);

(D) 10 parts by weight of a naphthalene type phenol resin (EXB-9500);

(E) 50 parts by weight of a molten cerium oxide (Fused silica) inorganic filler;

(F) 25 parts by weight of a phosphorus-containing flame retardant (PX-200);

(G) 0.01 parts by weight of zinc octoate catalyst (Zn);

(H) 20 parts by weight of methyl ethyl ketone (MEK).

Example 5 (E5)

A halogen-free, non-phosphorus resin composition comprising the following ingredients:

(A) 100 parts by weight of a tetrafunctional naphthalene type epoxy resin (HP-4700);

(B) 40 parts by weight of the benzoxazine resin of the formula 1;

(C) 20 parts by weight of a naphthalene type phenol resin (EXB-9500);

(D) 0.3 parts by weight of 2E4MI catalyst;

(E) 50 parts by weight of Boehmite inorganic filler;

(F) 20 parts by weight of methyl ethyl ketone (MEK).

Comparative Example 1 (C1)

A resin composition comprising the following ingredients:

(A) 100 parts by weight of dicyclopentadiene epoxy resin (HP-7200);

(B) 75 parts by weight of bisphenol A benzoxazine resin (BPA-BZ);

(C) 10 parts by weight of an amino triazine novolac (ATN);

(D) 30 parts by weight of DOPO-BPAN resin flame retardant;

(E) 80 parts by weight of a cerium oxide (Silica) inorganic filler;

(F) 0.3 parts by weight of 2E4MI catalyst;

(G) 20 parts by weight of methyl ethyl ketone.

Comparative Example 2 (C2)

A resin composition comprising the following ingredients:

(A) 50 parts by weight of dicyclopentadiene epoxy resin (HP-7200);

(B) 50 parts by weight of bisphenol A epoxy resin (BE-188E);

(C) 75 parts by weight of bisphenol A benzoxazine resin (BPA-BZ);

(D) 25 parts by weight of Styrene-maleic anhydride (SMA);

(E) 30 parts by weight of a phosphazene compound (SPB-100) flame retardant;

(F) 70 parts by weight of a molten cerium oxide (Fused silica) inorganic filler;

(G) 0.35 parts by weight of 2E4MI catalyst;

(H) 20 parts by weight of methyl ethyl ketone.

Comparative Example 3 (C3)

A resin composition comprising the following ingredients:

(A) 100 parts by weight of bisphenol A cyanate resin (BA-230S);

(B) 40 parts by weight of bisphenol A benzoxazine resin (BPA-BZ);

(C) 30 parts by weight of a polyphenylene ether resin (PPO);

(D) 10 parts by weight of a naphthalene type phenol resin (EXB-9500);

(E) 50 parts by weight of a molten cerium oxide (Fused silica) inorganic filler;

(F) 25 parts by weight of a phosphorus-containing flame retardant (PX-200);

(G) 0.01 parts by weight of zinc octoate catalyst (Zn);

(H) 20 parts by weight of methyl ethyl ketone (MEK).

Comparative Example 4 (C4)

A resin composition comprising the following ingredients:

(A) 100 parts by weight of a tetrafunctional naphthalene type epoxy resin (HP-4700);

(B) 40 parts by weight of bisphenol A benzoxazine resin (BPA-BZ);

(C) 20 parts by weight of a naphthalene type phenol resin (EXB-9500);

(D) 0.3 parts by weight of 2E4MI catalyst;

(E) 50 parts by weight of a cerium oxide (Silica) inorganic filler;

(F) 20 parts by weight of methyl ethyl ketone (MEK).

The resin compositions of the above Examples 2 to 5 and Comparative Examples 1 to 4 were uniformly mixed in a stirred tank, placed in an impregnation tank, and the glass fiber cloth was passed through the above-mentioned impregnation tank to adhere the resin composition to the resin composition. The glass fiber cloth is heated and baked into a semi-cured state to obtain a semi-cured film.

The semi-cured film prepared in batches above is taken from the same batch of semi-cured film four sheets and two 18 μm copper foils, which are laminated in the order of copper foil, four-ply semi-cured film and copper foil, and then vacuumed. A copper foil substrate was formed by pressing at 190 ° C for 2 hours, in which four sheets of semi-cured film were cured to form an insulating layer between the two copper foils.

