Resin composition, metal foil-clad laminated board containing same and application of metal foil-clad laminated board

Abstract

The invention provides a resin composition, a metal foil-coated laminated board containing the resin composition and application of the metal foil-coated laminated board, and the resin composition comprises the following components in parts by mass: 30-60 parts of epoxy resin, 15-30 parts of a reactive phosphorus-containing flame retardant, 3-15 parts of a curing agent and 180-300 parts of spherical composite silicon micro powder on the basis that the total mass of organic resin is 100 parts; the mass percentage of silicon dioxide in the spherical composite silicon micropowder is 50-70%, and the D50 particle size of the spherical composite silicon micropowder is less than or equal to 5 microns. Through the design of the spherical composite silica powder, the epoxy resin, the reactive phosphorus-containing flame retardant and the curing agent and the compounding of the spherical composite silica powder, the epoxy resin, the reactive phosphorus-containing flame retardant and the curing agent in specific dosages, the resin composition and the metal foil-clad laminated board containing the resin composition realize halogen-free flame retardance, high glass transition temperature and low linear thermal expansion coefficient; and the adhesive has excellent interlayer adhesive force and drilling processability, and can fully meet the requirement of a high-density communication substrate for thermal reliability.

Description

Technical Field

[0001] The present invention belongs to the technical field of printed circuits, and particularly relates to a resin composition, a metal-clad laminate containing the same, and their applications. Background Art

[0002] With the rapid development of new communication technologies and new models, data information is showing an explosive growth. To meet the need for processing massive information, terminal products tend to adopt faster IC operation chips. At the same time, the number of chips is increased, and the data processing and transmission rate is improved through parallel methods, but it also brings a large energy consumption problem. To reduce the energy consumption of chip operation, terminal manufacturers will control the start and stop of chips according to requirements. However, during the frequent start and stop process of chips, the phenomenon of sudden heating and cooling poses a serious challenge to the connection reliability between the chip and the PCB (printed circuit board) carrier substrate.

[0003] As a PCB substrate carrying chips for communication facilities, in order to meet the requirements of board flatness and dense circuits, the glass cloth reinforcement material used for the substrate is often thin 2116 cloth or thinner glass cloth. For existing ordinary high T g (glass transition temperature) materials, the coefficient of linear expansion (XY-axis CTE) of the board made of 2116 cloth is about 17 ppm / °C, which is much higher than that of the chip. In actual applications, it seriously affects the long-term reliability of the chip on the carrier substrate. Therefore, reducing the CTE difference between the PCB and the carried chip, improving the ability of the PCB substrate to resist thermal shock, and reducing the thermal expansion rate of the substrate, especially making the coefficient of linear expansion lower than 13 ppm / °C, have become urgent problems to be solved for communication substrate materials.

[0004] In a PCB substrate reinforced with glass fiber cloth and bonded with an organic resin, the coefficient of thermal expansion (CTE) of the organic resin used is generally between 50 - 70 ppm / °C. To reduce the CTE of the organic resin, aromatic rings or aromatic heterocyclic resins are often used, and maleimide, cyanate ester, etc. are introduced to increase the crosslinking density and the rigidity of the system. However, the CTE reduction of the resin materials obtained by such methods is limited, and the cost is relatively high. Since the CTE of inorganic fillers is one order of magnitude lower than that of organic resins, introducing inorganic fillers with a low expansion rate has become the most effective means to reduce the overall CTE of the resin.

[0005] CN103333459A discloses a resin composition with low cost and low thermal expansion. It uses biphenyl-type and anthracene-type polyfunctional epoxy resins, is compounded with cresol novolac resin, and introduces 55% by weight of silica filler. The coefficient of linear expansion of the board made of 7628 glass cloth can reach 12.5 ppm / °C. However, if thin 2116 glass cloth is used for reinforcement instead, since its glass fibers are finer than those of 7628, with lower modulus and less rigidity, the coefficient of linear expansion of the board made will greatly exceed the level of 13 ppm / °C. In addition, its resin system does not contain flame retardant components, making it difficult to meet the requirements of electronic products for low thermal expansion and flame retardancy.

