Resin composition, metal foil-clad laminated board and printed circuit board

Abstract

The invention provides a resin composition, a metal foil-coated laminated board and a printed circuit board. The resin composition is prepared from the following components in parts by mass: 50 to 80 parts of maleimide compound, 5 to 20 parts of epoxy resin, 5 to 20 parts of benzoxazine compound, 5 to 15 parts of double bond-containing phosphazene and 80 to 300 parts of filler, the indane structure-containing maleimide resin in the maleimide compound accounts for more than or equal to 50% by mass. Through component design and mutual compounding, the resin composition and the metal foil-clad laminated board containing the resin composition have the characteristics of high glass transition temperature, high adhesive force, high peel strength, low thermal expansion coefficient, low dielectric loss and good flame retardance, and the reliability of a substrate material and an electronic product is greatly improved.

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, and a printed circuit board. Background Art

[0002] Modern electronic products require fast information transmission rate and large information transmission volume, which promotes the development of digital signal technology towards high frequency. To achieve this goal, it is required that the substrate material has a low dielectric constant and a low dielectric loss tangent to reduce the damping effect on the electrical signal, thereby improving the signal transmission speed and reducing signal transmission loss. In addition, electronic devices tend to be highly integrated, high-density, and multi-functional. The integration degree of chips is continuously increasing, and the corresponding power consumption also increases; the increase in power consumption generates more heat, and continuous high temperature will cause the performance and reliability of electronic products to gradually deteriorate, manifested in the reduction of connection reliability caused by the mismatch of thermal expansion between the substrate material and the chip, which brings serious challenges to the overall reliability and stability of the product.

[0003] Among substrate materials, epoxy resin has good heat resistance, adhesiveness, and processability. However, when cured with conventional amine and phenolic resins, it will generate a polar group structure that hinders the further improvement of the dielectric properties of the resin. Therefore, the industry has turned its attention to active esters as curing agents to reduce and avoid the generation of polar groups, so that the product can have a low dielectric constant and dielectric loss factor. However, most active esters are bifunctional structures, and the curing crosslinking density is not high, resulting in a lower glass transition temperature T g of the board and large thermal expansion. JP2019006869A discloses a resin composition including an active ester resin and an epoxy resin. Through the technology of combining a biphenyl-type epoxy resin with an active ester curing agent, the made copper-clad laminate has good heat resistance, but its dielectric constant and dielectric loss are relatively high, unable to reach the level of low dielectric loss, and it is difficult to meet the needs of high-frequency signal large-capacity transmission.

[0004] In existing substrate materials, the coefficient of thermal expansion (CTE) of organic resins is usually relatively high, and the CTE of inorganic fillers is one order of magnitude lower than that of organic resins. To reduce the overall CTE of the substrate material, introducing inorganic fillers with a low expansion coefficient is one of the most effective means at present. However, after adding inorganic fillers, the interlayer adhesion of the board will decrease significantly, seriously affecting the long-term working stability of the substrate.

[0005] Therefore, how to provide a resin material with low dielectric loss characteristics, low thermal expansion rate, and high adhesiveness has become an urgent problem to be solved in the current field. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a resin composition, a metal-clad laminate, and a printed circuit board. Through the design and mutual compounding of components such as maleimide compounds, epoxy resins, benzoxazine compounds, double-bonded phosphazenes, and fillers, the resin composition and the metal-clad laminate achieve high glass transition temperatures, high adhesion and peel strength, low coefficient of thermal expansion, and low dielectric loss, with good flame retardancy, greatly improving the reliability and stability of the substrate material and electronic products.

[0007] To achieve this purpose, the present invention adopts the following technical solutions:

[0008] In the first aspect, the present invention provides a resin composition, which includes the following components in parts by mass:

[0009]

[0010] The maleimide compound includes an indane-structured maleimide resin, and the mass percentage content of the indane-structured maleimide resin in the maleimide compound is ≥50%.

