TW201313081A - Non-halogen pixel resin composition and its application of copper clad laminate and printed circuit board - Google Patents

Abstract

The present invention provides a non-halogen pixel resin composition, comprising:(a)100 parts by weight of cyanate resin; (b)5 to 50 parts by weight of styrene maleic anhydride; (c)5 to 100 parts by weight of polyphenylene oxide resin; (d)5 to 100 parts by weight of maleimide resin; (e)10 to 150 parts by weight of phosphazene compound; and (f)10 to 1000 parts by weight of the inorganic filler. The present invention includes a specific ingredient and ratio, to achieve a low dielectric constant, low dielectric loss, high heat resistance and high incombustibility; may be manufactured as a cured film or resin film, and achieve the purpose of can be applied to copper clad laminate and printed circuit board.

Description

Halogen-free resin composition and copper foil substrate and printed circuit board thereof

The present invention relates to a halogen-free resin composition, and more particularly to a halogen-free resin composition applied to a copper foil substrate and a printed circuit board.

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 low dielectric constant and dielectric loss. 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. 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 a 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 composition is combined with heat to form a semipreg film, and the prepreg film 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, and the combination of the phenol resin and the epoxy resin causes the epoxy group to form another hydroxyl group after ring opening. The hydroxyl group itself increases the dielectric constant and the dielectric loss value, and is easily combined with moisture to increase hygroscopicity.

The Republic of China Patent Publication No. I297346 discloses the use of a cyanate resin, a dicyclopentadienyl epoxy resin, vermiculite, and a thermoplastic resin as a thermosetting resin composition having a low dielectric constant and a low dielectric constant. Characteristics such as electrical loss. However, this manufacturing method must use a flame retardant containing a halogen (such as bromine) component, such as tetrabromocyclohexane, hexabromocyclodecane, and 2,4,6-tris(tribromophenoxy)-1. , 3,5-triazabenzene, and these bromine-containing flame retardants are easily polluted by the environment when the product is manufactured, used, or even recycled or discarded. In order to improve the heat and flame resistance of the copper foil substrate, low dielectric loss, low moisture absorption, high crosslink density, high glass transition temperature, high bondability, and appropriate thermal expansion, epoxy resin, hardener and reinforcing material Material selection has become a major factor.

In terms of electrical properties, the main considerations include the dielectric constant of the material and the dielectric loss (also known as the loss factor). 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 mental research and overcome it, and based on his accumulated experience in the industry for many years, he developed a halogen-free resin composition in order to achieve Low dielectric constant and high heat resistance and high flame resistance.

The main object of the present invention is to provide a halogen-free resin composition which can be made into a low dielectric constant, low dielectric loss, high heat resistance and high flame resistance by including a specific composition and ratio; A semi-cured film or a resin film is used for the purpose of being applied to a copper foil substrate and a printed circuit board.

In order to achieve the above object, the present invention provides a halogen-free resin composition comprising: (A) 100 parts by weight of a cyanate ester resin; (B) 5 to 50 parts by weight of styrene maleic anhydride (styrene) -maleic anhydride, SMA); (C) 5 to 100 parts by weight of polyphenylene oxide (PPO) resin; (D) 5 to 100 parts by weight of maleimide resin (maleimide); (E) 10 Up to 150 parts by weight of a phosphazene; and (F) 10 to 1000 parts by weight of an inorganic filler.

The use of the above composition is for producing a prepreg film, a resin film, a copper foil substrate, and a printed circuit board. Thereby, the halogen-free resin composition of the present invention can be made into a semi-cured by including a specific composition part and ratio so that a low dielectric constant, a low dielectric loss, a high heat resistance, and a high flame resistance can be achieved; Film or resin film, which can be applied to copper foil substrates and printed circuit boards.

In the halogen-free resin composition of the present invention, the component (A) cyanate resin is not particularly limited, and any of the cyanate resins conventionally used may be, for example, a compound having an (Ar-OC≡N) structure; Ar may be substituted or unsubstituted benzene, biphenyl, naphthalene, phenol novolac, bisphenol A, bisphenol A novolac, bisphenol F, double Phenol F novolac or phenolphthalein. Further, the above Ar may further bond a substituted or unsubstituted dicyclopentadiene.

