TWI417339B - Resin composition - Google Patents

Description

Resin composition

The present invention relates to a composition, and more particularly to a resin composition suitable for use in a printed circuit board.

Due to the popularity of cloud computing and the increasing use of high-speed transmission, the dielectric constant of existing FR-4 substrates has gradually failed to meet existing needs. In general, low dielectric constant materials are mainly used for high frequency transmission of printed circuit boards, insulation protection of electronic components, or laminated insulation films for lead frames. Since the aforementioned applications all involve high-temperature processes of printed circuit boards, polyphenylene ether having low dielectric properties is often used for low dielectric base film layers. In addition, since epoxy resin has excellent electrical properties, mechanical strength and chemical resistance, and has good adhesion effect on copper foil, low dielectric materials of general printed circuit boards often use polyphenylene ether as a main low dielectric material. The blended epoxy resin is an adhesive.

However, since the material composition existing in the prior art cannot fully meet the needs of the industry, it is necessary to propose a material which can improve the dielectric constant.

Inspired by the shortcomings of the prior art, the inventors exhausted their intellectual research and developed a novel resin composition based on their years of experience in the industry.

One of the objects of the present invention is to provide a resin composition, which comprises (1) 100 parts by weight of epoxy resin; (2) 20 to 100 parts by weight of a vinyl resin; (3) 10 to 50 parts by weight of styrene maleic anhydride (SMA); (4) 5 to 50 parts by weight of benzoxazine; (5) 0.5 to 5 parts by weight of the binder; (6) 10 to 150 parts by weight of the inorganic filler; (7) 0.2 to 25 parts by weight a peroxide; (8) 10 to 250 parts by weight of a phosphorus-containing flame retardant; and (9) 0.01 to 10 parts by weight of a catalyst.

Still another object of the present invention is to provide a film mainly comprising the aforementioned resin composition which is heated to be semi-cured.

Another object of the present invention is to provide a metal substrate which is mainly formed by sequentially laminating a copper foil, the film and a metal plate, and then pressing the copper foil by a microlithography process to form a circuit. Got it.

Still another object of the present invention is to provide a prepreg film which is mainly obtained by impregnating a glass fiber cloth with the resin composition and baking it.

Further, it is an object of the present invention to provide a copper foil laminate and a circuit board. The copper foil laminated board is obtained by pressing a copper foil and the prepreg film, and the circuit board is obtained by performing a circuit processing process on the circuit board composed of the copper foil laminated board.

A further object of the present invention is to provide a semi-cured composite film comprising the foregoing film and a polyethylene terephthalate (PET) film, a polyimide film (PI) film, and a thermoplastic type bonded to the film. Polyimine (TPI) film, thermally conductive polyimine (TCPI) film, metal foil (such as copper foil, aluminum foil, etc.), polyethylene naphthalate (PEN) film, liquid crystal polymer (LCP) film , carbon fiber cloth, aromatic aramid fiber or polytetrafluoroethylene (PTFE) film.

Still another object of the present invention is to provide a copper foil laminate which is obtained by press-bonding the above-mentioned semi-cured composite film between at least two copper foils.

To fully clarify the objects, features, and advantages of the present invention, those of ordinary skill in the art of the present invention can understand the present invention and can implement the present invention. The present invention will be described in detail by the following specific embodiments. The description is as follows.

The resin composition of the present invention mainly contains the following components: (1) 100 parts by weight of an epoxy resin; (2) 20 to 100 parts by weight of a vinyl resin; and (3) 10 to 50 parts by weight of styrene maleic anhydride; (4) 5 to 50 parts by weight of a benzox port well; (5) 0.5 to 5 parts by weight of a sealant; (6) 10 to 150 parts by weight of an inorganic filler; (7) 0.2 to 25 parts by weight a peroxide; (8) 10 to 250 parts by weight of a phosphorus-containing flame retardant; and (9) 0.01 to 10 parts by weight of a catalyst.

