Resin composition, prepreg and application thereof in laminate, copper clad laminate and wiring board

Abstract

The present application provides a kind of resin composition, by epoxy resin and benzoxazine resin are matched, and styrene maleic anhydride copolymer is coordinated, it is possible to improve the moisture resistance and water absorption rate of epoxy resin, reduce its dielectric constant and dielectric loss; At the same time, the mutual coordination between the flame retardant and the benzoxazine resin can further ensure that the resin composition has low dielectric properties, and maintain a low thermal expansion coefficient and good heat resistance. In addition, under the reasonable compatibility of each component and the adjustment of the content of each component, the solubility of styrene maleic anhydride copolymer can be enhanced, and the compatibility between the resin raw materials is increased. And the resin composition of the present application does not contain polyphenylene ether resin and cyanate resin with higher cost, which can effectively reduce the cost of raw materials.

Description

Technical Field

[0001] The present application belongs to the field of polymer materials, and specifically relates to a resin composition, a prepreg, and applications thereof in laminates, copper-clad boards, and wiring boards. Background Art

[0002] The continuous development of electronic products with higher capacity and higher speed requires the performance of printed circuit boards to be continuously improved. This places higher demands on the performance of substrate materials that carry electronic components, especially on the various properties of substrate materials such as glass transition temperature and dielectric properties.

[0003] Traditional substrate materials use polyphenylene ether resin in combination with cyanate ester resin and epoxy resin to achieve low dielectric properties. However, the raw material costs of polyphenylene ether resin and cyanate ester resin are relatively high, and the copper clad laminates prepared therefrom have the problems of high thermal expansion and low heat resistance. Summary of the invention

[0004] In view of the above problems existing in the prior art, the purpose of the present application is to provide a resin composition, a prepreg and its application in a laminate, a copper clad laminate and a wiring board. The resin composition can reduce the cost while having low dielectric properties, and maintain a low thermal expansion coefficient and good heat resistance.

[0005] The present application provides a resin composition, which comprises the following components in parts by weight:

[0006] Epoxy resin 50~150 parts,

[0007] 50 to 150 parts of benzoxazine resin,

[0008] 20 to 80 parts of styrene maleic anhydride copolymer,

[0009] Flame retardant 70~100 parts,

[0010] 1~50 parts of cross-linking agent,

[0011] Initiator 0.05~5 parts,

[0012] 0.01 to 5 parts of accelerator, and

[0013] Inorganic filler 0.05~300 parts;

[0014] Wherein, the softening point of the epoxy resin is 60°C~100°C.

[0015] In one embodiment, the epoxy resin comprises one or more of structural formulas (1-1) to (1-4):

[0016] , , , , where m1, m2, m3 and m4 are all positive integers.

[0017] In one embodiment, the epoxy resin has the structural formula .

[0018] In one embodiment, the benzoxazine resin includes one or more of long-chain benzoxazine, BPA-type benzoxazine, BPF-type benzoxazine and ODA-type benzoxazine.

[0019] Furthermore, the structure of the long-chain benzoxazine resin is shown in formula (2-1):

[0020] , R 1 O, -CH 2 -or-C(CH 3 ) 2 , R 2 -CH 2 -or-C(CH 3 ) 2 , R 3 -CH 2 -or-C(CH 3 ) 2 .

[0021] In one embodiment, the structural formula of the styrene maleic anhydride copolymer is ,

[0022] Among them, m and n are positive integers, and m:n is 1:(1~8).

[0023] In one embodiment, the structural formula of the styrene maleic anhydride copolymer has a ratio of m:n of 1:(3-5).

[0024] In one embodiment, the flame retardant includes one or more of phosphorus-containing phenolic resin, resorcinol bis(xylyl) phosphate and phosphazene compound.

