Resin composition, prepreg, laminate, copper clad laminate, wiring board

Abstract

The present application discloses a resin composition, a prepreg, a laminate, a copper-clad plate, and a wiring board, and belongs to the technical field of composite materials. The resin composition includes the following components by weight: 50-150 parts of a benzoxazine resin containing a double bond; 50-150 parts of a bismaleimide resin; 20-80 parts of a phosphorus silicon epoxy resin; 20-80 parts of an epoxy resin; 200-800 parts of an inorganic filler; 0-2 parts of a curing accelerator; 0-100 parts of a solvent; and the phosphorus silicon epoxy resin has a structure shown in Formula 1. The present application uses epoxy resin and phosphorus silicon epoxy resin to modify the composite system of benzoxazine resin and bismaleimide resin, and optimizes the amount of inorganic filler at the same time, which can give the composite material excellent flame retardant properties without adding a flame retardant, and at the same time improves heat resistance and mechanical properties, reduces the coefficient of thermal expansion, and can meet the application requirements of the packaging carrier.

Description

Technical Field

[0001] The present application relates to the technical field of composite materials, and in particular to a resin composition, a prepreg, a laminate, a copper clad laminate, and a wiring board. Background Art

[0002] In recent years, as semiconductors have become increasingly integrated, functional, and densely packaged, the requirements for laminates used in semiconductor packaging have become more diverse. In addition to the traditional requirements for heat resistance, chemical resistance, flame retardancy, and reliability, various properties such as low thermal expansion coefficient, high glass transition temperature, and high flexural modulus are now required.

[0003] On the other hand, with the continuous development of miniaturization and multifunctionality of electronic products and the continuous improvement of operating speed, the requirements for chip integration and chip packaging technology are getting higher and higher, and higher requirements are placed on the material properties of the substrate (i.e., laminate) that carries semiconductor components, especially the coefficient of thermal expansion (CTE). If the CTE difference between the semiconductor component and the substrate is too large, the substrate will easily warp due to the CTE difference under heating conditions, causing serious problems such as poor connection between the semiconductor component and the substrate, and between the substrate and the PCB. Therefore, the substrate material needs a lower CTE. However, achieving a lower X / Y axis CTE while maintaining a high flexural modulus is a technical challenge.

[0004] The traditional method uses high-performance resins such as maleimide resin and benzoxazine resin to meet the demand for high wiring density. Among them, bismaleimide resin is a high-performance thermosetting resin with excellent heat resistance, moisture and heat resistance, dielectric properties and good processability. It is often used to modify epoxy resin to make copper clad laminates; benzoxazine resin can generate a structure similar to phenolic resin after ring opening, effectively reducing the water absorption rate of the curing system and improving chemical resistance. It is also often used to modify epoxy resin to make copper clad laminates; epoxy resin has good compatibility with bismaleimide resin and benzoxazine resin, which can effectively improve the toughness of copper clad laminates. However, the copper clad laminate prepared by the above method has a large thermal expansion coefficient, poor heat resistance, and is prone to warping, and its performance still needs to be further improved. In addition, the current packaging substrate generally uses halogen-free flame retardants to ensure flame retardant requirements, but the addition of halogen-free flame retardants will lead to a sharp deterioration of mechanical properties and dielectric properties. Summary of the invention

[0005] Based on this, the main purpose of the present application is to provide a resin composition which has good flame retardancy, heat resistance and mechanical properties, and has a low thermal expansion coefficient, which can meet the application requirements of the packaging carrier.

[0006] In a first aspect of the present application, a resin composition is provided, comprising the following components by weight:

[0007] 50-150 parts of benzoxazine resin containing double bonds;

[0008] 50-150 parts of bismaleimide resin;

[0009] Phosphorus silicon epoxy resin 20-80 parts;

[0010] Epoxy resin 20-80 parts;

[0011] 200-800 parts of inorganic filler;

[0012] Curing accelerator 0-2 parts;

[0013] Solvent 0-100 parts;

[0014] The phosphorus silicon epoxy resin has a structure shown in Formula 1:

[0015] Formula 1;

[0016] Among them, R 1 , R 2 , R 3 and R 4 Each is independently selected from C1-C12 alkyl, C2-C12 alkenyl, aryl, substituted aryl and aryl-substituted C1-C5 alkyl; the substituted aryl contains 1-2 substituents, and the substituents are C1-C5 alkyl; n represents an integer of 0-2; m represents an integer of 1-3.

[0017] In some embodiments, the aryl group is phenyl, naphthyl, or biphenyl;

[0018] and / or the aryl group in the substituted aryl group is phenyl, naphthyl or biphenyl; and / or the aryl group in the C1-C5 alkyl group substituted by the aryl group is phenyl, naphthyl or biphenyl.