In one embodiment, the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and phenol novolac. Epoxy resin, bisphenol A novolac epoxy resin, o-cresol novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, Polyfunctional epoxy resin, dicyclopentadiene (DCPD) epoxy resin, phosphorus-containing epoxy resin, p-xylene epoxy resin, naphthalene type ( Naphthalene) epoxy resin, benzopyran epoxy resin, biphenyl novolac epoxy resin, phenolic phenyl benzene Phenol aralkyl novolac epoxy resin, antimony-containing epoxy resin, fluorine-containing epoxy resin, boron-containing epoxy resin, titanium-containing epoxy resin, epoxidized polybutadiene resin, polyester epoxy resin, An epoxy resin having a maleic amine structure or a combination thereof. By the presence of the epoxy resin, the properties of the resin composition of the present invention such as crosslinkability and heat resistance can be further improved.

In one embodiment, the vinyl resin is polybutadiene styrene divinylbenzene, such as Ricon® 250, which is commercially available from Sartomer Corporation.

In one embodiment, the vinyl resin is a vinyl benzyl ether compound, such as V-1000X or V-1100X, which is commercially available from Showa Highpolymer Co., LTD. and has the following structure:

Where n=3 to 5;

Wherein m = 3 to 5; R ₁ and R ₂ are each independently an aliphatic or aromatic functional group or H.

By the presence of the vinyl resin, the dielectric constant and thermal expansion coefficient of the resin composition can be lowered.

In one embodiment, the adhesion agent is 2,4,6-trimercapto-s-triazine (2,4,6-trimercapto-s-triazine, TSH), 2-di-n-butylamino-4,6 2-di-n-butylamino-4, 6-dimercapto-s-triazine (BSH), thiol propionic acid compound or a combination thereof. By the presence of the adhesive, the peel strength of the resin composition can be improved, and the copper foil and the insulating layer are less likely to be separated during processing.

In one embodiment, the benzox port well is VR-3000 available from Hitachi Chemical Co. Ltd. or 8280 from Huntsman Corporation.

In one embodiment, the styrene maleic anhydride is purchased from CRAY VALLEY and its S:A ratio can be any integer ratio of 1:1 to 12:1.

In one embodiment, the inorganic filler may comprise ceria (molten or non-molten), alumina, magnesia, magnesium hydroxide, calcium carbonate, talc, clay, aluminum nitride, boron nitride, hydroxide Aluminum, aluminum lanthanum carbide, tantalum carbide, sodium carbonate, titanium dioxide, zinc oxide, zirconium oxide, quartz, diamond powder, diamond powder, graphite, hydrotalcite, hollow cerium oxide, PTFE powder, glass beads, ceramic whiskers, nai The carbon nanotube, the nano-scale inorganic powder, the metal core outer shell is at least one of an insulator-modified powder particle or a calcined kaolin, and the inorganic filler may be spherical or irregular, and may selectively pass through the interface. Active agent pretreatment. 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 having a particle diameter of 1 μm. The following nano-sized granule powder. By the presence of the inorganic filler, the thermal conductivity of the resin composition can be increased, and the properties such as thermal expansion property and mechanical strength can be improved.

In one embodiment, the peroxide can be any organic oxide that can be used for crosslinking, such as those sold by PERGAN, including bis-(2,4-dichlorobenzhydryl)-peroxide, Terephthalic acid peroxide, tertiary butyl peroxybenzoate, dicumyl peroxide, etc., but not limited thereto.

In one embodiment, 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 crosslinkable with the resin, and may be, for example, Exolit OP 935 (available from Clariant). , SPB-100 (available from Otsuka Chemical), PX-200 (available from Da Ba Chemical); the latter is crosslinkable with the resin and can be, for example, bisphenol substituted by DOPO or its derivatives (bisphenol) Novolac, BPN) resin or phenol novolac (PN) resin.

In one embodiment, the catalyst is selected from the group consisting of boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenyl. Imidazole (2-phenyl-1H-imidazole, 2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP), 4-dimethyl One or more kinds of Lewis base such as 4-dimethylaminopyridine (DMAP), quaternary phosphonium salt, imidazole epoxy composite, urea catalyst, or the like, or selected from the group consisting of manganese, iron, cobalt, nickel, copper and zinc Metal salt compound, etc. one or more types of Lewis acid.