[0025] In one embodiment, the resin composition has one or more of the following characteristics:

[0026] (1) The crosslinking agent includes one or more of allyl compounds, styrene, divinylbenzene, acrylate compounds, methacrylate compounds, polybutadiene and bismaleimide compounds;

[0027] (2) The initiator includes one or more of α,α'-bis(tert-butylperoxym-isopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, benzoyl peroxide, 3,3',5,5'-tetramethyl-1,4-diphenolquinone, tetrachlorobenzoquinone, 2,4,6-tri-tert-butylphenoxy, tert-butylperoxyisopropylmonocarbonate and azobisisobutyronitrile;

[0028] (3) The accelerator includes one or more of boron trifluoride amine complex, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenylimidazole, ethyltriphenylphosphine chloride, triphenylphosphine, 4-methylaminopyridine and butyltriphenylphosphine bromide;

[0029] (4) The inorganic filler includes one or more of silicon dioxide, aluminum oxide, titanium oxide, mica, aluminum hydroxide, magnesium hydroxide, talc, aluminum borate, barium sulfate and calcium carbonate.

[0030] The present application provides a prepreg, which comprises a substrate and the resin composition described in any one of the above embodiments loaded on the substrate.

[0031] The present application also provides a use of the prepreg described in any of the above embodiments in the preparation of a laminate, a copper-clad laminate or a wiring board.

[0032] The present application provides a kind of resin composition, by epoxy resin and benzoxazine resin are matched, and styrene maleic anhydride copolymer is coordinated, it is possible to improve the moisture resistance and water absorption rate of epoxy resin, reduce its dielectric constant and dielectric loss; At the same time, the mutual coordination between the flame retardant and the benzoxazine resin can further ensure that the resin composition has low dielectric properties, and maintain a low thermal expansion coefficient and good heat resistance. In addition, under the reasonable compatibility of each component and the adjustment of the content of each component, the solubility of styrene maleic anhydride copolymer can be enhanced, and the compatibility between the resin raw materials is increased. And the resin composition of the present application does not contain polyphenylene ether resin and cyanate resin with higher cost, which can effectively reduce the cost of raw materials. DETAILED DESCRIPTION

[0033] The following is a further detailed description of the resin combination, prepreg and its application in laminate, copper clad plate and wiring board of the present application in conjunction with specific embodiments. The application can be realized 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 application more thorough and comprehensive. Of course, they are merely examples, and the purpose is not to limit the application.

[0034] When a numerical range is disclosed herein, the above range is considered to be continuous and includes 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 combined. In other words, unless otherwise indicated, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0035] 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. Unless otherwise specified or there is a contradiction, the terms or phrases used herein have the following meanings:

[0036] In the present application, 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.

[0037] In this application, when it comes to percentage concentration, unless otherwise specified, it refers to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of the component.

[0038] In the present application, "*" indicates a connection site.

[0039] In the present application, when a linking site is not specified in a group, it means that an optional linking site in the group can be used as a linking site.

[0040] In the present application, the single bond to which the substituent is connected runs through the corresponding ring, indicating that the substituent can be connected to any position of the ring, for example R is connected to any substitutable position of the benzene ring.

[0041] In this application, express .

[0042] The present application provides a resin composition, which comprises the following components in parts by weight:

[0043] Epoxy resin 50~150 parts,

[0044] 50 to 150 parts of benzoxazine resin,

[0045] 20 to 80 parts of styrene maleic anhydride copolymer,

[0046] Flame retardant 70~100 parts,

[0047] 1~50 parts of cross-linking agent,

[0048] Initiator 0.05~5 parts,

[0049] 0.01 to 5 parts of accelerator, and

[0050] Inorganic filler 0.05~300 parts;

[0051] Wherein, the softening point of the epoxy resin is 60°C~100°C.

[0052] The present application provides a kind of resin composition, by epoxy resin and benzoxazine resin are matched, and styrene maleic anhydride copolymer is coordinated, it is possible to improve the moisture resistance and water absorption rate of epoxy resin, reduce its dielectric constant and dielectric loss; At the same time, the mutual coordination between the flame retardant and the benzoxazine resin can further ensure that the resin composition has low dielectric properties, and maintain a low thermal expansion coefficient and good heat resistance. In addition, under the reasonable compatibility of each component and the adjustment of the content of each component, the solubility of styrene maleic anhydride copolymer can be enhanced, and the compatibility between the resin raw materials is increased. And the resin composition of the present application does not contain polyphenylene ether resin and cyanate resin with higher cost, which can effectively reduce the cost of raw materials.