The copper-containing substrate and the copper foil-etched copper-free substrate were respectively measured for physical properties, and the physical property measurement items included glass transition temperature (Tg), copper-containing substrate heat resistance (T288), and copper-containing substrate immersion tin test ( Solder dip 288 ° C, 10 seconds, measured heat resistance, S / D), dielectric constant (the lower Dk is better), dielectric loss (the lower the Df is better), flaming test (UL94, which rank The pros and cons are ranked as V-0>V-1>V-2).

The substrate physical property measurement results of the resin compositions of Examples 2 to 5 are listed in Table 2, and the substrate physical property measurement results of the resin compositions of Comparative Examples 1 to 4 are listed in Table 4. From Tables 2 and 4, comparing Comparative Examples 2 to 5 and Comparative Examples 1 to 4, it can be found that the benzoxazine resin disclosed in the present invention is bisphenol A benzoic compared to the prior art. The azine resin can improve the heat resistance of the substrate (Tg, T288, S/D). Further, the resin composition of Example 5 contained no flame retardant and was also able to meet the UL94 V-0 flame resistance standard, and Comparative Example 4 had only poor V-2 flame resistance.

As described above, the present invention fully complies with the three requirements of the patent: novelty, advancement, and industrial applicability. In terms of novelty and advancement, the present invention comprises a specific benzoxazine resin by a resin composition so that low dielectric constant, low dielectric loss, high rigidity and high heat resistance can be achieved; It is a semi-cured film or a resin film, and thus can be applied to laminated boards and circuit boards; in terms of industrial availability, the products derived from the present invention can fully satisfy the needs of the current market.

The invention has been described above in terms of the preferred embodiments, and it should be understood by those skilled in the art that the present invention is not intended to limit the scope of the invention. It should be noted that variations and permutations equivalent to those of the embodiments are intended to be included within the scope of the present invention. Therefore, the scope of the invention is defined by the scope of the following claims.

Claims (10)

A benzoxazine resin selected from one of the following compounds: Wherein n and m are any positive integers, and Y represents a hydrogen group, an aliphatic functional group or an aromatic functional group. A thermosetting resin composition comprising: (1) a benzoxazine resin as described in claim 1; and (2) a crosslinking agent. The composition of claim 2, wherein the crosslinking agent is selected from at least one of the group consisting of a phenol resin, an amine resin, a phenol resin, an acid anhydride resin, a styrene resin, a butadiene resin, Polyamide resin, polyimide resin, polyester resin, polyether resin, polyphenylene ether resin, cyanate resin, isocyanate resin, maleic imine resin, bisphenol A benzoxazine resin, bisphenol F benzoxazine resin, brominated resin, phosphorus-containing resin and nitrogen-containing resin. The composition of claim 2, further comprising an epoxy resin and a hardening accelerator. The composition of claim 4, wherein the epoxy resin is selected from at least one of the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, Bisphenol AD epoxy resin, novolac epoxy resin, bisphenol A phenolic epoxy resin, bisphenol F phenolic epoxy resin, o-cresol epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, and more Functional epoxy resin, dicyclopentadiene epoxy resin, phosphorus-containing epoxy resin, p-xylene epoxy resin, naphthalene epoxy resin, benzopyran epoxy resin, biphenolic epoxy resin and Phenolic phenylalkyl novolac epoxy resin. A halogen-free and phosphorus-free resin composition comprising: (1) a naphthalene type epoxy resin; (2) a benzoxazine resin as described in claim 1; (3) a hardening accelerator; and selectivity One of (4) aluminum hydroxide and boehmite or a combination thereof is added. The composition of claim 2 or 6, further comprising at least one selected from the group consisting of inorganic fillers, surfactants, toughening agents, flame retardants, organic fluorene elastomers, and Solvent. A semi-cured film comprising the composition of any one of claims 2 to 7. A laminated board comprising the prepreg as described in claim 9 of the patent application. A circuit board comprising the laminate as described in claim 10 of the patent application.