[0006] In order to meet the requirement of CTE less than 13 ppm / °C, it is obvious that a higher amount of inorganic filler needs to be introduced into the organic resin system. However, as the use of inorganic filler increases, especially when the filler amount is much higher than the resin amount, the viscosity of the resin system becomes very high, making it difficult to press the prepreg into a plate. The interlayer adhesion of the board made is significantly reduced, and the high filler amount also significantly increases the difficulty of drilling. Therefore, how to obtain a resin material with both low coefficient of thermal expansion, high interlayer adhesion and excellent drillability to meet the usage requirements in PCB substrates is an urgent problem to be solved in this field. Summary of the Invention

[0007] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a resin composition, a metal-clad laminate containing the same and its applications. Through the design of spherical composite silica powder and its compounding with epoxy resin, reactive phosphorus-containing flame retardant and curing agent in specific amounts, the resin composition and the metal-clad laminate containing the same achieve halogen-free flame retardancy, high glass transition temperature and low coefficient of linear thermal expansion, and have the characteristics of excellent interlayer adhesion and drillability.

[0008] To achieve this purpose, the present invention adopts the following technical solutions:

[0009] In the first aspect, the present invention provides a resin composition. Based on 100 parts by total mass of the organic resin, the resin composition includes the following components in parts by mass:

[0010]

[0011] The mass percentage content of silica in the spherical composite silica powder is 50 - 70%, and the D 50 particle size ≤ 5 μm.

[0012] The resin composition provided by the present invention includes a high filling amount of spherical composite silica powder, which is spherical in shape, D 50The particle size is ≤5 μm, and it contains 50-70% by mass of silicon dioxide. On the one hand, its hardness is relatively low, and combined with the spherical morphology, it can significantly reduce the thermal expansion coefficient of the resin composition and the board. On the other hand, the spherical composite silica powder can endow the resin composition and the board with excellent dielectric properties, while making the resin composition and its sizing agent have good fluidity, good formability for preparing prepregs and metal-clad laminates, and little wear of the filler on drilling processing, enabling the board to have excellent drilling processability. The present invention designs and screens specific spherical composite silica powder, and compound it with epoxy resin, reactive phosphorus-containing flame retardant, and curing agent in specific dosages, so that the resin composition and the metal-clad laminate containing it have the characteristics of halogen-free flame retardancy, high glass transition temperature and low linear thermal expansion coefficient, while having excellent interlayer adhesion and drilling processability, fully meeting the use requirements of high-performance PCB substrates.

[0013] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the purpose and beneficial effects of the present invention can be better achieved and realized.

[0014] In the present invention, based on 100 parts by mass of the total mass of the organic resin, the mass parts of the epoxy resin are 30-60 parts, for example, it can be 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts or 58 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the above range.

[0015] In the present invention, the "total mass of the organic resin" refers to the total mass (excluding solvents) of the epoxy resin, reactive phosphorus-containing flame retardant, curing agent and optionally hydroxy-terminated polysulfone (if any). When the same description is involved below, it has the same meaning.

[0016] In the present invention, based on 100 parts by mass of the total mass of the organic resin, the mass parts of the reactive phosphorus-containing flame retardant are 15-30 parts, for example, it can be 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts or 29 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the above range.

[0017] In the present invention, the reactive phosphorus-containing flame retardant has the functions of flame retardancy and assisting crosslinking. Based on 100 parts by mass of the total mass of the organic resin, its mass is 15-30 parts; if its dosage is too small, the flame retardant performance will decline; if its dosage is too large, the adhesiveness of the system will decline.

[0018] In the present invention, based on 100 parts by mass of the total mass of the organic resin, the mass parts of the curing agent are 3 - 15 parts. For example, it can be 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts or 14 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0019] In the present invention, the curing agent refers to other curing agents except for the reactive phosphorus-containing flame retardant, which undergoes a curing reaction with the epoxy resin to form a crosslinked structure in the resin system. Based on 100 parts by mass of the total mass of the organic resin, the mass of the curing agent is 3 - 15 parts; if its dosage is too small, the curing degree of the resin system will be insufficient, and the T of the resin composition and the board g will be too low; if its dosage is too high, the rigidity of the board will increase, the drilling wear will increase, and the drilling processability will be affected.

[0020] In the present invention, based on 100 parts by mass of the total mass of the organic resin, the mass parts of the spherical composite silica powder are 180 - 300 parts. For example, it can be 190 parts, 200 parts, 220 parts, 240 parts, 250 parts, 260 parts or 280 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0021] The present invention adopts a high-fill system. Based on 100 parts by mass of the total mass of the organic resin, the mass of the spherical composite silica powder is 180 - 300 parts; if its dosage is too small, the coefficient of thermal expansion CTE of the resin composition and the board containing it will be too large; if its dosage is too high, the adhesion of the board will decrease and the drilling wear will be large.