[0053] It can be understood that the softening point of the present application can be any value measured by a conventional softening point measurement method. Specifically, the value measured using a softening point meter can be listed. The basic principle is to heat at a specified speed in a glycerin bath under the action of a steel ball to the temperature when the steel ball falls 25 mm.

[0054] In one example, the resin composition includes 50 to 150 parts of epoxy resin by weight. Specifically, the weight of the epoxy resin includes but is not limited to 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 120 parts, 140 parts or 150 parts.

[0055] In one example, the resin composition includes 50 to 150 parts of benzoxazine resin by weight. Specifically, the weight of the benzoxazine resin includes but is not limited to 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 120 parts, 140 parts or 150 parts.

[0056] In one example, the resin composition includes 20 to 80 parts of styrene maleic anhydride copolymer by weight. Specifically, the weight of the styrene maleic anhydride copolymer includes but is not limited to 20 parts, 30 parts, 40 parts, 50 parts, 55 parts, 60 parts, 70 parts or 80 parts.

[0057] In one example, the resin composition includes 70 to 100 parts of a flame retardant by weight. Specifically, the flame retardant includes, but is not limited to, 70, 80, 90, 95 or 100 parts by weight.

[0058] In one example, the resin composition includes 1 to 50 parts of a cross-linking agent by weight. Specifically, the weight of the cross-linking agent includes but is not limited to 1 part, 10 parts, 20 parts, 30 parts, 40 parts or 50 parts.

[0059] In one example, the resin composition includes 0.05 to 5 parts of an initiator by weight. Specifically, the weight of the initiator includes but is not limited to 0.05, 0.1, 0.15, 0.2, 1, 2, 3, 4 or 5 parts.

[0060] In one example, the resin composition includes 0.01 to 5 parts of an accelerator by weight. Specifically, the weight of the accelerator includes but is not limited to 0.01, 0.05, 0.1, 0.15, 0.2, 1, 2, 3, 4 or 5 parts.

[0061] In one example, the resin composition includes 0.05 to 300 parts of inorganic filler by weight. Specifically, the weight of the inorganic filler includes but is not limited to 0.05, 0.1, 10, 20, 50, 100, 150, 180, 200, 220, 280, 290 or 300 parts.

[0062] In one example, the epoxy resin includes one or more of structural formulas (1-1) to (1-4):

[0063] , , , , where m1, m2, m3 and m4 are all positive integers.

[0064] In the present application, the epoxy resins in the structural formula (1-1) to the structural formula (1-4) are selected, which have high crosslinking density after curing and good mechanical properties.

[0065] Preferably, the epoxy resin is a naphthalene epoxy resin. The structure of the naphthalene epoxy resin includes but is not limited to .

[0066] In one example, the benzoxazine resin includes one or more of long-chain benzoxazine, BPA-type benzoxazine, BPF-type benzoxazine and ODA-type benzoxazine.

[0067] In one example, the benzoxazine resin includes one or more of structural formulas (2-1) to (2-4):

[0068] , , , , R 1 O, -CH 2 -or-C(CH 3 ) 2 , R 2 -CH 2 -or-C(CH 3 ) 2 , R 3 -CH 2 -or-C(CH 3 ) 2 .

[0069] Preferably, the benzoxazine resin is a long-chain benzoxazine, and the structure of the long-chain benzoxazine resin includes but is not limited to structural formula (2-1): .

[0070] In one example, the structural formula of the styrene maleic anhydride copolymer is ,

[0071] Among them, m and n are positive integers, and m:n is 1:(1~8).

[0072] It can be understood that the ratio of m to n in the styrene maleic anhydride copolymer can be any resin between 1: (1-8). Specifically, the ratio of m to n in the styrene maleic anhydride copolymer includes but is not limited to 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7 or 1:8.

[0073] Preferably, in the structural formula of the styrene maleic anhydride copolymer, m:n is 1:(3-5).

[0074] In one specific example, the m:n ratio of the styrene maleic anhydride copolymer is 1:4.