In one embodiment, the resin composition of the present invention further comprises terminal acrylic modified butadiene, maleated butadiene, PU modified butadiene, high molecular weight liquid polybutadiene, polyphenylene ether resin. , Ethylene polyphenylene ether resin, benzocyclobutene resin, acrylylated biguanide-based double norbornene resin, bismaleimide-cyanuric acid, cyanate resin, benzene Parallel mouth well resin, polyimine, polyamidimide resin, ruthenium-containing polyimide resin and combinations thereof.

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 The modifications and variations achieved are within the scope of the invention:

Embodiment 1

40 g of Ricon 250 was dissolved in 160 g of toluene to prepare a 20% vinyl-toluene solution. 100 g of biphenyl type epoxy resin, 46 g of SMA resin, 15 g of benzophenium boring well, 90 g of aluminum hydroxide, 10 g of talc, and 4 g of dicumyl peroxide were sequentially added to a 1000 mL reaction flask. 1 g of dicyanodiamide (DICY), 8 g of diamino diphenyl sulfone (DDS), 30 g of OP 935, 1 g of TSH, 0.2 g of 2E4MI, and then 200 g of a vinyl-toluene solution was added to the aforementioned reaction. The bottle is prepared to complete the dispersed epoxy resin main agent.

Embodiment 2

40 g of Ricon 250 was dissolved in 160 g of toluene to prepare a 20% vinyl-toluene solution. 100 g of biphenyl type epoxy resin, 26 g of SMA resin, 30 g of benzophenium boring well, 90 g of aluminum hydroxide, 10 g of talc, 4 g of bisisophenylpropyl peroxide, 0.5 g of DICY were sequentially added to a 1000 mL reaction flask. 8 g of DDS, 25 g of OP 935, 1.5 g of TSH, 0.2 g of 2E4MI, and then 200 g of a vinyl-toluene solution were added to the aforementioned reaction flask to prepare a dispersed epoxy resin main agent.

Comparative example one

100 g of a phosphorus-containing epoxy resin, 26 g of phenolic resin, 90 g of aluminum hydroxide, 10 g of talc, 4 g of DICY, and 0.2 g of 2E4MI were sequentially added to a 1000 mL reaction flask to prepare a dispersed epoxy resin main component.

Comparative example two

100 g of a phosphorus-containing epoxy resin, 26 g of a phenol resin, 90 g of aluminum hydroxide, 10 g of talc, and 0.2 g of 2E4M1 were sequentially added to a 1000 mL reaction flask to prepare a dispersed epoxy resin main component.

Comparative example three

100 g of phosphorus-containing epoxy resin, 26 g of phenolic resin, 65 g of benzoxanthine well, 8 g of bisisophenylpropyl peroxide, 90 g of aluminum hydroxide, 10 g of talc, 0.2 g of 2E4MI, and the like, were sequentially added to a 1000 mL reaction flask. 36 g SMA resin, prepared to complete the dispersion of epoxy resin main agent.

The composition of the foregoing embodiment and the comparative example is formed into a film by coating and baking, and a copper foil is respectively laminated on both sides of the film, and then the laminated structure is pressed under high temperature and high pressure to form a copper foil. The substrate and the copper foil on the copper foil substrate are appropriately etched to form a test piece (copper foil) peel strength, coefficient of thermal expansion (CTE) and glass transition temperature (Tg), Dk and Df of a thickness of 25 μm. The results are shown in Table 1:

When the examples and the comparative examples were observed, it was found that the composition of the examples had characteristics such as low dielectric constant (Dk), low dielectric loss (Df), low coefficient of thermal expansion (CTE), high peel strength, and high glass transition temperature.

Embodiment 3

40 g of Ricon 250 was dissolved in 160 g of toluene to prepare a 20% vinyl-toluene solution. Add 100g to the 1000mL reaction bottle. Biphenyl type epoxy resin, 20g V-1100X resin, 15g benzo port mouth well, 16g SMA resin, 90g aluminum hydroxide, 10g talc, 4g bisisophenylpropyl peroxide, 1g DICY, 8g DDS, 40g OP 935, 1 g of TSH, 0.2 g of 2E4MI, and then 200 g of a vinyl-toluene solution was added to the aforementioned reaction flask to prepare a dispersed epoxy resin main agent.