[0011] The present invention has found through research that a maleimide compound is a compound with an unsaturated imide ring at the end prepared by the ring-opening nucleophilic substitution reaction of maleic anhydride with a diamine and / or polyamine. The maleimide compound has the potential of high rigidity and low dielectric properties. Using it as the main resin can bring characteristics such as a relatively high glass transition temperature, good heat resistance, low dielectric constant, and low dielectric loss, but it has the weaknesses of a high self-polymerization temperature and difficulty in reacting with epoxy groups. In the resin composition of the present invention, a small amount of benzoxazine compound and epoxy resin are introduced to promote the ring-opening of the benzoxazine structure, and the generated hydroxyl groups copolymerize with the double bonds in the imide ring and initiate a self-polymerization reaction, thereby significantly reducing the curing temperature of the maleimide compound. Further, in order to improve the flame retardancy, a double-bonded phosphazene is introduced into the resin composition of the present invention to introduce a phosphorus group into the resin structure, and a synergistic flame retardant effect is formed with the imide, aromatic ring, etc. in the system, so that excellent flame retardant effects can be obtained as a whole.

[0012] In the resin composition provided by the present invention, maleimide compounds, epoxy resins, benzoxazine compounds, and double-bonded phosphazenes are mutually compounded and combined with fillers. In the curing reaction, there are cross-linking reactions between maleimide compounds and benzoxazine compounds and double-bonded phosphazenes, and between epoxy resins and benzoxazine compounds, as well as self-polymerization reactions of maleimide compounds and benzoxazine compounds, thereby forming a highly cross-linked system in which different structural molecules penetrate each other. Different rigid structures are superimposed, and the main chain of the molecule is not easily affected by polarization. Therefore, the cured product and the metal-clad laminate containing it have a high glass transition temperature (T g) The effects of low coefficient of thermal expansion (CTE), high peel strength, low dielectric constant and low dielectric loss tangent, good flame retardant performance, and excellent dielectric stability greatly improve the reliability of the substrate material and electronic products.

[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 objectives and beneficial effects of the present invention can be better achieved and realized.

[0014] The mass parts of the maleimide compound are 50 - 80 parts, for example, it can be 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts or 78 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 scope.

[0015] The mass parts of the epoxy resin are 5 - 20 parts, for example, it can be 6 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 simplicity, the present invention does not exhaustively list the specific point values included in the scope.

[0016] The mass parts of the benzoxazine compound are 5 - 20 parts, for example, it can be 6 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 simplicity, the present invention does not exhaustively list the specific point values included in the scope.

[0017] The mass parts of the double - bond - containing phosphazene are 5 - 15 parts, for example, it can be 6 parts, 8 parts, 10 parts, 12 parts, 14 parts or 15 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 scope.

[0018] The mass parts of the filler are 80 - 300 parts, for example, it can be 100 parts, 120 parts, 150 parts, 160 parts, 180 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 scope.

[0019] In the present invention, the maleimide compound is a maleimide resin containing at least 2 (such as 2, 3, 4, 5, 6, 8, 10, 12, 15, 16, 18, etc.) imide ring structures in its molecular structure.

[0020] In the present invention, the mass percentage content of the indane structure-containing maleimide resin in the maleimide compound is ≥ 50%, and for example, it can be 52%, 55%, 58%, 60%, 65%, 68%, 70%, 75%, 80%, 85%, 90%, 92%, 95%, 98%, 99% or 100%, 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] In the present invention, the maleimide compound includes an indane structure-containing maleimide resin, and the mass content of the indane structure-containing maleimide resin is ≥ 50%. When it is compounded with an epoxy resin, a benzoxazine compound, and a double-bond-containing phosphazene, it can be cured to form a highly crosslinked system, so that the cured product and the metal-clad laminate have high T g , high heat resistance, low CTE, low dielectric constant and low dielectric loss tangent. If the mass content of the indane structure-containing maleimide resin in the maleimide compound is < 50%, it will lead to a decline in dielectric properties.