More specifically, the cyanate resin is preferably selected from at least one of the following groups:

Wherein X ₁ and X ₂ are each independently at least one R, Ar, SO ₂ or O; and R is selected from the group consisting of -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -CH ₂ - and substituted or not Substituted dicyclopentadienyl; Ar is selected from substituted or unsubstituted benzene, biphenyl, naphthalene, phenolic, bisphenol A, esters, cyclic hydrazine, hydrogenated bisphenol A, bisphenol A phenolic, bisphenol F and bisphenol F phenolic functional groups; n is an integer greater than or equal to 1; Y is an aliphatic functional group or an aromatic functional group. The cyanate resin of the present invention is commercially available as: Primaset PT-15, PT-30S, PT-60S, CT-90, BADCY, BA-100-10T, BA-200, BA-230S, Methylcy, ME-240S, etc. Cyanate resin produced by Lonza.

The ratio of styrene (S) to maleic anhydride (MA) of styrene maleic anhydride (SMA) of the present invention may be 1/1, 2/1, 3/1, 4/1, 6/1 or 8/1 One or a combination thereof, such as styrene maleic anhydride copolymers such as SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60, and EF-80.

The halogen-free resin composition of the present invention is characterized in that 5 to 50 parts by weight of styrene maleic anhydride is added based on 100 parts by weight of the cyanate resin, and the styrene maleic anhydride content in the range of addition can be adjusted. The halogen-free resin composition lowers the overall dielectric constant electrical value (Dk). If the content of the styrene maleic anhydride is less than 5 parts by weight, the electrical property value is not obtained, and if it exceeds 50 parts by weight, the half is caused. The cured film has a poor appearance and is easy to fall off, resulting in a decrease in the process yield of the semi-cured film.

The polyphenylene ether resin of the present invention is selected from at least one of the following groups:

Wherein X ₆ is selected from the group consisting of a covalent bond, -SO ₂ -, -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -CH ₂ -; Z ₁ to Z ₁₂ are each independently selected from the group consisting of hydrogen and W is a hydroxyl group, a vinyl group, a styryl group, a propenyl group, a butenyl group, a butadienyl group or an epoxy functional group; and n is an integer greater than or equal to 1.

In the present invention, since the polyphenylene ether resin can effectively improve the dielectric properties of the resin composition, the addition of the polyphenylene ether resin to the nitrogen-oxygen heterocyclic compound and the cyanate resin can further reduce the resin composition. The value of the dielectric loss, and its effect is more pronounced at high frequencies (such as 1 GHz to 10 GHz). Further, since the polyphenylene ether resin also has flame resistance, the resin composition of the present invention can achieve the V-1 flame retardant effect of the UL 94 specification without the addition of a flame retardant.

The maleic imide resin of the present invention is selected from at least one of the group consisting of: 4,4'-diphenylmethane bismaleimide, benzylmethane maleate Oligomer of phenylmethane maleimide, m-phenylenebismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (3,3'-dimethyl-5,5'-diethyl-4, 4'-diphenylmethane bismaleimide), 4-methyl-1,3-phenylene bismaleimide and 1,6-bismaleimide-( 2,2,4-trimethyl)hexane (1,6-bismaleimide-(2,2,4-trimethyl)hexane).

The halogen-free resin composition of the present invention is added with 5 to 100 parts by weight of maleic imine based on 100 parts by weight of the cyanate resin, and the content of maleimide in the range of addition can be adjusted. The halogen-free resin composition has a high Tg (high glass transition temperature); if the content of maleimide is less than 5 parts by weight, the Tg requirement is not obtained. In addition, because of the high cost of the maleimide raw material, the use of more than 100 parts by weight of the maleimide may result in an increase in the cost of the resin composition.

The phosphorus-nitrogen-based compound of the present invention is a compound containing phosphorus and a nitrogen atom, and has a flame-retarding function as shown in the following structural formula, and the halogen-free resin is composed of a substrate formed by hardening, and the phosphorus-nitrogen group is burned. The phosphorus atoms of the compound form coke-like phosphoric acid covering the surface of the substrate and block the air from entering to block combustion. Compared with the conventional use of a halogen-containing flame retardant such as a bromide flame retardant, the phosphorus-nitrogen-based compound used in the present invention is a halogen-free compound, and does not generate harmful substances such as dioxin when burned.