Embodiment 4

40 g of Ricon 250 was dissolved in 160 g of toluene to prepare a 20% vinyl-toluene solution. 100 g of biphenyl type epoxy resin, 26 g of V-1100X resin, 30 g of benzophene sputum well, 36 g of SMA resin, 90 g of aluminum hydroxide, 10 g of talc, 4 g of bisisophenyl propyl group were sequentially added to a 1000 mL reaction flask. Oxide, 0.5 g of DICY, 8 g of DDS, 45 g of OP 935, 1.5 g of TSH, 0.2 g of 2E4MI, and then 200 g of a vinyl-toluene solution were added to the aforementioned reaction flask to prepare a dispersed epoxy master.

Comparative example four

40 g of Ricon 250 was dissolved in 160 g of toluene to prepare a 20% vinyl-toluene solution. 100 g of biphenyl type epoxy resin, 30 g of benzophene boring well, 90 g of aluminum hydroxide, 10 g of talc, 4 g of bisisophenyl propyl peroxide, 0.5 g of DICY, 8 g of DDS, and the like are sequentially added to a 1000 mL reaction flask. 25 g of OP 935, 1.5 g of TSH, 0.2 g of 2E4MI, and then 200 g of a vinyl-toluene solution was added to the aforementioned reaction flask to prepare a dispersed epoxy resin main agent.

Comparative example five

100 g of phosphorus-containing epoxy resin, 26 g of phenolic resin, 90 g of aluminum hydroxide, 10 g of talc, 0.2 g were sequentially added to a 1000 mL reaction flask. 2E4MI, prepared to complete the dispersion of the epoxy resin main agent.

The composition of the foregoing examples and comparative examples were tested for peel strength, coefficient of thermal expansion (CTE) and glass transition temperature (Tg), Dk and Df in a test piece having a thickness of 25 μm. The results are shown in Table 2:

When the examples and the comparative examples were observed, it was found that the composition of the examples had characteristics such as low dielectric constant (Dk), low dielectric loss (Df), low coefficient of thermal expansion (CTE), and high glass transition temperature.

Embodiment 5

An exposed resin composition is uniformly mixed in a stirring tank and then coated on a PET film, and then baked into a semi-cured state by heating, and the PET film is removed to obtain a film.

Embodiment 6

The five prepared films are laminated in the order of copper foil, film, and aluminum plate, and then pressed by a high temperature and high pressure process to form an aluminum substrate, wherein the cured film is used as an insulating layer between the copper foil and the aluminum plate. .

Example 7

The resin composition disclosed in the third embodiment is uniformly mixed in a stirring tank, placed in an impregnation tank, and the glass fiber cloth is passed through the impregnation tank to adhere the resin composition to the glass fiber cloth, and is heated and baked. A semi-cured film is obtained.

Example eight

Two pieces of copper foil are laminated on at least one side of the semi-cured film prepared in the seventh embodiment, and then pressed by a high temperature and high pressure process to obtain a copper foil laminated board, wherein the semi-cured film is cured to form two copper foils. Insulation between.

Example nine

The resin composition of the present invention is applied onto a PET film, and the resin composition is semi-cured by heating to form a semi-cured composite film.

Example ten

Two pieces of copper foil are laminated on at least one side of the semi-cured composite film prepared in the ninth embodiment, and then pressed at a high temperature and a high pressure to obtain a kind A copper foil laminate, wherein the semi-cured composite film serves as an insulating layer between the two copper foils.

Embodiment 11

A plurality of copper foil laminates prepared in the eighth embodiment and/or the tenth embodiment are subjected to a photolithography process to form a surface circuit, and are interleaved with two layers of the semi-cured film prepared in the seventh embodiment. The foil substrate is then subjected to a high temperature and high pressure pressing process to form a circuit substrate, and processed by a circuit board processing process to obtain a circuit board.

The present invention has been disclosed in its preferred embodiments, and it should be understood by those of ordinary skill 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 considered to be within the scope of the invention. Therefore, the scope of the invention is defined by the scope of the following claims.