[0019] In some embodiments, the epoxy resin is a novolac epoxy resin.

[0020] In some embodiments, the epoxy novolac resin includes an o-methyl epoxy novolac resin and / or a naphthalene epoxy novolac resin.

[0021] In some embodiments, the softening point of the novolac epoxy resin is 80-95°C.

[0022] In some embodiments, the benzoxazine resin containing a double bond is a benzoxazine resin containing a double bond at a terminal end.

[0023] In some embodiments, the double bond-containing benzoxazine resin includes at least one of a BPA-type benzoxazine resin, a BPF-type benzoxazine resin, an ODA-type benzoxazine resin, and a BPS-type benzoxazine resin.

[0024] In some embodiments, the bismaleimide resin includes at least one of 4,4'-diphenylmethane bismaleimide, N-2,6-dimethylphenyl maleimide, N-(2,3-dimethylphenyl) maleimide, N-phenyl maleimide, 1,6-dimaleimidohexane, N,N-(4-methyl-1,3-phenylene) bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide, N'-m-phenylene bismaleimide, diphenylmethane maleimide, biphenyl type bismaleimide resin, polyphenylmethane maleimide and bis(3-ethyl-5-methyl-4-maleimidophenyl) methane.

[0025] In some embodiments, the inorganic filler includes a metal salt and / or a metal hydroxide;

[0026] In some embodiments, the average particle size of the inorganic filler is 0.1-10 μm.

[0027] In some embodiments, the curing accelerator includes at least one of an imidazole curing accelerator, an amine curing accelerator, an organic metal salt, an inorganic metal salt, an organic peroxide, and an azo compound.

[0028] In some embodiments, the solvent includes at least one of methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide and propylene glycol methyl ether.

[0029] In some embodiments, the resin composition further comprises one or more of phenolic resin, acid anhydride, benzoxazine resin without double bonds, rubber and modified polytetrafluoroethylene.

[0030] The second aspect of the present application provides a prepreg, the raw materials of which include the resin composition and reinforcing material described in the first aspect.

[0031] The third aspect of the present application provides a laminate comprising the resin composition described in the first aspect or the prepreg described in the second aspect.

[0032] A fourth aspect of the present application provides a copper clad laminate comprising the resin composition described in the first aspect or the prepreg described in the second aspect.

[0033] The fifth aspect of the present application provides a wiring board, comprising the resin composition of the first aspect, the prepreg of the second aspect, the laminate of the third aspect or the copper clad board of the fourth aspect.

[0034] The beneficial effects of this application are:

[0035] 1. Epoxy resin has low dielectric loss and good compatibility with benzoxazine resin and bismaleimide resin, while the phosphorus silicon epoxy resin shown in Formula 1 has excellent flame retardant properties. At the same time, because it contains rigid structures such as benzene rings and biphenyls, Si-O-Si segments and epoxy groups, it has a high glass transition temperature, a low thermal expansion coefficient and good compatibility with. This application uses epoxy resin and phosphorus silicon epoxy resin to modify the benzoxazine resin and bismaleimide resin composite system, and optimizes the amount of inorganic filler, which can give the composite material excellent flame retardant properties without adding flame retardants, and at the same time improves heat resistance and mechanical properties, reduces thermal expansion coefficient, and can meet the application requirements of packaging carriers.

[0036] 2. The resin composition of the present application has good solubility and compatibility, and has obvious advantages in glass transition temperature. The laminate prepared by using it has a lower X / Y axis CTE, good flame retardancy, and can be used for semiconductor packaging substrates. DETAILED DESCRIPTION

[0037] In order to facilitate the understanding of the present application, the present application will be described more comprehensively below in conjunction with specific embodiments. Preferred embodiments of the present application are provided hereinafter. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0038] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0039] In this article, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0040] In this article, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the quantity of the indicated technical features.

[0041] In the description herein, "at least one" means more than one, including one, two, three, etc.; "plurality" means more than two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0042] Herein, when it comes to numerical ranges, unless otherwise specified, the numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0043] In this article, when referring to the unit of a data range, if there is a unit only after the right endpoint, it means that the units of the left and right endpoints are the same. For example, 500-600rpm means that the units of the left endpoint "500" and the right endpoint "600" are both rpm (revolutions per minute).

[0044] The temperature parameters herein, unless otherwise specified, allow for both constant temperature treatment and treatment within a certain temperature range. The constant temperature treatment allows for temperature fluctuations within the precision range of instrument control.