[0075] In one example, the flame retardant includes one or more of phosphorus-containing phenolic resin, resorcinol bis-xylyl phosphate, and phosphazene compound.

[0076] In one example, the flame retardant includes one or more of structural formula (5-1) to structural formula (5-3): , , , where n1 and n2 are positive integers, and X is .

[0077] More preferably, the flame retardant is , where n1 is a positive integer and X is .

[0078] In one example, the cross-linking agent includes one or more of an allyl compound, styrene, divinylbenzene, an acrylate compound, a methacrylate compound, polybutadiene, and a bismaleimide compound.

[0079] Preferably, the crosslinking agent includes one or more of triallyl isocyanurate, 2,2'-diallylbisphenol A and diallylbisphenol.

[0080] More preferably, the crosslinking agent is triallyl isocyanurate. The structural formula of triallyl isocyanurate is .

[0081] In one example, the initiator includes one or more of α,α'-bis(tert-butylperoxym-isopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, benzoyl peroxide, 3,3',5,5'-tetramethyl-1,4-diphenolquinone, tetrachlorobenzoquinone, 2,4,6-tri-tert-butylphenoxy, tert-butylperoxyisopropyl monocarbonate and azobisisobutyronitrile.

[0082] The selection of initiator is considered from the viewpoint of the reaction starting temperature, preferably a dialkyl organic peroxide, and α, α'-bis(tert-butylperoxym-isopropyl)benzene is preferably used in the above example. α, α'-bis(tert-butylperoxym-isopropyl)benzene has a relatively high reaction starting temperature, so it can inhibit the promotion of the curing reaction when the prepreg is dried, etc., when curing is not required. By inhibiting the curing reaction, the storage property of the resin composition can be suppressed from being reduced. Furthermore, α, α'-bis(tert-butylperoxym-isopropyl)benzene has low volatility, so it will not volatilize when the prepreg is dried or stored, and has good stability. In addition, the organic peroxide can be used alone or in combination of two or more.

[0083] In one example, the accelerator includes one or more of boron trifluoride amine complex, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenylimidazole, ethyltriphenylphosphine chloride, triphenylphosphine, 4-methylaminopyridine and butyltriphenylphosphine bromide.

[0084] In one example, the inorganic filler includes one or more of silicon dioxide, aluminum oxide, titanium oxide, mica, aluminum hydroxide, magnesium hydroxide, talc, aluminum borate, barium sulfate and calcium carbonate.

[0085] The present application provides a prepreg, which comprises a substrate and a resin composition described in any one of the above examples loaded on the substrate.

[0086] In the present application, inorganic fillers are used as fillers of resin compositions. Inorganic fillers can improve the heat resistance and flame retardancy of the cured product of the resin composition. The inorganic filler can be spherical, fibrous, plate-like, granular, flaky or needle-like. One inorganic filler can be used alone, or two or more inorganic fillers can be used in combination. In addition, the inorganic filler can be used directly, or an inorganic filler surface-treated with a silane coupling agent can be used. As the inorganic filler, preferably silica, mica and talc, more preferably spherical silica.

[0087] In one example, the resin composition further includes a solvent.

[0088] 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 invention is not particularly limited, and can be any one or more solvents suitable for dissolving or diluting the aforementioned resin composition, and specific examples include but are not limited to: methanol, ethanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, acetone, butanone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide and other solvents and mixtures thereof.

[0089] In one example, the resin composition may further include other functional resins.

[0090] In one example, the other functional resins include one or more of epoxy resin, phenolic resin, acid anhydride, benzoxazine resin, rubber and modified PTFE.

[0091] The present application also provides a use of the prepreg described in any of the above embodiments in the preparation of a laminate, a copper-clad laminate or a wiring board.

[0092] The present application also provides a method for preparing a prepreg, the preparation method comprising the following steps:

[0093] Mixing the components of the resin composition in a solvent to prepare the resin composition;

[0094] The resin composition is loaded on a substrate to prepare a prepreg.