Claims (14)

A resin composition comprising: (1) 100 parts by weight of an epoxy resin; (2) 20 to 100 parts by weight of a vinyl resin; (3) 10 to 50 parts by weight of styrene maleic anhydride; (4) 5 To 50 parts by weight of a benzox port well; (5) 0.5 to 5 parts by weight of a sealant; (6) 10 to 150 parts by weight of an inorganic filler; (7) 0.2 to 25 parts by weight of a peroxide; (8) 10 to 250 parts by weight of the phosphorus-containing flame retardant; and (9) 0.01 to 10 parts by weight of the catalyst. The resin composition according to claim 1, wherein the vinyl resin is polybutadiene-styrene-divinylbenzene, ethylene benzyl ether compound or a combination thereof. The resin composition according to claim 1, wherein the adhesive agent is 2,4,6-trimethyl-s-three wells, 2-di-n-butylamino-4,6-dimercapto-s - three wells, thiopropionic acid compounds or combinations thereof. The resin composition according to claim 1, wherein the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolac epoxy resin, bisphenol A phenolic epoxy resin, o-cresol epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, polyfunctional epoxy resin, dicyclopentadiene epoxy resin, phosphorus-containing epoxy resin, pair Xylene epoxy resin, naphthalene epoxy resin, benzopyran epoxy resin, biphenolic epoxy resin, phenolic phenylalkyl phenolic epoxy resin, cerium-containing epoxy resin A grease, a fluorine-containing epoxy resin, a boron-containing epoxy resin, a titanium-containing epoxy resin, an epoxidized polybutadiene resin, a polyester epoxy resin, an epoxy resin having a maleimide structure, and a combination thereof. The resin composition as described in claim 1 further comprises terminal acrylic modified butadiene, maleic anhydride butadiene, PU modified butadiene, high molecular weight liquid polybutadiene, polyphenylene. Ether resin, vinylated polyphenylene ether resin, benzocyclobutene resin, acrylylated biguanide-based double norbornene resin, bismaleimide-cyanuric resin, cyanate resin Benzene mouth-filled well resin, polyimide, polyamidamine resin, ruthenium-containing polyimide resin and combinations thereof. The resin composition according to claim 1, wherein the inorganic filler is selected from the group consisting of cerium oxide, aluminum oxide, magnesium oxide, magnesium hydroxide, calcium carbonate, talc, clay, aluminum nitride, and boron nitride. , aluminum hydroxide, aluminum lanthanum carbide, tantalum carbide, sodium carbonate, titanium dioxide, zinc oxide, zirconia, quartz, diamond, diamond-like, graphite, calcined kaolin, hydrotalcite, hollow cerium oxide, PTFE powder, glass beads, ceramics Whiskers, carbon nanotubes, nano-scale inorganic powders, powdered particles with metal core outer shells as insulators and combinations thereof. The resin composition according to claim 1, wherein the catalyst is selected from the group consisting of boron trifluoride amine complex, ethyl triphenylphosphonium chloride, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, 4-dimethylaminopyridine, and metal salt compounds of manganese, iron, cobalt, nickel, copper and zinc, quaternary phosphonium salts, imidazole epoxy Complex, urea catalyst and combinations thereof. A film comprising the method of any one of claims 1 to 7 A resin composition in which the resin composition is in a semi-cured state. A metal substrate comprising a metal plate, a copper foil, and a film according to item 8 of the patent application, wherein the film is interposed between the metal plate and the copper foil. A semi-cured film comprising a glass fiber cloth and a resin composition according to any one of claims 1 to 7, wherein the resin composition is in a semi-cured state and covers the glass fiber cloth. A copper foil laminate comprising at least one copper foil and a prepreg according to claim 10, wherein the prepreg is pressed to the copper foil. A circuit board comprising at least one copper foil laminate as described in claim 11 of the patent application. A semi-cured composite film comprising a film according to item 8 of the patent application and a polyethylene terephthalate film, a polyimide film, a thermosetting polyimide film, A thermally conductive polyimide film, a metal foil, a polyethylene naphthalate film, a liquid crystal polymer film, a polytetrafluoroethylene film, a carbon fiber cloth or an aromatic polyamide fiber. A copper foil laminate comprising at least two copper foils and a semi-cured composite film according to claim 13 wherein the semi-cured composite film is press-bonded between the copper foils.