[0045] In this article, "optional", "preferable" and "preferred" refer to embodiments of the present application that can provide certain beneficial effects in certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not applicable, nor is it intended to exclude other embodiments from the scope of this application.

[0046] In the present application, when it comes to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​in the numerical interval is considered to be continuous, and includes the two numerical endpoints (i.e., the minimum value and the maximum value) of the numerical interval, and each numerical value between the two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to the integers in the numerical interval, it includes the two endpoint integers of the numerical range, and each integer between the two endpoints, which is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical range disclosed herein should be understood to include any and all sub-ranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. "Numerical interval" allows broadly including numerical interval types such as percentage intervals, ratio intervals, and ratio intervals.

[0047] In the present application, in the expression of carbon number, i.e., the number after the capital letter "C", such as "C1-C12", "C1-C4", etc., the number after "C", such as "1", "4" or "12", represents the number of carbons in the specific functional group. That is, the functional group may include 1-12 carbon atoms and 1-4 carbon atoms, respectively. For example, "C1-C12 alkyl" refers to an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms. Suitable examples include, but are not limited to, methyl (Me, -CH 3 ), ethyl (Et, -CH 2 CH 3 ), 1-propyl (n-Pr, n-propyl, -CH 2 CH 2 CH 3 ), 2-propyl (i-Pr, i-propyl, -CH (CH 3 ) 2 ), 1-butyl (n-Bu, n-butyl, -CH 2 CH 2 CH 2 CH 3 ), 2-methyl-1-propyl (i-Bu, i-butyl, -CH 2 CH(CH 3 ) 2 ), 2-butyl (s-Bu, s-butyl, -CH (CH 3 )CH 2 CH 3 ), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH 3 ) 3 ), 1-pentyl (n-pentyl, -CH 2 CH 2 CH 2 CH 2 CH 3 ), 2-pentyl (-CH(CH 3 )CH 2 CH 2 CH 3 ), 3-pentyl (-CH(CH 2 CH 3 ) 2 ), 2-methyl-2-butyl (-C(CH 3 ) 2 CH 2 CH 3 ), 3-methyl-2-butyl (-CH(CH 3 )CH(CH 3 ) 2 ), 3-methyl-1-butyl (-CH 2 CH2 CH(CH 3 ) 2 ) and 2-methyl-1-butyl (-CH 2 CH(CH 3 )CH 2 CH 3 )、1-hexyl (-CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ), 2-hexyl (-CH(CH 3 )CH 2 CH 2 CH 2 CH 3 ), 3-hexyl (-CH(CH 2 CH 3 )(CH 2 CH 2 CH 3 ))、2-methyl-2-pentyl (-C(CH 3 ) 2 CH 2 CH 2 CH 3 ), 3-methyl-2-pentyl (-CH(CH 3 )CH(CH 3 )CH 2 CH 3 ), 4-methyl-2-pentyl (-CH(CH 3 )CH 2 CH(CH 3 ) 2 ), 3-methyl-3-pentyl (-C(CH 3 )(CH 2 CH 3 ) 2 ), 2-methyl-3-pentyl (-CH(CH 2 CH 3 )CH(CH 3 ) 2 )、2,3-dimethyl-2-butyl (-C(CH 3 ) 2 CH(CH 3 ) 2 )、3,3-dimethyl-2-butyl (-CH(CH 3 )C(CH 3 ) 3 .

[0048] In the present application, "C1-C12 alkyl" is expected to be a straight chain saturated hydrocarbon structure with 1-12 carbon atoms or a branched or cyclic hydrocarbon structure with 3-12 carbon atoms. When specifying an alkyl with a specific carbon number, it is expected to cover all geometric isomers with this carbon number. Therefore, for example, "butyl" means to include normal-butyl, sec-butyl, isobutyl, the tert-butyl and cyclobutyl. "propyl" means to include normal-propyl, isopropyl and cyclopropyl. C1-C12 alkyl includes, but is not limited to methyl, ethyl, normal-propyl, isopropyl, cyclopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl, cyclobutyl, normal-pentyl, isopentyl, neopentyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, normal-hexyl, isohexyl, cyclohexyl, normal-heptyl, octyl, nonyl, decyl, cyclopropyl, cyclobutyl, norbornyl etc. In addition, alkyl can be optionally substituted.