(where n is a positive integer greater than 1)

The phosphorus-nitrogen-based compound of the present invention is added in an amount of 5 to 150 parts by weight based on 100 parts by weight of the cyanate resin, and less than 5 parts by weight, the flame retardancy is not good, and more than 150% by weight The cost increases and the substrate properties deteriorate. In the halogen-free resin composition of the present invention, the addition of the phosphorus-nitrogen-based compound has an advantage in that the flame retardancy of the halogen-free resin composition and the cured product thereof can be increased. By the addition of the flame-retardant compound, the halogen-free resin composition of the present invention can achieve the V-0 flame resistance effect of the UL94 specification, and the laminate and the circuit board using the halogen-free resin composition have good flame retardancy. effect.

The main advantage of the present invention using a phosphorus-nitrogen-based compound as a flame retardant is that the phosphorus-nitrogen-based compound does not have a free hydroxyl group (OH group), and thus addition to the resin composition does not increase the dielectric property of the resin composition. In addition, the phosphorus-nitrogen compound also has a high phosphorus content (13%, high temperature content), and a temperature-dependent temperature (Td, delaminated temperature, 5% weight loss temperature) (higher than other types of phosphorus-containing flame retardant) Agent), good hydrolysis resistance, lower hygroscopic property and high Tg temperature.

Compared with conventional phosphorus-containing flame retardants, such as phosphate flame retardants (OP-930, OP-935) have poor resistance to hydrolysis, such as phosphorus-containing phenol hardener DOPO-HQ (or HCA- HQ) and Fyrol PMP, having a polar functional hydroxyl group, result in an electrical increase in the resin composition and a lower thermal cracking temperature (less than 340 ° C).

In order to further improve the flame retardant properties of the halogen-free resin composition, in the preferred embodiment, the present invention may optionally further add at least one specific flame retardant compound in addition to the phosphorus-nitrogen compound. The flame retardant compound selected may be a phosphate compound or a nitrogen-containing phosphate compound, but is not limited thereto. More specifically, the flame retardant compound preferably comprises at least one of the following compounds: bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone-bis-(biphenyl) Hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenylphosphate), tris(2-carboxyethyl)phosphine (tri(2) -carboxyethyl)phosphine, TCEP), tris(isopropyl chloride) phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), resorcinol Resorcinol dixylenylphosphate (RDXP (such as PX-200)), melamine polyphosphate, azophosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, DOPO) and its derivatives or resins, melamine cyanurate and tris-hydroxyethyl isocyanuric acid Tri-hydroxy ethyl isocyanurate, etc., but not limited to this. For example, the flame retardant compound may be a DOPO compound, a DOPO resin (such as DOPO-HQ, DOPO-PN, DOPO-BPN), a DOPO bonded epoxy resin, etc., wherein the DOPO-BPN may be DOPO-BPAN, DOPO. a bisphenol phenolic compound such as BPFN or DOPO-BPSN.

The main function of the inorganic filler of the present invention is to increase the thermal conductivity of the halogen-free resin composition, to improve the thermal expansion property and the mechanical strength, and the inorganic filler is preferably uniformly distributed in the halogen-free resin composition.

Wherein, the inorganic filler may comprise cerium oxide (molten state, non-molten state, porous or hollow type), aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, 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), Zinc molybdate, ammonium molybdate, zinc borate, calcium phosphate, calcined talc, talc, tantalum nitride, molybdenite, kaolin kaolin, clay, basic magnesium sulfate whisker, molybdenum whisker, barium sulfate, hydrogen Magnesium oxide whiskers, magnesium oxide whiskers, calcium oxide whiskers, carbon nanotubes, nano-sized cerium oxide and related inorganic powders, or powder particles modified with an organic core outer shell as an insulator. The inorganic filler may be in the form of spheres, fibers, plates, granules, flakes or whiskers, and may be optionally pretreated via a decane coupling agent.

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 nm to 20 μm, preferably a nanometer-sized particle powder having a particle diameter of 1 μm or less; an whisker-like inorganic filler; It can be a powder having a diameter of 50 μm or less and a length of 1 to 200 μm.

The inorganic filler of the present invention is added in an amount of 10 to 1000 parts by weight based on 100 parts by weight of the cyanate resin. When the content of the inorganic filler is less than 10 parts by weight, the properties of the inorganic filler are not significantly improved, and the thermal expansion properties and mechanical strength are improved. When the content exceeds 1000 parts by weight, the fluidity of the pore-filling of the halogen-free resin composition is deteriorated. It deteriorates with the copper foil.