[0022] Preferably, the indane structure-containing maleimide resin has the structure shown in Formula I:

[0023]

[0024] In Formula I, m is selected from integers from 1 to 10, and for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0025] In Formula I, R1 and R2 are each independently selected from any one of straight-chain or branched-chain alkyl groups having 1 to 5 carbon atoms (such as C1, C2, C3, C4, C5), alkoxy groups having 1 to 5 carbon atoms (such as C1, C2, C3, C4, C5), or phenyl groups.

[0026] In Formula I, p1 and p2 respectively represent the number of substituents R1 and R2, and are each independently selected from integers from 0 to 4, and for example, they can be 0, 1, 2, 3 or 4.

[0027] It should be noted that when p1 is 0, it means that there are no other substituents connected to the corresponding benzene ring, and all 4 sites are H; when p1 ≥ 2, multiple R1 are the same or different groups; the same applies to p2. When similar expressions are involved below, they all have similar meanings. For the sake of simplicity, they will not be elaborated one by one.

[0028] Preferably, the maleimide compound further includes a second maleimide resin.

[0029] Preferably, the second maleimide resin has the structure shown in Formula II:

[0030]

[0031] In formula II, L is selected from any one of the following groups:

[0032]

[0033] ——* represents the connection site of the group.

[0034] R3, R4, and R5 are each independently selected from any one of C1-C5 (such as C1, C2, C3, C4, C5) straight-chain or branched-chain alkyl groups and phenyl groups.

[0035] n1 is selected from integers from 1 to 10, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and more preferably 2-10.

[0036] m1, m2, and m3 respectively represent the number of substituents R3, R4, and R5, and are each independently selected from integers from 0 to 3, for example, they can be 0, 1, 2, or 3. When m1≥2, multiple R3 groups are the same or different groups; when m2≥2, multiple R4 groups are the same or different groups; when m3≥2, multiple R5 groups are the same or different groups.

[0037] Preferably, m1 is 2, that is, there are 2 R3 groups connected to the benzene ring, one of which is a methyl group and the other is a methyl group, an ethyl group, or a propyl group; and / or, m2 is 2, that is, there are 2 R4 groups connected to the benzene ring, one of which is a methyl group and the other is a methyl group, an ethyl group, or a propyl group.

[0038] Preferably, the maleimide compound can be a commercially available product, and exemplary ones include, but are not limited to: any one or a combination of at least two of X9-470, NE-X-9500 from DIC Corporation, BMI-2300 from Daiwa Chemical, DFE936, DFE950, DFE969 from Dongcai Technology Co., Ltd., MIR-3000, MIR-5000 from Nippon Kayaku Co., Ltd.

[0039] Preferably, in the resin composition of the present invention, based on 100 parts by mass of the total mass of the organic resin, the mass of the maleimide compound is 50-80 parts, for example, it can be 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts, or 78 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. If the amount of the maleimide compound used is too small, the heat resistance of the resin cured product and the sheet will decrease; if the amount used is too large, the hardness of the cured product and the sheet will be too high, which is not conducive to machining.

[0040] In the present invention, the "total mass of the organic resin" refers to the total mass of the maleimide compound, epoxy resin, benzoxazine compound, double-bond-containing phosphazene, and optionally the epoxy curing agent (if any). When the same description is involved hereinafter, it shall have the same meaning.

[0041] 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.

[0042] Preferably, the epoxy resin includes any one or a combination of at least two of linear phenolic epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, naphthol novolac 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, biphenyl phenol type epoxy resin, tetramethyl biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, dicyclopentadiene phenol type epoxy resin, dicyclopentadiene novolac epoxy resin, aralkyl type epoxy resin, aralkyl novolac epoxy resin, epoxy resin containing an arylene ether structure, epoxy resin containing an arylene ester structure, alicyclic epoxy resin, polyol type epoxy resin, silicon-containing epoxy resin, nitrogen-containing epoxy resin, phosphorus-containing epoxy resin, glycidylamine epoxy resin, and glycidyl ester epoxy resin.