[0022] In the present invention, the mass percentage content of silicon dioxide in the spherical composite silica powder is 50 - 70%, for example, it can be 52%, 54%, 55%, 56%, 58%, 60%, 62%, 64%, 65%, 66% or 68%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range; thereby, the resin composition and the board containing the spherical composite silica powder have excellent dielectric properties, appropriate hardness and excellent drilling processability. If the content of silicon dioxide in the spherical composite silica powder is too low, its dielectric constant will increase, affecting the electrical properties of the resin composition and the board; if the content of silicon dioxide is too high, its hardness will increase significantly, resulting in poor drilling processability of the fabricated board.

[0023] In addition, the D of the spherical composite silica powder 50The particle size is ≤5 μm, which makes the resin composition (adhesive solution) containing it have good fluidity, good formability for preparing prepregs and metal-clad laminates, and avoids defects such as voids. If its particle size is too large, it will lead to a decrease in the fluidity of the resin system, poor formability when making prepregs and metal-clad laminates, easy generation of voids, and increased drilling wear.

[0024] In the present invention, the epoxy resin is a polyfunctional epoxy resin containing at least 2 (such as 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.) epoxy groups in the molecule.

[0025] Exemplarily, the epoxy resin includes any one or a combination of at least two of linear phenolic epoxy resin, cresol phenolic epoxy resin, bisphenol A type phenolic epoxy resin, trifunctional phenolic epoxy resin, tetrafunctional phenolic epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, naphthol phenolic epoxy resin, anthracene type epoxy resin, phenolphthalein type epoxy resin, phenoxy type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, dicyclopentadiene phenolic epoxy resin, aralkyl type epoxy resin, aralkyl phenolic epoxy resin, epoxy resin containing an arylene ether structure in the molecule, alicyclic epoxy resin, polyol type epoxy resin, silicon-containing epoxy resin, nitrogen-containing epoxy resin, phosphorus-containing epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin.

[0026] Preferably, the epoxy resin includes a polyfunctional epoxy resin containing an aromatic ring and / or a heteroaromatic ring.

[0027] Preferably, the aromatic ring includes at least one of a benzene ring, a naphthalene ring, and an anthracene ring.

[0028] In order to improve the heat resistance and thermal expansion characteristics of the resin composition and reduce the coefficient of thermal expansion, the epoxy resin further preferably includes any one or a combination of at least two of linear phenolic epoxy resin, cresol phenolic epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, naphthol phenolic epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, aralkyl phenolic epoxy resin, dicyclopentadiene type epoxy resin, dicyclopentadiene phenolic epoxy resin, epoxy resin containing an arylene ether structure in the molecule.

[0029] Preferably, the epoxy equivalent of the epoxy resin is 150-500 g / eq, for example, it can be 180 g / eq, 200 g / eq, 220 g / eq, 250 g / eq, 280 g / eq, 300 g / eq, 320 g / eq, 350 g / eq, 380 g / eq, 400 g / eq, 450 g / eq or 480 g / eq, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0030] Preferably, the reactive phosphorus-containing flame retardant includes phosphorus-containing phenolic resin and / or phosphorus-containing active ester.

[0031] Preferably, the phosphorus-containing phenolic resin includes the condensate of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) or diphenylphosphine oxide (DPO) with phenol and formaldehyde; exemplarily, the phosphorus-containing phenolic resin has the structure shown in Formula I:

[0032]

[0033] In Formula I, R is selected from -* represents the connection site of the group.

[0034] In Formula I, m≥0, for example, it can be 0, 1, 2, 3, 4, 5 or 6, etc.

[0035] In Formula I, n≥0, for example, it can be 0, 1, 2, 3, 4, 5 or 6, etc.

[0036] In Formula I, a, b, and c respectively represent the number of groups R, and are each independently an integer from 0 to 4, for example, it can be 0, 1, 2, 3 or 4, preferably an integer from 0 to 2; and a + b + c≥1.

[0037] Preferably, the hydroxyl equivalent of the phosphorus-containing phenolic resin is 250-450 g / eq, for example, it can be 280 g / eq, 300 g / eq, 320 g / eq, 350 g / eq, 380 g / eq, 400 g / eq or 420 g / eq, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0038] Exemplarily, the phosphorus-containing active ester has the structure shown in Formula II:

[0039]

[0040] In Formula II, n 2 ≥1, for example, it can be 1, 2, 3, 4, 5 or 6, etc., preferably 2-4.