The resin composition of the present invention preferably uses one of a filler such as molten cerium oxide, porous cerium oxide, hollow cerium oxide, or spherical cerium oxide, in consideration of a preferred electrical property. Or a combination thereof.

In the resin composition of the present invention, at least one selected from the group consisting of epoxy resin, phenol resin, phenol resin, amine resin, phenoxy resin, benzoxazine resin, or the like may be further added. Styrene resin, polybutadiene resin, polyamide resin, polyimide resin, polyester resin.

The halogen-free resin composition of the present invention may further be an epoxy resin selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol S. Epoxy resin, bisphenol AD epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, o-cresol novolac epoxy resin, Trifunctional epoxy resin, tetrafunctional epoxy resin, multifunctional epoxy resin, dicyclopentadiene (DCPD) epoxy resin, phosphorus ring Oxygen resin, DOPO-containing epoxy resin, DOPO-HQ epoxy resin, p-xylene epoxy resin, naphthalene epoxy resin, benzopyran epoxy Resin, biphenyl novolac epoxy resin, phenol aralkyl novolac epoxy resin or a combination thereof.

The halogen-free resin composition of the present invention is preferably a dicyclopentadiene epoxy resin or a naphthalene epoxy resin. Among them, the addition of dicyclopentadiene epoxy resin can reduce the hygroscopicity of the resin composition; the addition of a naphthalene type epoxy resin can increase the rigidity and heat resistance of the resin composition.

Further, the halogen-free resin composition of the present invention may optionally comprise a surfactant, a silane coupling agent, a curing accelerator, a toughening agent or a solvent. ) and other additives. The main purpose of adding a surfactant is to improve the uniform dispersibility of the inorganic filler in the resin composition and to avoid aggregation of the inorganic filler. The main purpose of adding a toughening agent is to improve the toughness of the resin composition. The main function of adding a hardening accelerator is to increase the reaction rate of the resin composition. 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.

The decane coupling agent may include a silane compound and a siloxane compound, and may be further classified into an amino silane or an amino siloxane depending on the type of the functional group. Epoxy silane and epoxy siloxane.

The hardening accelerator may comprise a catalyst such as Lewis base or Lewis acid. Among them, the Lewis base may comprise imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-benzene. 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MZ), triphenylphosphine (TPP) and 4-dimethyl One or more of 4-dimethylaminopyridine (DMAP). The Lewis acid system may contain a metal salt compound such as a metal salt compound such as manganese, iron, cobalt, nickel, copper or zinc, such as a metal catalyst such as zinc octoate or cobalt octoate.

The toughening agent is selected from the group consisting of rubber (rubber) resin, carboxyl-terminated butadiene acrylonitrile rubber (CTBN), and core-shell rubber.

The solvent may include methanol, ethanol, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone (methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl A solvent such as acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide or propylene glycol methyl ether or a mixed solvent thereof.

In order to achieve low dielectric constant and low dielectric loss characteristics, the resin composition of the present invention must minimize the number of remaining hydroxyl groups. That is, the crosslinking density between the resins is increased. Therefore, the cross-linking action between the respective components of the resin composition disclosed in the present invention can promote the optimization of crosslinking according to the disclosed addition ratio, and the residual resin contains unreacted functional groups.

Another object of the present invention is to disclose a resin film having low dielectric properties, heat and flame resistance, low moisture absorption, halogen-free properties, and the like, and can be applied to an insulating layer of a laminate and a circuit board. material.

The resin film of the present invention comprises the aforementioned halogen-free resin composition which is formed into a semi-cured state via a heating process. For example, the halogen-free resin composition may be placed on a polyethylene terephthalate (PET) film and heated to form a resin film.

Still another object of the present invention is to disclose a resin coated copper foil (RCC) comprising at least one copper foil and at least one insulating layer. The copper foil may further comprise an alloy of copper and a metal such as aluminum, nickel, platinum, silver or gold. The resin film disclosed in the present invention is bonded to at least one piece of copper foil, the PET film is removed, and the resin film and the copper foil are heat-cured under high temperature and high pressure to form an insulation which is tightly bonded to the copper foil. Floor.