[0049] In one aspect of the present application, a resin composition is provided, comprising the following components in parts by weight:

[0050] 50-150 parts of benzoxazine resin containing double bonds;

[0051] 50-150 parts of bismaleimide resin;

[0052] Phosphorus silicon epoxy resin 20-80 parts;

[0053] Epoxy resin 20-80 parts;

[0054] 200-800 parts of inorganic filler;

[0055] Curing accelerator 0-2 parts;

[0056] Solvent 0-100 parts;

[0057] The phosphorus silicon epoxy resin has a structure shown in Formula 1:

[0058] Formula 1;

[0059] Among them, R 1 , R 2 , R 3 and R 4 Each is independently selected from C1-C12 alkyl, C2-C12 alkenyl, aryl, substituted aryl and aryl-substituted C1-C5 alkyl; the substituted aryl contains 1-2 substituents, and the substituents are C1-C5 alkyl; n represents an integer of 0-2; m represents an integer of 1-3.

[0060] Epoxy resin has low dielectric loss and good compatibility with benzoxazine resin and bismaleimide resin, while the phosphorus silicon epoxy resin shown in Formula 1 has excellent flame retardant properties. At the same time, because it contains rigid structures such as benzene rings and biphenyls, Si-O-Si segments and epoxy groups, it has a high glass transition temperature, a low thermal expansion coefficient and good compatibility with. The present application uses epoxy resin and phosphorus silicon epoxy resin to modify the benzoxazine resin and bismaleimide resin composite system, which can give the composite material excellent flame retardant properties without adding flame retardants, and at the same time improve heat resistance and mechanical properties, reduce thermal expansion coefficient, and meet the application requirements of packaging carriers.

[0061] In a specific example, the C1-C12 alkyl group is an alkyl group containing 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, including but not limited to methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, octyl, nonyl, decyl, cyclopropyl, cyclobutyl, norbornyl, 2-ethylhexyl, and the like.

[0062] In a specific example, the C2-C12 alkenyl group is an alkenyl group containing 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, including but not limited to ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, isopentenyl, etc.

[0063] In a specific example, the aryl group is phenyl, naphthyl or biphenyl;

[0064] In a specific example, the aryl group in the substituted aryl group is phenyl, naphthyl or biphenyl; and / or the aryl group in the C1-C5 alkyl group substituted by the aryl group is phenyl, naphthyl or biphenyl.

[0065] In a specific example, the substituted aryl group is an aryl group monosubstituted or disubstituted by an alkyl group having 1, 2, 3, 4 or 5 carbon atoms, such as tolyl, xylyl and the like.

[0066] In a specific example, the aryl-substituted C1-C5 alkyl group is an alkylene group containing 1, 2, 3, 4 or 5 carbon atoms substituted by an aryl group, such as benzyl, phenethyl, and the like.

[0067] In a specific example, R 1 , R 2 , R 3 and R 4 Each is independently selected from methyl, ethyl, phenyl or benzyl, more preferably methyl or phenyl, further preferably methyl.

[0068] In a specific example, n can be 0, 1 or 2; preferably, n is 0-1, and more preferably n is 0 for compatibility considerations.

[0069] In a specific example, m may be 0, 1, 2 or 3; preferably, m is 1-2, and m is more preferably 1 for consideration of resin wettability.

[0070] There is no special requirement for the specific type of epoxy resin. In some embodiments, the epoxy resin is a phenolic epoxy resin; the phenolic epoxy resin includes an o-methyl phenolic epoxy resin and / or a naphthalene phenolic epoxy resin. The above phenolic epoxy resins can be added to the resin composition of the present application alone or in combination.

[0071] It is understandable that the phenolic epoxy resin has a high crosslinking density after curing and has good mechanical properties. The o-methyl phenolic epoxy resin and the naphthalene phenolic epoxy resin have good flame retardancy and excellent electrical properties, so they are more preferred. The structures of the o-methyl phenolic epoxy resin and the naphthalene phenolic epoxy resin are shown in Formula 2 and Formula 3:

[0072] Formula 2;

[0073] Formula 3.

[0074] It is understandable that the softening point of the phenolic epoxy resin is not particularly limited. In some embodiments, the softening point of the phenolic epoxy resin is 80-95°C. The softening point of the phenolic epoxy resin shown in Formula 2 can be 85-95°C, and the softening point of the phenolic epoxy resin shown in Formula 3 can be 83-93°C. It should be noted that the softening point can be a value obtained by measuring the softening point using a conventional softening point measuring method, such as a value measured using a softening point measuring instrument. The basic principle is to heat the glycerol bath at a specified speed under the action of a steel ball to a temperature when the steel ball falls 25 mm.

[0075] In some embodiments, the benzoxazine resin containing double bonds is a benzoxazine resin containing double bonds at the end groups, and the end groups are not particularly limited, and may contain double bonds (C=C), including but not limited to allyl, methacrylate, polybutadiene, etc. The benzoxazine resin containing double bonds includes at least one of BPA type benzoxazine resin, BPF type benzoxazine resin, ODA type benzoxazine resin, and BPS type benzoxazine resin.