[0095] It is understandable that the present application does not limit the method of mixing the components in the solvent, as long as the method can be used to mix the components. For example, the components that can be dissolved in the organic solvent can be first put into the organic solvent to completely dissolve, and heating can be performed as needed; then the components that are insoluble in the organic solvent, such as flame retardants and inorganic fillers, are added and stirred and mixed using a ball mill, a bead mill, a planetary mixer, a roller mill, etc.

[0096] The present application does not limit the manner in which the resin composition is loaded on a substrate. Examples include impregnation, coating, and spraying. In addition, as a method for manufacturing a prepreg, the resin composition is loaded on a substrate and then dried and heated. In addition, the impregnation, coating, and spraying steps in the present application may be repeated multiple times as needed. In addition, multiple thermosetting resin compositions with different compositions and solid contents may be used for repeated impregnation to adjust to the final composition and glue content.

[0097] The present application also provides a prepreg, which comprises a substrate and the resin composition described in any one of the above embodiments loaded on the substrate.

[0098] In the present application, the substrate is a conventional inorganic or organic fiber material, and the inorganic fiber substrate includes but is not limited to glass fiber cloth, carbon fiber, silicon carbide fiber or asbestos fiber. The organic fiber substrate includes but is not limited to nylon, ultra-high molecular weight polyethylene fiber, aramid fiber, polyimide fiber, polyester fiber or cotton fiber. The glass fiber cloth includes but is not limited to the types of E, NE, D, S, and T.

[0099] Preferably, the substrate is glass fiber cloth.

[0100] More preferably, the substrate is a flattened glass fiber cloth. The flattening process is a process of continuously pressing the glass cloth with a pressing roller at an appropriate pressure to compress the yarn into a flat state.

[0101] The present application also provides a method for preparing a prepreg, comprising the following steps:

[0102] The prepreg is heated to prepare the prepreg.

[0103] In one example, the heating process parameters include: the temperature is set to 80°C~200°C, and the time is set to 1min~20min.

[0104] Furthermore, the heating process parameters include: the temperature is set to 110°C~190°C, and the time is set to 2min~10min.

[0105] The present application also provides a laminate, which includes the prepreg described in the above embodiment.

[0106] The present application also provides a method for preparing a laminate, comprising the following steps:

[0107] One or more prepregs are selected and laminated to prepare the laminate.

[0108] In one example, the lamination process parameters include: the temperature is set to 170℃~250℃, the pressure is set to 10 kgf / cm 2 ~30kgf / cm 2 , vacuum degree <2kPa, hot pressing forming 60min~120min.

[0109] The present application also provides a copper clad laminate, which includes the prepreg described in the above embodiment and a metal foil covering one side or both sides of the laminated prepreg.

[0110] In one example, the thickness of the metal foil is 3 μm to 70 μm.

[0111] The present application also provides a wiring board, which includes the prepreg described in the above embodiment.

[0112] In order to make the purpose and advantages of the present application clearer, the resin composition and copper clad laminate of the present application are further described in detail in conjunction with specific examples. It should be understood that the specific examples described herein are only used to explain the present application and shall not be used to limit the present application. The following examples do not include other components except inevitable impurities unless otherwise specified. The drugs and instruments used in the examples are conventionally selected in the art unless otherwise specified. The experimental methods for which specific conditions are not specified in the examples are implemented according to conventional conditions, such as the conditions described in the literature and books or the methods recommended by the manufacturer.

[0113] The raw materials used in the following examples and comparative examples are as follows:

[0114] [Epoxy phenolic resin]

[0115] 704, o-methylphenolic epoxy resin, manufactured by Nan Ya Company;

[0116] 7200H, dicyclopentadiene phenolic epoxy resin, manufactured by DIC Corporation of Japan;

[0117] NC-3000H, biphenyl phenolic epoxy resin, manufactured by Nippon Kayaku Co., Ltd.;

[0118] NC-7000L, naphthalene-type phenolic epoxy resin, manufactured by Nippon Kayaku Co., Ltd.;

[0119] [Benzoxazine resin]

[0120] LZ-36, long-chain benzoxazine, structural formula , manufactured by Oasis Company;

[0121] CB3170, BPA-type benzoxazine, structural formula , manufactured by Keyi Company;