[0041] Preferably, the ester group equivalent of the phosphorus-containing active ester is 150-400 g / eq, for example, it can be 200 g / eq, 220 g / eq, 250 g / eq, 280 g / eq, 300 g / eq, 320 g / eq, 350 g / eq or 380 g / eq, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the specific point values included in the scope of the present invention are not exhaustively listed herein.

[0042] To better achieve the purpose of flame retardancy, as a preferred technical solution of the present invention, the phosphorus content of the resin composition system is ≥1.6%; when the dosage of the reactive phosphorus-containing flame retardant is insufficient to meet the requirement of the system phosphorus content, any one or at least two combinations of phosphorus-containing epoxy, non-reactive phosphorus-containing flame retardant, and nitrogen-containing flame retardant can also be introduced to make up for it.

[0043] Exemplarily, the non-reactive phosphorus-containing flame retardant and nitrogen-containing flame retardant include any one or at least two combinations of phosphonitrile, ammonium polyphosphate, tris(2-carboxyethyl)phosphine, tris(isopropyl chloride)phosphate, trimethyl phosphate, dimethyl-methyl phosphate, resorcinol bis(dimethylphenyl)phosphate, phosphazene compound, melamine polyphosphate, melamine cyanurate, tris(2-hydroxyethyl)isocyanurate.

[0044] Preferably, the curing agent includes aromatic amine curing agent and / or benzoxazine resin.

[0045] In the present invention, the aromatic amine curing agent is a compound containing an aromatic ring and having ≥2 active primary amine groups in the molecule. Exemplarily, the aromatic amine curing agent has the structure shown in Formula III:

[0046]

[0047] In Formula III, X is selected from any one of a single bond, -CH 2 -, -O-, -S(O) 2 -, or -C(CH 3 ) 2 -.

[0048] In Formula III, R 1 , R 2 are each independently any one of C1-C3 straight-chain or branched-chain alkyl groups, such as any one of methyl, ethyl, n-propyl or isopropyl.

[0049] In Formula III, s 1 , s 2 respectively represent the number of substituents R 1 , R 2 , and are each independently selected from integers of 0-4, for example, can be 0, 1, 2, 3 or 4.

[0050] Preferably, the aromatic amine curing agent includes any one or a combination of at least two of diaminodiphenylmethane, diaminodiphenylsulfone, and diaminodiphenyl ether.

[0051] In the present invention, the benzoxazine resin is polymerized from aromatic amine, phenol, and formaldehyde.

[0052] Preferably, the benzoxazine resin includes any one or a combination of at least two of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, diamine type benzoxazine resin, phenolphthalein type benzoxazine resin, dicyclopentadiene type benzoxazine resin, and bisphenol fluorene type benzoxazine resin. Further preferably, it is any one or a combination of at least two of bisphenol F type benzoxazine resin, diamine type benzoxazine resin, phenolphthalein type benzoxazine resin, and bisphenol fluorene type benzoxazine resin.

[0053] Preferably, the resin composition further includes hydroxy-terminated polyethersulfone.

[0054] Preferably, based on 100 parts by mass of the total mass of the organic resin, the mass of the hydroxy-terminated polyethersulfone in the resin composition is ≤ 20 parts, for example, it can be 0, 1 part, 2 parts, 5 parts, 6 parts, 7 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, or 18 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range. Further preferably, it is 5 - 20 parts.

[0055] As a preferred technical solution of the present invention, the resin composition includes hydroxy-terminated polyethersulfone, which is a high heat-resistant resin with a long-chain structure containing ether bonds, sulfone groups, and benzene rings in its molecule. After crosslinking with the epoxy system, it can bring about an improvement in the toughness of the resin system, increase the adhesion between the substrate and the resin, improve the interlayer bonding force, and enhance the processing reliability of the product. Preferably, based on 100 parts by mass of the total mass of the organic resin, the resin composition includes 5 - 20 parts by mass of hydroxy-terminated polyethersulfone, which effectively exerts the effects of enhancing adhesion and toughening. If the dosage is too small, the effects of promoting adhesion and toughening are not obvious. If the dosage is too large, the glass transition temperature of the resin composition and the plate will significantly decrease.