[0076] The double bond-containing benzoxazine resin may be an allyl-modified BPA-type benzoxazine resin, and the allyl-modified BPA-type benzoxazine resin may include at least one of the benzoxazine resins having structures shown in Formula 4 to Formula 6:

[0077]

[0078] Formula 4 Formula 5

[0079]

[0080] Formula 6.

[0081] The bismaleimide resin is a compound, monomer, mixture, oligomer or polymer having one or more maleimide functional groups in the molecule. Unless otherwise specified, the bismaleimide resin used in the present application is not particularly limited, and can be any one or more maleimide resins suitable for making prepregs, prepregs with copper foil, resin films, resin films with copper foil, laminates or printed circuit boards. In some embodiments, the bismaleimide resin includes at least one of 4,4'-diphenylmethane bismaleimide, N-2,6-dimethylphenyl maleimide, N-(2,3-dimethylphenyl) maleimide, N-phenyl maleimide, 1,6-dimaleimidohexane, N,N-(4-methyl-1,3-phenylene) bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide, N'-m-phenylene bismaleimide, diphenylmethane maleimide, biphenyl type bismaleimide resin, polyphenylmethane maleimide and bis(3-ethyl-5-methyl-4-maleimidophenyl) methane.

[0082] As a specific example, the bismaleimide resin may be a bismaleimide resin produced by Daiwakasei, with trade names such as BMI-70, BMI-80, BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000H, BMI-5000, BMI-5100, BMI-7000 and BMI-7000H.

[0083] Among them, the molecular structures of BMI-2300 and BMI-5100 are shown in Formula 7 and Formula 8:

[0084]

[0085] Formula 7 Formula 8

[0086] As a product example, the bismaleimide resin may be MIR-3000 manufactured by Nippon Kayaku Co., Ltd. MIR-3000 has excellent flame retardancy in the cured product due to its biphenyl structure. At the same time, due to its phenolic varnish-like structure and many cross-linking points, the glass transition temperature of the cured product can be effectively increased. The molecular structure of MIR-3000 is shown in Formula 9:

[0087]

[0088] Formula 9.

[0089] The type of the inorganic filler is not particularly limited, and its function is to fill the resin composition and improve the heat resistance and flame retardancy of the cured product of the resin composition. In some embodiments, the inorganic filler includes metal salts and metal hydroxides; specifically, the metal salt includes at least one of silica, alumina, titanium oxide and mica, aluminum hydroxide, magnesium hydroxide, talc, aluminum borate, barium sulfate and calcium carbonate. The inorganic filler may be spherical, fibrous, plate-like, granular, flaky or needle-like. The filling material can be used alone or in combination of two or more; it can be used directly or after surface treatment with a silane coupling agent. As the inorganic filler, silica, mica and talc are preferred, and spherical silica is more preferred.

[0090] There is no special requirement for the average particle size of the inorganic filler. In some embodiments, the average particle size of the inorganic filler is 0.1-10 μm, preferably 0.3-8 μm. By setting the average particle size to be above 0.1 μm, good fluidity can be maintained when highly filled in the resin, and by further setting it to be below 10 μm, the probability of mixing with coarse particles can be reduced, avoiding the occurrence of defects caused by coarse particles. Here, the average particle size refers to the particle size equivalent to the point of exactly 50% of the volume when the cumulative particle size distribution curve is calculated with the entire volume of the particle as 100%, which can be measured by laser diffraction scattering method.

[0091] The curing accelerator is not particularly limited, and the curing accelerator can promote the curing reaction of the resin. In some embodiments, the curing accelerator includes at least one of an imidazole curing accelerator, an amine curing accelerator, an organic metal salt, an inorganic metal salt, an organic peroxide, and an azo compound. Specifically, the imidazole curing accelerator can be triphenylimidazole; the amine curing accelerator can include at least one of 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutylene diamine, and N-methylpiperidine; the organic metal salt can include at least one of lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate, alkyl tin, and alkyl tin oxide; the inorganic metal salt can include at least one of tin chloride, zinc chloride, and aluminum chloride. The curing accelerator can be used alone or in combination of two or more. Triphenylimidazole is advantageous in promoting the curing reaction, improving the glass transition temperature and thermal expansion coefficient, and is more preferred.

[0092] The solvent is not particularly limited. In the present application, the main function of adding a solvent is to change the solid content of the resin composition and adjust the viscosity of the resin composition. If not specifically specified, the solvent used in the present application is not particularly limited, and may be any one or more solvents suitable for dissolving or diluting the aforementioned resin composition. In some embodiments, the solvent includes at least one of methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide and propylene glycol methyl ether.