[0122] CB4170, BPF type benzoxazine, structural formula , manufactured by Keyi Company;

[0123] PF3500, ODA type benzoxazine, structural formula , manufactured by Changchun Company;

[0124] [Styrene maleic anhydride copolymer]

[0125] SMA-EF30, styrene maleic anhydride copolymer (S:MA=3:1), manufactured by Cray Valley Company;

[0126] SMA-EF40, styrene maleic anhydride copolymer (S:MA=4:1), manufactured by Cray Valley Company;

[0127] SMA-EF60, styrene maleic anhydride copolymer (S:MA=6:1), manufactured by Cray Valley Company;

[0128] [Crosslinking agent]

[0129] TAIC, triallyl isocyanurate, manufactured by Nippon Chemical Industry Co., Ltd.

[0130] [Halogen-free flame retardant]

[0131] XQ-83006, phosphorus-containing phenolic resin, P% = 10%, manufactured by Lanco Company;

[0132] PX-200, resorcinol dixylyl phosphate, P% = 9%, manufactured by Daba Company;

[0133] SPB-100, phosphazene compound, P% = 13%, manufactured by Otsuka Corporation;

[0134] [Inorganic filler]

[0135] NQ1029, spherical silica, manufactured by Lianrui Company;

[0136] [Initiator]

[0137] PERBUTYL P, 1,3-bis(butylperoxyisopropyl)benzene, manufactured by NOF Corporation of Japan;

[0138] [Accelerator]

[0139] 2-MI, 2-methylimidazole, manufactured by Shikoku Chemical Co., Ltd.;

[0140] [Fiberglass cloth]

[0141] Fiberglass cloth, 2116 cloth, manufactured by Honghe Company.

[0142] The compositions of the resin compositions provided in the examples and comparative examples are as follows (in parts by weight):

[0143]

[0144]

[0145] The preparation process of the resin composition of the embodiment and the comparative example is as follows:

[0146] Styrene maleic anhydride copolymer is mixed with acetone, and the mixture is heated to 60°C and stirred sufficiently to fully dissolve the styrene maleic anhydride copolymer in acetone to obtain an acetone solution with a solid content of 40% by mass. Then, phenolic epoxy resin and benzoxazine resin are added thereto to reach the proportions in each embodiment and comparative example in the table, and stirred for 2 hours to fully dissolve them. Finally, a halogen-free flame retardant, an inorganic filler, an initiator and an appropriate amount of acetone are further added, and the mixture is fully dispersed using a bead mill to obtain a resin composition.

[0147] The preparation process of the prepregs of the embodiments and comparative examples is as follows:

[0148] The glass fiber cloth was immersed in the resin composition prepared in the embodiment and the comparative example, the temperature was set to 160°C, and heated for 5 minutes to prepare a prepreg. At this time, the solid content of the resin composition can be adjusted to obtain a prepreg with a mass ratio of 50%.

[0149] The preparation process of the copper clad laminate of the embodiment and the comparative example is as follows:

[0150] Eight prepregs prepared in each embodiment and comparative example were stacked, 35 μm copper foil was placed on both sides, and heated and pressed for 2 hours at a temperature of 200° C. and a pressure of 3 MPa to prepare a copper clad laminate with a thickness of about 0.9 mm.

[0151] Performance Tests of Copper Clad Laminates of Examples and Comparative Examples

[0152] 1. Peel strength: Tested using a universal tensile testing machine in accordance with IPC-TM-650 2.4.8.

[0153] 2. Glass transition temperature (Tg): The glass transition temperature (Tg) is measured using a differential scanning calorimeter (DSC) (Q20 manufactured by TA Instruments) with a heating rate of 20°C / min. The test specification for glass transition temperature uses the Institute for Interconnecting and Packaging Electronic Circuits (IPC) IPC-TM-650 2.4.25 test method.

[0154] 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.

[0155] 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.

[0156] 5. Test of thermal expansion coefficient and expansion rate in the Z-axis direction: Measured by TA instrument company's TA Q800 thermal expansion analyzer, with a measuring temperature of 50℃~260℃ and a heating rate of 10℃ / min, to test the thermal expansion coefficient and expansion rate of the sample in each direction (X / Y / Z axis direction).