Still another object of the present invention is to disclose a semi-cured film having high mechanical strength, low dielectric constant and low dielectric loss, heat and flame resistance, low moisture absorption, and halogen-free properties. Accordingly, the prepreg film disclosed in the present invention may comprise a reinforcing material and the aforementioned halogen-free resin composition, wherein the halogen-free resin composition is attached to the reinforcing material and is heated to a semi-cured state by high temperature. 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.

Another object of the present invention is to disclose a copper foil substrate which has low dielectric properties, heat and flame resistance, low moisture absorption, high mechanical strength and halogen-free characteristics, and is particularly suitable for high-speed and high-frequency signal transmission. The circuit board. Accordingly, the present invention provides a copper foil substrate comprising two or more copper foils and at least one insulating layer. The copper 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 above-mentioned semi-cured 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 copper foil substrate of the present invention has at least one of the following advantages: low dielectric constant and low dielectric loss, excellent heat resistance and flame retardancy, low hygroscopicity, high thermal conductivity, and preferably thermal expansion. Better mechanical strength and environmental protection without halogen. After the copper foil substrate is further processed by a manufacturing process or the like, a circuit board can be formed, 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.

A further object of the present invention is to disclose a printed circuit board having low dielectric properties, heat and flame resistance, low moisture absorption, high mechanical strength, 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 copper foil substrates, 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 and the accompanying drawings.

The resin compositions of Examples 1 to 5 are listed in Table 1, and the resin compositions of Comparative Examples 1 to 8 are listed in Table 3, respectively.

Example 1 (E1)

A resin composition comprising the following ingredients:

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

(B) 50 parts by weight of styrene maleic anhydride EF-40;

(C) 100 parts by weight of polyphenylene ether resin MX-90;

(D) 100 parts by weight of maleic imine resin BMI-2300;

(E) 65 parts by weight of the phosphorus-nitrogen compound SPB-100;

(F) 125 parts by weight of molten cerium oxide (filler);

(G) 200 parts by weight of methyl ethyl ketone (solvent);

(H) 0.01 parts by weight of zinc octoate (catalyst).

Example 2 (E2)

A resin composition comprising the following ingredients:

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

(B) 5 parts by weight of styrene maleic anhydride EF-40;

(C) 100 parts by weight of polyphenylene ether resin MX-90;

(D) 100 parts by weight of maleic imine resin BMI-2300;

(E) 55 parts by weight of a phosphorus-nitrogen based compound SPB-100;

(F) 110 parts by weight of molten cerium oxide (filler);

(G) 170 parts by weight of methyl ethyl ketone (solvent);

(H) 0.01 parts by weight of zinc octoate (catalyst).

Example 3 (E3)

A resin composition comprising the following ingredients:

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

(B) 50 parts by weight of styrene maleic anhydride EF-40;

(C) 5 parts by weight of polyphenylene ether resin MX-90;

(D) 100 parts by weight of maleic imine resin BMI-2300;

(E) 45 parts by weight of a phosphorus-nitrogen based compound SPB-100;

(F) 90 parts by weight of molten cerium oxide (filler);

(G) 130 parts by weight of methyl ethyl ketone (solvent);

(H) 0.01 parts by weight of zinc octoate (catalyst).

Example 4 (E4)

A resin composition comprising the following ingredients:

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

(B) 50 parts by weight of styrene maleic anhydride EF-40;

(C) 100 parts by weight of polyphenylene ether resin MX-90;

(D) 5 parts by weight of maleic imine resin BMI-2300;

(E) 45 parts by weight of a phosphorus-nitrogen based compound SPB-100;

(F) 90 parts by weight of molten cerium oxide (filler);

(G) 130 parts by weight of methyl ethyl ketone (solvent);

(H) 0.01 parts by weight of zinc octoate (catalyst).

Example 5 (E5)

A resin composition comprising the following ingredients:

(A) 50 parts by weight of cyanate resin BA-230S;

(B) 50 parts by weight of cyanate resin PT-30S;

(C) 25 parts by weight of styrene maleic anhydride EF-30;

(D) 25 parts by weight of styrene maleic anhydride EF-40;

(E) 50 parts by weight of polyphenylene ether resin MX-90;

(F) 25 parts by weight of maleic imine resin BMI-2300;

(G) 25 parts by weight of maleic imide resin Homide 121;

(H) 50 parts by weight of a phosphorus-nitrogen based compound SPB-100;

(I) 15 parts by weight of DCPD epoxy resin;

(J) 15 parts by weight of a naphthalene type epoxy resin;

(K) 50 parts by weight of molten cerium oxide (filler);

(L) 50 parts by weight of spherical cerium oxide (filler);

(M) 140 parts by weight of methyl ethyl ketone (solvent);

(N) 0.02 parts by weight of zinc octoate (catalyst);

(O) 0.2 parts by weight of 2E4MI (catalyst).