[0043] Preferably, the epoxy resin includes a polyfunctional epoxy resin containing an aromatic ring and / or a heteroaromatic ring.

[0044] Preferably, the aromatic ring includes at least one of a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring.

[0045] More preferably, the epoxy resin includes any one or a combination of at least two of linear phenolic epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, naphthol novolac epoxy resin, biphenyl type epoxy resin, biphenyl phenol type epoxy resin, dicyclopentadiene phenol type epoxy resin, dicyclopentadiene novolac epoxy resin, aralkyl type epoxy resin, aralkyl novolac epoxy resin, dicyclopentadiene type epoxy resin, and epoxy resin containing an arylene ether structure.

[0046] Preferably, the epoxy equivalent of the epoxy resin is 150-500 g / eq, for example, it can be 170 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.

[0047] Preferably, in the resin composition of the present invention, based on 100 parts by mass of the total mass of the organic resin, the mass of the epoxy resin is 5-20 parts, for example, it can be 6 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 simplicity, the present invention does not exhaustively list the specific point values included in the range. If the amount of the epoxy resin used is too small, the adhesiveness of the metal-clad laminate containing it will be poor; if the amount used is too large, the dielectric properties of the sheet will deteriorate.

[0048] In the present invention, the benzoxazine compound can also be referred to as "benzoxazine resin", or a compound having a dihydrobenzoxazine ring. It is a benzoxazine six-membered heterocyclic compound synthesized from phenol, primary amine and formaldehyde, and can form a nitrogen-containing and phenolic resin-like network structure through ring-opening polymerization.

[0049] Preferably, the benzoxazine compound includes a diamine-type benzoxazine resin and / or a diphenol-type benzoxazine resin.

[0050] Preferably, the benzoxazine compound includes any one or a combination of at least two of the compounds having the structure shown in Formula III and the compounds having the structure shown in Formula IV;

[0051]

[0052] Among them, X1 is selected from any one of the following groups:

[0053] ——* represents the connection site of the group; preferably, X1 is selected from

[0054] X2 is selected from any one of -CH2-, -O-, -S(O)2- or -C(CH3)2-, and further preferably -CH2- or -O-.

[0055] R 11 、R 12 Each independently is selected from any one of vinyl, propenyl, allyl or phenyl, and further preferably allyl or phenyl.

[0056] R 13 and R 14 are each independently selected from any one of C1-C5 (such as C1, C2, C3, C4, C5) linear or branched alkyl groups, and further preferably methyl or ethyl.

[0057] In formula IV, n1 and n2 respectively represent the number of substituents R 13 and R 14 , and are each independently selected from integers of 0-4. For example, they can be 0, 1, 2, 3 or 4. When n1≥2, multiple R 13 are the same or different groups; when n2≥2, multiple R 14 are the same or different groups.

[0058] Preferably, in the resin composition of the present invention, based on 100 parts by mass of the total mass of the organic resin, the mass of the benzoxazine compound is 5-20 parts. For example, it can be 6 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 simplicity, the present invention does not exhaustively list all the specific point values included in the range. If the dosage of the benzoxazine compound is too much, it will cause a decrease in the dielectric properties of the board, etc.; if the dosage is too little, it will reduce the glass transition temperature (T g ) of the resin cured product and the board, and the adhesion will decrease.

[0059] Preferably, the benzoxazine compound includes a diamine-type benzoxazine resin and / or a diphenol-type benzoxazine resin. The diamine-type benzoxazine resin includes an MDA-type benzoxazine and / or an ODA-type benzoxazine; and / or, the diphenol-type benzoxazine resin includes a benzoxazine containing an allyl structure.