[0056] Exemplarily, the hydroxy-terminated polyethersulfone includes a structural unit as shown in Formula IV:

[0057]

[0058] Preferably, the number-average molecular weight of the hydroxyl-terminated polyethersulfone is 10,000 - 50,000, and it can be, for example, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000 or 48,000, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0059] In the present invention, the relevant data of the molecular weight (including the weight-average molecular weight M w , number-average molecular weight M n , etc.) can be referred to the records in Standard GB / T 21863-2008, based on polystyrene calibration, and obtained by gel permeation chromatography (GPC) method.

[0060] Preferably, the hydroxyl content in the hydroxyl-terminated polyethersulfone is 50 - 500 μeq / g, and it can be, for example, 80 μeq / g, 100 μeq / g, 150 μeq / g, 200 μeq / g, 250 μeq / g, 300 μeq / g, 350 μeq / g, 400 μeq / g, 450 μeq / g or 480 μeq / g, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0061] Preferably, the spherical composite silica powder further includes any one or a combination of at least two of alumina, calcium oxide, magnesium oxide, and boron oxide.

[0062] In the present invention, the D 50 particle size of the spherical composite silica powder ≤ 5 μm, and it can be, for example, 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm or 4.8 μm, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Preferably, it is 0.1 - 5 μm, and more preferably 0.3 - 4 μm.

[0063] In the present invention, the term "D 50 particle size" means "median particle size" and "average particle size". Exemplarily, the particle size data can be obtained by using a MS3000 Malvern laser particle size analyzer.

[0064] As a preferred technical solution of the present invention, to improve the reactivity of the resin, an appropriate curing accelerator can be added to the resin composition; the curing accelerator includes any one or a combination of at least two of imidazole compounds, organic phosphines, and tertiary amines.

[0065] Preferably, the imidazole compound includes any one or a combination of at least two of 2-methylimidazole, 2-methyl-4-ethylimidazole, 2-undecylimidazole, 2-phenylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole.

[0066] Preferably, the organic phosphine includes tributylphosphine and / or triphenylphosphine.

[0067] Preferably, the tertiary amine includes benzyldimethylamine.

[0068] As a preferred technical solution of the present invention, in order to make the spherical composite silica powder disperse uniformly in the resin system, a dispersant and / or a silane coupling agent can be added to the resin composition to improve the bonding performance between the organic resin and the inorganic and reinforcing materials, so as to achieve the purpose of uniform dispersion.

[0069] Preferably, based on 100 parts by mass of the spherical composite silica powder, the mass of the dispersant and the silane coupling agent are each independently 0.1 - 2 parts, for example, it can be 0.2 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts or 1.8 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list all the specific point values included in the range. If the dosage of the dispersant and the silane coupling agent is too high, the reaction may be accelerated, affecting the storage time of the resin composition; if the dosage of the dispersant and the silane coupling agent is too small, it is difficult to achieve the effect of improving the interfacial bonding property.

[0070] A solvent can also be added to the above resin composition. The addition amount of the solvent is selected by those skilled in the art according to experience and process requirements, so that the resin composition reaches a suitable viscosity for impregnation, coating, etc. of the resin composition. Subsequently, during the drying, semi-curing or full-curing process, the solvent in the resin composition will partially or completely volatilize.

[0071] As the solvent of the present invention, there is no particular limitation. Generally, ketones such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, aromatic hydrocarbons such as toluene, xylene, mesitylene, esters such as ethyl acetate, butyl acetate, ethoxyethyl acetate, alcohols such as methanol, ethanol, butanol, ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, butyl carbitol, nitrogen-containing compounds such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone can be selected; the solvent can be used alone or in combination of two or more. Preferably, any one or a combination of at least two of toluene, xylene, mesitylene, acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone is selected.

[0072] The resin composition provided by the present invention is prepared by the following method, and the preparation method includes: mixing and uniformly dispersing each component in the resin composition to obtain the resin composition.

[0073] In a second aspect, the present invention provides a resin film, and the material of the resin film includes the resin composition as described in the first aspect.

[0074] Preferably, the resin film is prepared by coating the resin composition on a release material and drying and / or semi-curing.

[0075] In a third aspect, the present invention provides a resin-coated copper foil, and the resin-coated copper foil includes a copper foil layer and a resin layer, and the material of the resin layer includes the resin composition as described in the first aspect.

[0076] Preferably, the resin-coated copper foil is prepared by coating the resin composition on a copper foil and drying and / or semi-curing.

[0077] In a fourth aspect, the present invention provides a prepreg, and the prepreg includes a reinforcing material and the resin composition as described in the first aspect attached to the reinforcing material.

[0078] Preferably, the resin composition is attached to the reinforcing material after impregnation and drying.