[0093] The resin composition may further include other functional resins, such as one or more of phenolic resin, acid anhydride, benzoxazine resin without double bonds, rubber and modified polytetrafluoroethylene.

[0094] In a specific example, the method for preparing the resin composition comprises the following steps:

[0095] The bismaleimide resin, the benzoxazine resin containing double bonds, the phosphorus silicon epoxy resin, the epoxy resin and the solvent are mixed, and an inorganic filler and a curing accelerator are added to disperse and prepare the resin composition.

[0096] It is understandable that the dispersion can be achieved by a ball mill, a bead mill, a planetary mixer, a roller mill, etc., and stirred for a sufficient time to disperse to a uniform state.

[0097] The second aspect of the present application provides a prepreg, the raw materials of which include the resin composition and reinforcing material described in the first aspect.

[0098] In a specific example, the method for preparing the prepreg comprises the following steps:

[0099] The resin composition is impregnated into a reinforcing material and heated to prepare a prepreg.

[0100] It is understandable that the impregnation can be carried out by impregnation or coating, and the impregnation can be repeated multiple times as needed. In addition, multiple resin compositions with different compositions can be used for repeated impregnation to adjust the final desired composition and glue content. By heating the reinforcing material impregnated with the resin composition under desired heating conditions, such as 80-200°C for 1-20 minutes, a semi-cured prepreg, i.e., a semi-cured sheet, can be obtained. The heating conditions are preferably: temperature 110-190°C, time 2-10 minutes.

[0101] The reinforcing material is a well-known inorganic or organic fiber material, and the inorganic fiber reinforcing material includes but is not limited to at least one of glass fiber cloth (including different types such as E, NE, D, S, T, etc.), carbon fiber, silicon carbide fiber and asbestos fiber. The organic fiber reinforced substrate includes but is not limited to at least one of nylon, ultra-high molecular weight polyethylene fiber, aramid fiber, polyimide fiber, polyester fiber and cotton fiber. It should be noted that if glass fiber cloth is used, a laminate with excellent mechanical strength can be obtained, and glass cloth that has been flattened is more preferred. Flattening processing is to continuously apply appropriate pressure to the glass cloth through a pressure roller to compress the yarn into a flat shape.

[0102] The third aspect of the present application provides a laminate comprising the resin composition described in the first aspect or the prepreg described in the second aspect.

[0103] In a specific example, the method for preparing the laminate comprises: laminating at least one of the prepregs to prepare the laminate. The lamination conditions include: a temperature of 150-250°C, a pressure of 10-40 kgf / cm 2 , vacuum degree <2kPa, hot pressing 60-180min.

[0104] A fourth aspect of the present application provides a copper clad laminate comprising the resin composition described in the first aspect or the prepreg described in the second aspect.

[0105] In a specific example, the method for preparing the copper clad laminate comprises: stacking at least one of the prepregs, placing copper foil on both sides, and laminating several of the prepregs, i.e., one side or both sides of the laminate, to form a laminate to prepare the copper clad laminate. The thickness of the metal copper foil is 3μm-105μm.

[0106] The fifth aspect of the present application provides a wiring board, comprising the resin composition of the first aspect, the prepreg of the second aspect, the laminate of the third aspect or the copper clad board of the fourth aspect.

[0107] It is worth noting that the raw materials used in the examples of the present application are all common commercially available products, and their sources are not specifically limited.

[0108] The sources of some components in the embodiments and comparative examples are as follows:

[0109] 1. Phosphorus silicon epoxy resin:

[0110] CE1900, phosphorus silicon epoxy resin, EEW=1600, P%=2.0%, manufactured by Keyi Company;

[0111] 2. Epoxy resin:

[0112] 704, o-methylphenolic epoxy resin, softening point 85-95°C, manufactured by Nan Ya Company;

[0113] NC-7000L, naphthalene-type phenolic epoxy resin, softening point 83-93°C, manufactured by Nippon Kayaku Co., Ltd.

[0114] 3. Double bond benzoxazine resin:

[0115] KZH-5031, allyl benzoxazine, manufactured by Kolon;

[0116] LZ-32, double-bond modified benzoxazine, manufactured by Huaibei Oasis Company;

[0117] 4. Bismaleimide resin:

[0118] BMI-2300, polyphenylmethane maleimide, manufactured by Yamato Chemical Co., Ltd., Japan;

[0119] BMI-5100, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, manufactured by Yamato Chemical Co., Ltd., Japan;

[0120] MIR-3000, biphenyl bismaleimide, manufactured by Nippon Kayaku Co., Ltd.;

[0121] 5. Inorganic fillers:

[0122] SC2050-MTX, double bond treated spherical silica slurry, manufactured by Admatechs;

[0123] 6. Curing accelerator:

[0124] 2,4,5-Triphenylimidazole, manufactured by Tokyo Chemical Industry Co., Ltd.