[0060] Preferably, the double-bond-containing phosphazene is a cyclophosphazene resin containing a C═C unsaturated double bond.

[0061] Preferably, the double-bond-containing phosphazene includes any one or a combination of at least two of the compounds having the structure shown in formula V and the compounds having the structure shown in formula VI:

[0062]

[0063] Among them, Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, Ar7, Ar8 are each independently selected from R is selected from any one of vinyl, allyl, acryloyl or methacryloyl.

[0064] In each of the above compounds, the molar amount of the group is n11 , group The molar mass is n 12 , n 11 :n 12 It is 1:(0.3-3), for example, it can be 1:0.33, 1:0.5, 1:0.67, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.2, 1:2.5 or 1:2.8, etc.

[0065] Preferably, the double-bond-containing phosphazene may be a commercially available product, including but not limited to SPV-100 (Otsuka Chemical, Japan) and / or FP-700TP (Fushimi Pharmaceutical Co., Ltd., Japan).

[0066] Preferably, in the resin composition of the present invention, the mass of the double-bond phosphazene is 5-15 parts, for example, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts or 15 parts, and specific values ​​between the above points. Due to space limitations and for simplicity, the present invention no longer exhaustively lists the specific points included in the range. If the amount of double-bond phosphazene is too small, the flame retardancy of the resin composition and the board will be insufficient; if it is too much, the glass transition temperature of the cured resin and the board will decrease.

[0067] Preferably, the resin composition of the present invention may further include other epoxy curing agents for further curing the epoxy resin.

[0068] Preferably, in the resin composition, the mass fraction of the epoxy curing agent is ≤20 parts, for example, it can be 0, 0.1 parts, 1 parts, 2 parts, 3 parts, 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts or 18 parts, as well as 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 range.

[0069] Further preferably, in the resin composition of the present invention, based on the total mass of the organic resin as 100 parts, the mass of the epoxy curing agent is 0-20 parts, for example, it can be 0.1 parts, 1 parts, 2 parts, 3 parts, 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts or 18 parts, and specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range. Preferably, the epoxy curing agent includes an amine curing agent and / or an active ester curing agent.

[0070] The active ester curing agent is a material having an ester structure in the molecule that can react with an epoxy group. Exemplarily, the active ester curing agent has a structure as shown in Formula VII:

[0071]

[0072] Among them, X is selected from a benzene ring or a naphthalene ring, and L1 is selected from any one of a benzene ring structure, a naphthalene ring structure, a benzene ring-dicyclopentadiene structure, and a naphthalene ring-dicyclopentadiene structure.

[0073] Preferably, the active ester curing agent includes the compound shown as AR-1 and / or the compound shown as AR-2:

[0074]

[0075]

[0076] In AR-1, X is selected from a benzene ring or a naphthalene ring; R6 and R7 are each independently selected from a methyl group or H, k is 0 or 1, and the equivalent of m4 is 0.2 - 2, and can be, for example, 0.3, 0.5, 0.6, 0.8, 1, 1.2, 1.4, 1.5, 1.6, 1.8, etc.

[0077] Preferably, a commercially available example of the active ester curing agent represented by AR-1 is HPC-8000-65T manufactured by DIC Corporation.

[0078] In AR-2, X is selected from a benzene ring or a naphthalene ring; R8 is each independently selected from a methyl group, H, or an ester group, q is an integer of 1 - 3, and can be, for example, 1, 2, or 3; m5 is an integer of 1 - 10, and can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; m6 is an integer of 1 - 10, and can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0079] Preferably, a commercially available example of the active ester curing agent represented by AR-2 is HPC-8150-62T manufactured by DIC Corporation.

[0080] Preferably, the filler is an inorganic filler and / or an organic filler.