Comparative Example 1 (C1)

A resin composition comprising the following ingredients:

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

(B) 3 parts by weight of styrene maleic anhydride EF-40;

(C) 100 parts by weight of polyphenylene ether resin MX-90;

(D) 100 parts by weight of maleic imine resin BMI-2300;

(E) 55 parts by weight of OP-935 (flame retardant);

(F) 110 parts by weight of molten cerium oxide (filler);

(G) 170 parts by weight of methyl ethyl ketone (solvent);

(H) 0.01 parts by weight of zinc octoate (catalyst).

Comparative Example 2 (C2)

A resin composition comprising the following ingredients:

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

(B) 60 parts by weight of styrene maleic anhydride EF-40;

(C) 100 parts by weight of polyphenylene ether resin MX-90;

(D) 100 parts by weight of maleic imine resin BMI-2300;

(E) 65 parts by weight of OP-935 (flame retardant);

(F) 130 parts by weight of molten cerium oxide (filler);

(G) 200 parts by weight of methyl ethyl ketone (solvent);

(H) 0.01 parts by weight of zinc octoate (catalyst).

Comparative Example 3 (C3)

A resin composition comprising the following ingredients:

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

(B) 50 parts by weight of styrene maleic anhydride EF-40;

(C) 3 parts by weight of polyphenylene ether resin MX-90;

(D) 100 parts by weight of maleic imine resin BMI-2300;

(E) 45 parts by weight of OP-935 (flame retardant);

(F) 90 parts by weight of molten cerium oxide (filler);

(G) 130 parts by weight of methyl ethyl ketone (solvent);

(H) 0.01 parts by weight of zinc octoate (catalyst).

Comparative Example 4 (C4)

A resin composition comprising the following ingredients:

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

(B) 50 parts by weight of styrene maleic anhydride EF-40;

(C) 110 parts by weight of polyphenylene ether resin MX-90;

(D) 100 parts by weight of maleic imine resin BMI-2300;

(E) 65 parts by weight of OP-935 (flame retardant);

(F) 130 parts by weight of molten cerium oxide (filler);

(G) 200 parts by weight of methyl ethyl ketone (solvent);

(H) 0.01 parts by weight of zinc octoate (catalyst).

Comparative Example 5 (C5)

A resin composition comprising the following ingredients:

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

(B) 50 parts by weight of styrene maleic anhydride EF-40;

(C) 100 parts by weight of polyphenylene ether resin MX-90;

(D) 3 parts by weight of maleic imine resin BMI-2300;

(E) 45 parts by weight of OP-935 (flame retardant);

(F) 90 parts by weight of molten cerium oxide (filler);

(G) 130 parts by weight of methyl ethyl ketone (solvent);

(H) 0.01 parts by weight of zinc octoate (catalyst).

Comparative Example 6 (C6)

A resin composition comprising the following ingredients:

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

(B) 50 parts by weight of styrene maleic anhydride EF-40;

(C) 100 parts by weight of polyphenylene ether resin MX-90;

(D) 120 parts by weight of maleic imine resin BMI-2300;

(E) 65 parts by weight of OP-935 (flame retardant);

(F) 130 parts by weight of molten cerium oxide (filler);

(G) 210 parts by weight of methyl ethyl ketone (solvent);

(H) 0.01 parts by weight of zinc octoate (catalyst).

Comparative Example 7 (C7)

A resin composition comprising the following ingredients:

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

(B) 3 parts by weight of styrene maleic anhydride EF-40;

(C) 3 parts by weight of polyphenylene ether resin MX-90;

(D) 3 parts by weight of maleic imine resin BMI-2300;

(E) 30 parts by weight of OP-935 (flame retardant);

(F) 30 parts by weight of DCPD epoxy resin;

(G) 30 parts by weight of a naphthalene type epoxy resin;

(H) 60 parts by weight of molten cerium oxide (filler);

(I) 60 parts by weight of methyl ethyl ketone (solvent);

(J) 0.01 parts by weight of zinc octoate (catalyst).