[0079] Preferably, the raw material of the reinforcing material includes any one or at least two combinations of natural fibers, organic synthetic fibers, inorganic fibers, and organic fabrics; for example, glass fiber cloth, quartz glass fiber blended cloth, non-woven fabric, quartz cloth, fiber paper, wood pulp paper, etc.

[0080] Exemplarily, the preparation method of the prepreg includes: infiltrating the reinforcing material with the resin solution of the resin composition, and then drying to obtain the prepreg.

[0081] Preferably, the temperature of the drying is 100-180°C, for example, it can be 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C or 175°C, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.

[0082] Preferably, the time of the drying is 1-30 min, for example, it can be 2 min, 5 min, 8 min, 10 min, 15 min, 20 min or 25 min, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.

[0083] On the other hand, the present invention provides a laminate, which comprises at least one prepreg as described in the fourth aspect.

[0084] In a fifth aspect, the present invention provides a metal foil-clad laminate, which comprises at least one of the resin film as described in the second aspect, the resin-coated copper foil as described in the third aspect, and the prepreg as described in the fourth aspect.

[0085] Preferably, the metal foil in the metal foil-clad laminate comprises any one or a combination of at least two of copper foil, aluminum foil, nickel foil, and alloy foil, and copper foil is further preferred.

[0086] Preferably, the metal foil is copper foil, and the metal foil-clad laminate is a copper-clad laminate.

[0087] Preferably, the number of prepregs in the metal foil-clad laminate is 1-20, for example, it can be 2, 3, 5, 7, 9, 10, 11, 13, 15, 17, or 19, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the above range.

[0088] Exemplarily, the method for preparing the metal foil-clad laminate includes: laminating a metal foil on one side or both sides of a prepreg and curing to obtain the metal foil-clad laminate; or laminating at least two prepregs into a laminate, and then laminating a metal foil on one side or both sides of the laminate and curing to obtain the metal foil-clad laminate.

[0089] Preferably, the curing is carried out in a press.

[0090] Preferably, the curing temperature is 170-280 °C, for example, 180 °C, 190 °C, 200 °C, 210 °C, 220 °C, 230 °C, 240 °C, 250 °C, 260 °C, or 270 °C, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the above range, and 200-220 °C is further preferred.

[0091] Preferably, the curing pressure is 10-60 kgf / cm 2 , for example, it can be 15 kgf / cm 2 , 20 kgf / cm 2 , 25 kgf / cm 2 , 30 kgf / cm 2 , 35 kgf / cm 2 , 40 kgf / cm 2 , 45 kgf / cm 2 , 50 kgf / cm 2 or 55 kgf / cm2 , and the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the said range.

[0092] Preferably, the curing time is 60 - 300 min, such as 80 min, 100 min, 120 min, 150 min, 180 min, 200 min, 220 min, 240 min, 260 min or 280 min, and the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the said range.

[0093] In a sixth aspect, the present invention provides a printed circuit board, which comprises at least one of the resin film as described in the second aspect, the resin-coated copper foil as described in the third aspect, the prepreg as described in the fourth aspect, and the metal-clad laminate as described in the fifth aspect.

[0094] Compared with the prior art, the present invention has the following beneficial effects:

[0095] (1) In the resin composition provided by the present invention, through the mutual compounding of epoxy resin, reactive phosphorus-containing flame retardant, curing agent and highly filled spherical composite silica powder in specific amounts, on the one hand, a relatively high crosslinking density can be obtained by curing, so that the cured product has a relatively high glass transition temperature and excellent heat resistance; on the other hand, the resin system and the spherical composite silica powder with a specific silica content act together, which can significantly reduce the thermal expansion rate and reduce the wear of the filler on the drilling process, and improve the mechanical processing characteristics of the product. Based on the design of spherical composite silica powder, epoxy resin, reactive phosphorus-containing flame retardant and curing agent and their compounding in specific amounts, the resin composition and the metal-clad laminate containing it achieve halogen-free flame retardancy, high glass transition temperature and low linear thermal expansion coefficient, and have the characteristics of excellent interlayer adhesion and drilling processability, which can effectively improve the ability of the manufactured PCB to resist frequent thermal shocks and fully meet the requirements of high-density communication substrates for thermal reliability.