[0157] 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.

[0158] The test results of the copper clad laminates of the above embodiments and comparative examples are as follows:

[0159]

[0160] From the performance of the copper-clad laminate provided by the above-mentioned embodiments and comparative examples, it can be known that when the resin composition in Example 1 is used, a halogen-free high glass transition temperature, good dielectric properties and excellent heat resistance can be achieved, and the resin composition contains a naphthalene-type phenolic epoxy resin, a long-chain benzoxazine resin, a styrene maleic anhydride copolymer and a cross-linking agent. The copper-clad laminate prepared by the resin composition in Example 1 has a Tg of 185°C, a Peel of 8.0lb / in, a Df of 0.0070 at 10GHz, excellent heat resistance, a low thermal expansion coefficient, and a flame retardant of 94UL-V0 level. The types and portions of flame retardants in Comparative Examples 1 and 2 are different from those in Example 1. The Tg of the copper-clad laminate in Comparative Examples 1 and 2 decreases, and the heat resistance is poor. At the same time, the thermal expansion coefficients of Comparative Examples 1 and 2 are large, and the dielectric loss is large. By comparing Comparative Example 3 with Example 1, it is found that the addition of inorganic fillers plays an important role in reducing the thermal expansion coefficient of the copper-clad laminate, improving the heat resistance of the copper-clad laminate, and reducing the dielectric loss. In comparative example 4, the phosphorus-containing phenolic resin in the resin composition is insufficient, resulting in the flame retardancy of the cured product only meeting the 94UL-V1 level. In comparative example 5, no initiator is added to the resin composition, and the crosslinking agent cannot be cured, resulting in insufficient Tg of the cured product and failure to pass the heat resistance test.

[0161] 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.

[0162] The above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several variations and improvements can be made, which all belong to the protection scope of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the protection scope of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the content of the attached claims, and the description can be used to interpret the content of the claims.

Claims

1. A resin composition, characterized in that In parts by weight, it includes the following components: Epoxy resin 50~150 parts, 50 to 150 parts of benzoxazine resin, 20 to 80 parts of styrene maleic anhydride copolymer, Flame retardant 70~100 parts, 1~50 parts of cross-linking agent, Initiator 0.05~5 parts, 0.01 to 5 parts of accelerator, and Inorganic filler 0.05~300 parts; The softening point of the epoxy resin is 83°C to 93°C; the structural formula of the epoxy resin is ; Wherein, m4 is a positive integer; The flame retardant is a phosphorus-containing phenolic resin; The initiator includes 1,3-bis(butylperoxyisopropyl)benzene; The structural formula of the styrene maleic anhydride copolymer is , where m and n are positive integers, and m:n is 1:(3~5).

2. The resin composition according to claim 1, characterized in that The benzoxazine resin includes one or more of long-chain benzoxazine, BPA-type benzoxazine, BPF-type benzoxazine and ODA-type benzoxazine; Wherein, the brand of the long-chain benzoxazine resin is LZ-36.

3. The resin composition according to claim 1, characterized in that The crosslinking agent includes one or more of allyl compounds, styrene, divinylbenzene, acrylate compounds, polybutadiene and bismaleimide compounds.

4. The resin composition according to claim 1, characterized in that The accelerator includes one or more of boron trifluoride amine complex, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenylimidazole, ethyltriphenylphosphine chloride, triphenylphosphine, 4-methylaminopyridine and butyltriphenylphosphine bromide.

5. The resin composition according to any one of claims 1 to 4, characterized in that The inorganic filler includes one or more of silicon dioxide, aluminum oxide, titanium oxide, mica, aluminum hydroxide, magnesium hydroxide, talc, aluminum borate, barium sulfate and calcium carbonate.

6. A prepreg, characterized in that: The prepreg comprises a substrate and the resin composition according to any one of claims 1 to 5 supported on the substrate.

7. Use of the prepreg according to claim 6 in the preparation of laminates, copper-clad boards or wiring boards.

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