(K) 0.35 parts by weight of 2E4MI (catalyst).

Comparative Example 8 (C8)

A resin composition comprising the following ingredients:

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

(B) 60 parts by weight of styrene maleic anhydride EF-40;

(C) 110 parts by weight of polyphenylene ether resin MX-90;

(D) 120 parts by weight of maleic imine resin BMI-2300;

(E) 70 parts by weight of OP-935 (flame retardant);

(F) 140 parts by weight of molten cerium oxide (filler);

(G) 220 parts by weight of methyl ethyl ketone (solvent);

(H) 0.02 parts by weight of zinc octoate (catalyst).

The resin compositions of the above Examples 1 to 5 and Comparative Examples 1 to 8 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 220 ° 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 after etching the copper-containing foil substrate and the copper foil is respectively measured for physical properties, and the physical property measurement items include glass transition temperature (Tg), heat resistance (T288), substrate thermal cracking temperature (Td), and copper content. Substrate immersion tin test (solder dip 288 ° C, 10 seconds, heat resistance count), copper substrate PCT moisture immersion tin test (pressure cooking at 121 ° C, after 3 hours, measured solder dip 288 ° C, 20 seconds watch Whether there is a blasting plate), peeling strength (P/S, half ounce copper foil), dielectric constant (Dk), dielectric loss (Df), flame resistance (flaming test) , UL94, which ranks V-0 better than V-1), four-layer board drilling (pressing the four-layer board and measuring the nail head and the needle loss).

The physical property measurement results of the substrates prepared in the resin compositions of Examples 1 to 5 are listed in Table 2, and the substrate physical property measurement results of the resin compositions of Comparative Examples 1 to 8 are shown in Table 4. From Tables 2 and 4, comparing Comparative Examples 1 to 5 and Comparative Examples 1 to 8, it was found that flame retardants were respectively SPB-100 and OP-935, and the results of Comparative Examples 1 to 8 showed the addition of OP. The substrate of -935 has a significantly lower Td value and a poorer flaming test with a V-1 rating. The resin composition of the present invention uses SPB-100 to significantly increase the Td value of the substrate, improve the heat resistance of the substrate, and have a better V-0 rating for the flaming test.

Comparing Examples 1 and 2, the results show that increasing the content of styrene maleic anhydride (SMA) can lower the Dk value; from Comparative Example 2, the SMA content exceeding 50 parts by weight causes the substrate heat resistance (T288, Td, S/D, PCT (3hr)) decreased, and the appearance of the semi-cured film deteriorated, reducing the yield yield; from Comparative Example 1, the SMA content was less than 5 parts by weight, the substrate Dk value became high, and the desired low dielectric constant was not achieved. .

Comparing Examples 1 and 3, the results show that increasing the content of polyphenylene ether resin (PPO) can lower the Df value; from Comparative Example 4, the PPO content exceeding 100 parts by weight causes the substrate heat resistance (T288, Td, PCT (3 hr)) The difference is that the appearance of the semi-cured film is deteriorated, and the productivity is lowered. From Comparative Example 3, when the PPO content is less than 5 parts by weight, the Df value of the substrate becomes high, failing to achieve the desired low dielectric loss.

Comparing Examples 1 and 4, the results show that increasing the content of maleimide resin (BMI-2300) can increase the heat resistance (Tg) of the substrate; from Comparative Example 6, the BMI content exceeding 100 parts by weight causes the cost of the resin composition. Increasing, reducing competitiveness; by Comparative Example 5, a BMI content of less than 5 parts by weight causes a decrease in substrate heat resistance (Tg).

Comparing Examples 1 to 5 and Comparative Examples 1 to 8, the results show that a substrate having a better physical property can be obtained according to the composition and ratio of the resin composition disclosed in the present invention.

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 halogen-free resin composition of the present invention can achieve low dielectric constant, low dielectric loss, high heat resistance and high flame resistance by including specific component parts and ratios. It can be made into a semi-cured film or a resin film to achieve the purpose of being applied to a copper foil substrate and a printed circuit board; in terms of industrial availability, the products derived from the present invention can fully satisfy the current market. Demand.