[0096] (2) Through the component design and further optimization of the resin composition, the present invention enables the copper clad laminate to achieve V-0 grade flame retardancy, T g ≥175 °C, X / Y-CTE ≤ 13 ppm / °C, and can further achieve X / Y-CTE < 13 ppm / °C, interlayer adhesion ≥ 0.23 N / mm, milling board length ≥ 26 m, which is a substrate material with high T g , high heat resistance, low thermal expansion coefficient, high interlayer adhesion and excellent drilling processability. Specific Embodiments

[0097] The technical solution of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0098] In the specific embodiments of the present invention, the materials for which the preparation methods are not provided are all commercially available chemicals, and the specific information is shown in the following table:

[0099]

[0100]

[0101] The resin composition, metal-clad laminate and their applications of the present invention will be described in detail below with multiple embodiments as examples, but the resin composition, metal-clad laminate and their applications are not limited to these embodiments.

[0102] Examples 1-7, Comparative Examples 1-4

[0103] A resin composition, the types and dosages of each component are shown in Table 1, and the dosage unit of each component is "parts" (parts by mass).

[0104] A prepreg and a copper-clad laminate comprising the resin composition are prepared as follows:

[0105] (1) Charge each component of the resin composition according to the formulation amounts in Table 1, add 120 parts of methyl ethyl ketone, and mechanically stir for 4 h to dissolve and cure to prepare a glue solution;

[0106] (2) Immerse 2116E-glass fiber cloth in the glue solution obtained in step (1), remove part of the liquid resin through the nip of the roller press, so that the resin on the glass fiber cloth is controlled at about 65%, and then dry the impregnated glass fiber cloth in an oven at a temperature of 145 °C for 4.5 min to prepare a prepreg with a thickness of 0.1 mm;

[0107] (3) Prepare an electrolytic copper foil with a thickness of 18 μm, stack 12 prepregs obtained in step (2), and align the four sides neatly. After covering one prepared electrolytic copper foil on each of the upper and lower surfaces of the stack, put it into a laminator and laminate it under the following conditions:

[0108] Heat up the laminator, apply full pressure when reaching 90 °C, and the full pressure is 30 kgf / cm 2 ; Continue to heat up. When reaching 120 °C, control the heating rate of the material temperature at 2 °C / min until 200 °C, and keep it for 120 min for curing to obtain the copper-clad laminate.

[0109] The performance of the copper-clad laminate is tested, and the specific method is as follows:

[0110] (1) Glass transition temperature (T g ) of the sheet material: Measured by differential scanning calorimetry (DSC) according to the DSC method specified in IPC-TM-650 2.4.25;

[0111] (2) Coefficient of thermal expansion (X / Y-CTE): Tested by thermomechanical analysis (TMA) according to the method specified in IPC-TM-650 2.4.41, and the X / Y-axis coefficient of thermal expansion in the temperature range of 50 - 125 °C is taken;

[0112] (3) Interlayer adhesion: A stripping band with a width of 3.0 mm and a depth of about 0.5 mm is milled in the center of the sample plate (longitudinal direction). Starting from one end of the stripping band, the bonding sheet layer with a 2116 bonding sheet is peeled off and fixed on the pressing device of the peel tester. A tensile force is applied in the vertical direction at a speed of 50 mm / min to cause the interlayer bonding sheet to peel off, and the interlayer adhesion is obtained by dividing the peeling force by the sample width;

[0113] (4) Milling plate length: The sample plates are stacked one by one on the milling machine. A milling cutter with a diameter of 1.5 mm is used, the spindle speed is 30000 revolutions / min, the milling speed is 15 mm / s, and the sample plate is milled until the milling cutter breaks. The total length of the broken milling cutters of three sample plates is measured;

[0114] (5) Flame retardancy: Tested and classified according to the material flammability method specified in UL-94.

[0115] The performance test data are shown in Table 1.

[0116] Table 1

[0117]

[0118]

[0119] According to the performance data in Table 1, it can be seen that through the design of highly filled spherical composite silica powder and its mutual compounding with components such as epoxy resin, reactive phosphorus-containing flame retardant, curing agent, and hydroxyl-terminated polyethersulfone, the resin composition and the metal-clad laminate containing it achieve halogen-free flame retardancy, high glass transition temperature, and low linear thermal expansion coefficient, and at the same time have excellent interlayer adhesion and drilling processability; among them, the copper-clad laminates of Examples 1 - 6 achieve V-0 grade flame retardancy, T g is 175 - 194 °C, X / Y-CTE is 11.3 - 12.9 ppm / °C, the interlayer adhesion is 0.23 - 0.35 N / mm, and the milling plate length is 26 - 44 m, which can fully meet the requirements of high-density communication substrates for thermal reliability.