[0125] The following are specific embodiments.

[0126] Examples 1-6 and Comparative Examples 1-4

[0127] The formulas of the resin compositions of Examples 1-6 and Comparative Examples 1-4 are shown in Table 1. The preparation method of the resin compositions is as follows:

[0128] First, bismaleimide resin is mixed with acetone, and the mixture is heated to 60°C and stirred thoroughly to fully dissolve the bismaleimide resin in acetone to obtain an acetone solution with a solid content of 40% by mass. Then, phosphorus silicon epoxy resin, epoxy resin, and double bond benzoxazine resin are added thereto, and stirred for 2 hours to fully dissolve them. Finally, inorganic fillers and curing accelerators are further added, and an appropriate amount of acetone is added again to adjust the viscosity to 10s (Zahn cup measurement), and a bead mill is used to fully disperse it to obtain a resin composition.

[0129] Preparation method of prepreg:

[0130] The resin compositions prepared in the various embodiments and comparative examples were immersed in glass fiber cloth (2116 cloth produced by Honghe Company) and baked at 100-180° C. for about 2-8 minutes to obtain a semi-cured sheet with a mass ratio of 50%.

[0131] The preparation method of copper clad laminate is as follows:

[0132] Eight prepregs prepared in each embodiment and comparative example were stacked, and 35 μm copper foil was placed on both sides. 2 Under vacuum conditions, high temperature and high pressure pressing for 2 hours, a copper clad laminate with a thickness of about 0.8 mm was obtained.

[0133] Test Case

[0134] The copper clad laminates of each embodiment and comparative example were tested for performance, and the results are shown in Table 1. The specific testing methods are as follows:

[0135] 1. Peel strength: Tested using a universal tensile testing machine in accordance with IPC-TM-650 2.4.8.

[0136] 2. Glass transition temperature (Tg): The glass transition temperature (Tg) was measured using a dynamic mechanical analyzer (DMA850 manufactured by TA Instruments) at a heating rate of 3°C / min.

[0137] 3. Dielectric constant and dielectric loss measurement: Agilent E5071C network analyzer was used to measure the dielectric constant (Dk) and dielectric loss (Df) at an operating frequency of 10 MHz according to IPC-TM-650 2.5.5.13.

[0138] 4. 288℃ solder resistance heat resistance test: Immerse the test piece that has been steamed in a PCT pressure cooker for 2 hours in a 288℃ solder furnace for 6 minutes, and record whether the test piece explodes.

[0139] 5. Test of thermal expansion coefficient in X / Y axis direction: Measured by TA instrument company's TA Q800 thermal expansion analyzer, with the measuring temperature of 50℃-260℃ and the heating rate of 10℃ / min, and test the thermal expansion coefficient of the sample in the X / Y axis direction (before Tg).

[0140] 6. Flame retardant test: Refer to UL-94 specification, use Bunsen burner, methane gas and ammeter to test the time it takes for the sample to automatically extinguish after burning, and determine the grade based on this time.

[0141] 7. Elastic modulus: According to GB / T 22315-2008, the elastic modulus is tested using a universal tensile machine.

[0142] Table 1 Summary of formulations and properties of examples and comparative examples

[0143]

[0144] It can be seen from Table 1 that when the resin composition of Examples 1-6 is used, a halogen-free copper clad laminate having a high glass transition temperature (Tg ≥ 300°C), a high flexural modulus (elastic modulus ≥ 30 GPa), a high peel strength (peel strength ≥ 8 lb / in), excellent dielectric properties (Df ≤ 0.0090 at 10 GHz) and a low XY linear expansion coefficient (≤ 9.0 ppm / °C) can be obtained.

[0145] In addition, the resin compositions in Comparative Examples 1 and 3 do not use phosphorus silicon epoxy resin, the glass transition temperature of the cured product cannot reach above 270°C, and the XY linear expansion coefficient is difficult to drop below 12ppm / °C; in Comparative Example 4, phosphorus silicon epoxy resin is used entirely, and no epoxy resin is used, and the dielectric property Df of the cured product is significantly degraded; in Comparative Example 2, the filler ratio of the resin composition is insufficient, the elastic modulus of the cured product is low, and the XY linear expansion coefficient becomes larger. It can be seen that in the composite system of benzoxazine resin and bismaleimide resin, the composite use of epoxy resin and phosphorus silicon epoxy resin can obtain the ideal comprehensive performance.