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 (11)

A halogen-free resin composition comprising: (A) 100 parts by weight of a cyanate ester resin; (B) 5 to 50 parts by weight of styrene-maleic anhydride (SMA); C) 5 to 100 parts by weight of a polyphenylene oxide (PPO) resin; (D) 5 to 100 parts by weight of a maleimide resin (maleimide); (E) 10 to 150 parts by weight of a phosphorus-nitrogen group a compound (phosphazene); and (F) 10 to 1000 parts by weight of an inorganic filler. The halogen-free resin composition according to claim 1, wherein the cyanate resin is selected from at least one of the following groups: Wherein X ₁ and X ₂ are each independently at least one R, Ar, SO ₂ or O functional group; R is selected from the group consisting of -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -CH ₂ - and substituted Or unsubstituted dicyclopentadienyl; Ar is selected from substituted or unsubstituted benzene, biphenyl, naphthalene, phenolic, bisphenol A, bisphenol A phenolic, bisphenol F and bisphenol F phenolic functional a group; n is an integer greater than or equal to 1; Y is an aliphatic functional group or an aromatic functional group. The halogen-free resin composition according to claim 1, wherein the polyphenylene ether resin is selected from at least one of the following groups: Wherein X ₆ is selected from the group consisting of a covalent bond, -SO ₂ -, -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -CH ₂ -; Z ₁ to Z ₁₂ are each independently selected from the group consisting of hydrogen and W is a hydroxyl group, a vinyl group, a styryl group, a propenyl group, a butenyl group, a butadienyl group or an epoxy functional group; and n is an integer greater than or equal to 1. The halogen-free resin composition according to claim 1, wherein the maleic imide resin is selected from at least one of the group consisting of 4,4'-diphenylmethane bismaleimide. (4,4'-diphenylmethane bismaleimide), oligomer of phenylmethane maleimide, m-phenylenebismaleimide, bisphenol A diphenyl Bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (3 ,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide), 4-methyl-1,3-phenylene bismaleimide (4-methyl-1,3-phenylene) Bismaleimide) and 1,6-bismaleimide-(2,2,4-trimethyl)hexane. The halogen-free resin composition according to claim 1, wherein the inorganic filler is selected from at least one of the group consisting of cerium oxide (molten state, non-molten state, porous or hollow type). , alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum carbide tantalum, 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), zinc molybdate, ammonium molybdate, zinc borate, calcium phosphate, calcined talc, talc, tantalum nitride, mo Lai Shi, Duan Shao Kaolin, clay, basic magnesium sulfate whiskers, Molyite whiskers, barium sulfate, magnesium hydroxide whiskers, magnesium oxide whiskers, calcium oxide whiskers, carbon nanotubes, nanometer two Cerium oxide and its related inorganic powder and powder particles modified with an organic core outer shell as an insulator. The halogen-free resin composition according to any one of claims 1 to 5, further comprising at least one selected from the group consisting of bisphenol diphenyl phosphate, polyphosphoric acid Ammonium polyphosphate, hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenylphosphate) )), tri(2-carboxyethyl)phosphine (TCEP), tris(isopropyl chloride) phosphate, trimethyl phosphate (TMP), dimethyl- Methyl phosphate (DMMP), resorcinol dixylenyl phosphate (RDXP (such as PX-200)), melamine polyphosphate, azo phosphate, 9, 10-Dihydro-9-oxa-10-phenanthrene-10-oxide (DOPO) and its derivatives or resins, melamine cyanide Melamine cyanurate and tri-hydroxy ethyl isocyanurate. The halogen-free resin composition according to any one of claims 1 to 5, further comprising at least one selected from the group consisting of epoxy resins, phenol resins, phenol resins, Amine resin, phenoxy resin, benzoxazine resin, styrene resin, polybutadiene resin, polyamide resin, polyimide resin, polyester resin. The halogen-free resin composition according to any one of claims 1 to 5, further comprising at least one selected from the group consisting of a hardening accelerator, a toughening agent, a flame retardant, and a dispersing agent , organic germanium elastomers and solvents. A semi-cured film comprising the halogen-free resin composition as described in any one of claims 1 to 8. A copper foil substrate comprising the prepreg as described in claim 9 of the patent application. A printed circuit board comprising the copper foil substrate as described in claim 10 of the patent application.