[0120] According to the examples and Comparative Examples 1-4, in Comparative Example 1, spherical silica powder with a silica mass content of 99.6% was used. The high hardness of the filler led to a significant reduction in the processability of the adopted board, and the milling board length became shorter. In Comparative Example 2, angular composite silica powder with a high filling amount was used, and the processability of the resin composition could not meet the requirements for board making, making it difficult to obtain a qualified copper clad laminate. In Comparative Example 3, the amount of spherical composite silica powder used was low, resulting in a significant increase in the linear thermal expansion coefficient of the board, which could not meet the requirement of less than 13 ppm / °C. In Comparative Example 4, angular composite silica powder with a low filling amount was used, which could meet the requirements for board making, but the obtained copper clad laminate had a high thermal expansion coefficient.

[0121] The applicant declares that the resin composition of the present invention, the metal foil-clad laminate containing the same, and its applications are illustrated by the above examples. However, the present invention is not limited to the above examples, that is, it does not mean that the present invention must rely on the above examples to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of each raw material of the products of the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A resin composition, characterized in that Based on 100 parts by total weight of the organic resin, the resin composition comprises the following components by weight: The mass percentage of silicon dioxide in the spherical composite silicon micropowder is 50-70%. 50 Particle size ≤5μm.

2. The resin composition according to claim 1, characterized in that The epoxy resin includes a multifunctional epoxy resin containing an aromatic ring and / or a heteroaromatic ring; Preferably, the epoxy resin includes any one of linear phenolic epoxy resin, cresol phenolic epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, naphthol phenolic epoxy resin, biphenyl epoxy resin, arylalkyl epoxy resin, arylalkyl phenolic epoxy resin, dicyclopentadiene epoxy resin, dicyclopentadiene phenolic epoxy resin, and an epoxy resin containing a arylene ether structure in the molecule, or a combination of at least two of them.

3. The resin composition according to claim 1 or 2, characterized in that The reactive phosphorus-containing flame retardant includes phosphorus-containing phenolic resin and / or phosphorus-containing active ester; Preferably, the curing agent comprises an aromatic amine curing agent and / or a benzoxazine resin; Preferably, the aromatic amine curing agent includes any one of diaminodiphenylmethane, diaminodiphenyl sulfone, and diaminodiphenyl ether, or a combination of at least two thereof; Preferably, the benzoxazine resin includes any one of bisphenol A benzoxazine resin, bisphenol F benzoxazine resin, diamine benzoxazine resin, phenolphthalein benzoxazine resin, dicyclopentadiene benzoxazine resin, and bisphenol fluorene benzoxazine resin, or a combination of at least two thereof.

4. The resin composition according to any one of claims 1 to 3, characterized in that The resin composition also includes hydroxyl-terminated polyethersulfone; Preferably, based on 100 parts of the total mass of the organic resin, the mass of the hydroxy-terminated polyethersulfone in the resin composition is ≤20 parts, more preferably 5-20 parts; Preferably, the number average molecular weight of the hydroxy-terminated polyethersulfone is 10000-50000; Preferably, the hydroxyl content of the hydroxyl-terminated polyethersulfone is 50-500 μeq / g.

5. The resin composition according to any one of claims 1 to 4, characterized in that The spherical composite silicon powder also includes any one of aluminum oxide, calcium oxide, magnesium oxide, and boron oxide, or a combination of at least two thereof; Preferably, the D of the spherical composite silicon powder is 50 The particle size is 0.1-5 μm, more preferably 0.3-4 μm.

6. A resin film, characterized in that: The material of the resin film comprises the resin composition according to any one of claims 1 to 5.

7. A resin-coated copper foil, characterized in that: The resin-coated copper foil comprises a copper foil layer and a resin layer, and the material of the resin layer comprises the resin composition according to any one of claims 1 to 5.

8. A prepreg, characterized in that: The prepreg comprises a reinforcing material and the resin composition according to any one of claims 1 to 5 attached to the reinforcing material.

9. A metal foil-clad laminate, characterized in that: The metal foil-clad laminate includes at least one of the resin film according to claim 6 , the resin-coated copper foil according to claim 7 , and the prepreg according to claim 8 .

10. A printed circuit board, characterized in that: The printed circuit board comprises at least one of the resin film according to claim 6, the resin-coated copper foil according to claim 7, the prepreg according to claim 8, and the metal foil-clad laminate according to claim 9.

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