[0146] In summary, the present application uses epoxy resin and phosphorus silicon epoxy resin to modify the benzoxazine resin and bismaleimide resin composite system, and optimizes the dosage of inorganic filler, which can give the composite material excellent flame retardant properties without adding flame retardants, and at the same time improve the heat resistance and mechanical properties, reduce the thermal expansion coefficient, and meet the application requirements of the packaging carrier.

[0147] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0148] The above-mentioned embodiments only express various implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the attached claims.

Claims

1. A resin composition, characterized in that The components are as follows by weight: 50-150 parts of benzoxazine resin containing double bonds; 50-150 parts of bismaleimide resin; Phosphorus silicon epoxy resin 20-80 parts; Epoxy resin 20-80 parts; 200-800 parts of inorganic filler; Curing accelerator 0-2 parts; Solvent 0-100 parts; The phosphorus silicon epoxy resin has a structure shown in Formula 1: Formula 1; Wherein, R1, R2, R3 and R4 are each independently selected from C1-C12 alkyl, C2-C12 alkenyl, aryl, substituted aryl and aryl-substituted C1-C5 alkyl; the substituted aryl contains 1-2 substituents, and the substituents are C1-C5 alkyl; n represents an integer of 0-2; m represents an integer of 1-3.

2. The resin composition according to claim 1, characterized in that The aryl group is phenyl, naphthyl or biphenyl; and / or the aryl group in the substituted aryl group is phenyl, naphthyl or biphenyl; and / or the aryl group in the C1-C5 alkyl group substituted by the aryl group is phenyl, naphthyl or biphenyl.

3. The resin composition according to claim 1, characterized in that One or more of the following conditions are met: (1) The epoxy resin is a phenolic epoxy resin; (2) The benzoxazine resin containing double bonds is a benzoxazine resin containing double bonds at the terminal groups; (3) The bismaleimide resin includes at least one of 4,4'-diphenylmethane bismaleimide, N-2,6-dimethylphenyl maleimide, N-(2,3-dimethylphenyl) maleimide, N-phenyl maleimide, 1,6-dimaleimidohexane, N,N-(4-methyl-1,3-phenylene) bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide, N'-m-phenylene bismaleimide, diphenylmethane maleimide, biphenyl type bismaleimide resin, polyphenylmethane maleimide and bis(3-ethyl-5-methyl-4-maleimidophenyl) methane; (4) The inorganic filler includes metal salt and / or metal hydroxide; (5) The curing accelerator includes at least one of an imidazole curing accelerator, an amine curing accelerator, an organic metal salt, an inorganic metal salt, an organic peroxide and an azo compound; (6) The solvent includes at least one of methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide and propylene glycol methyl ether.

4. The resin composition according to claim 3, characterized in that One or more of the following conditions are met: (1) The phenolic epoxy resin includes o-methyl phenolic epoxy resin and / or naphthalene phenolic epoxy resin; (2) The softening point of the phenolic epoxy resin is 80-95°C; (3) The double bond-containing benzoxazine resin includes at least one of a BPA-type benzoxazine resin, a BPF-type benzoxazine resin, an ODA-type benzoxazine resin and a BPS-type benzoxazine resin; (4) The average particle size of the inorganic filler is 0.1-10 μm.

5. The resin composition according to any one of claims 1 to 4, characterized in that R1, R2, R3 and R4 are each independently selected from C1-C12 alkyl, C2-C6 alkenyl, aryl, substituted aryl and aryl-substituted C1-C2 alkyl; the substituted aryl contains 1-2 substituents, and the substituents are C1-C2 alkyl; n represents an integer of 0-1; m represents an integer of 1-2.

6. The resin composition according to any one of claims 1 to 4, characterized in that The resin composition further comprises one or more of phenolic resin, acid anhydride, benzoxazine resin without double bonds, rubber and modified polytetrafluoroethylene.

7. A prepreg, characterized in that: The raw materials include the resin composition as described in any one of claims 1 to 6 and a reinforcing material.

8. A laminated board, characterized in that: The method comprises the resin composition according to any one of claims 1 to 6 or the prepreg according to claim 7.

9. A copper clad laminate, characterized in that: The method comprises the resin composition according to any one of claims 1 to 6 or the prepreg according to claim 7.

10. A wiring board, characterized in that: The invention comprises the resin composition according to any one of claims 1 to 6, the prepreg according to claim 7, the laminate according to claim 8, or the copper clad laminate according to claim 9.

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