[0081] Preferably, the inorganic filler includes any one or a combination of at least two of silica, hollow glass microspheres, aluminum nitride, boron nitride, silicon carbide, silicon nitride, titanium dioxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide, magnesium oxide, calcium carbonate, zinc oxide, zirconium oxide, mica, boehmite, calcined talc, talc powder, and calcined kaolin.

[0082] Preferably, the silica includes any one or a combination of at least two of crystalline silica, synthetic silica, spherical silica, fused silica, hollow silica, chemically spherical silica, and composite silica.

[0083] Preferably, the organic filler includes any one or a combination of at least two of polytetrafluoroethylene, polyphenylene sulfide, and polyethersulfone.

[0084] Preferably, the average particle size (D 50 particle size) of the filler is 0.01 - 50 μm, for example, it can be 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, and 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. Further preferably, it is 0.01 - 30 μm, and more preferably 0.2 - 10 μm.

[0085] Exemplarily, the particle size of the filler is obtained by testing with an MS3000 Malvern laser particle size analyzer.

[0086] Preferably, in the resin composition of the present invention, based on 100 parts by mass of the total organic resin, the mass of the filler is 80 - 300 parts, for example, it can be 100 parts, 120 parts, 150 parts, 160 parts, 180 parts, 200 parts, 220 parts, 240 parts, 250 parts, 260 parts or 280 parts, and 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. If the amount of the filler used is too small, the rigidity of the plate is insufficient and the thermal expansion rate is relatively high; if the amount of the filler used is too large, the hardness of the plate is high, which is not conducive to drilling processing.

[0087] Preferably, a radical initiator may also be included in the resin composition of the present invention.

[0088] Preferably, the radical initiator includes organic peroxides, more preferably including any one or a combination of at least two of di-tert-butyl peroxide, benzoyl peroxide, dilauroyl peroxide, cumyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxy pivalate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxy-3,5,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, 2,2-bis(tert-butylperoxy)butane, bis(4-tert-butylcyclohexyl) peroxydicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydicarbonate, di-tert-amyl peroxide, diisopropylbenzene peroxide, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,3-dimethyl-2,3-diphenylbutane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-amyl hydroperoxide, tert-butyl hydroperoxide, cumene tert-butyl peroxide, diisopropylbenzene hydroperoxide, tert-butyl peroxy-2-ethylhexyl carbonate, tert-butyl peroxy-2-ethylhexyl carbonate, n-butyl 4,4-bis(tert-butylperoxy)valerate, methyl ethyl ketone peroxide, cyclohexanone peroxide.

[0089] Preferably, the mass parts of the radical initiator in the resin composition are 0 - 3 parts. For example, it can be 0.001 part, 0.005 part, 0.01 part, 0.05 part, 0.08 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.8 part, 1 part, 1.2 part, 1.5 part, 1.8 part, 2 part, 2.2 part, 2.5 part or 2.8 part, 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. More preferably, the resin composition further includes 0.001 - 3 parts of the radical initiator by mass parts.

[0090] Preferably, a crosslinking agent may also be included in the resin composition.

[0091] Preferably, the crosslinking agent includes any one or a combination of at least two of triallyl isocyanurate, triallyl cyanurate, tricyclodecane dimethanol dimethacrylate, trimethylolpropane trimethacrylate.

[0092] As a preferred technical solution of the present invention, an additive is further included in the resin composition.

[0093] It should be noted that the present invention has no special restrictions on the specific types and dosages of the additives, and those skilled in the art can add them according to the types and requirements of the additives.

[0094] Preferably, the additive includes any one or a combination of at least two of a surfactant, an emulsifier, a toughening agent, a viscosity regulator, a pigment, and a curing accelerator. Typical but non-limiting combinations include: a combination of an emulsifier and a surfactant, a combination of a toughening agent, a curing accelerator, and a pigment, a combination of a surfactant, an emulsifier, a toughening agent, a viscosity regulator, a pigment, and a curing accelerator, etc.

[0095] 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, in the drying, semi-curing or full-curing process, the solvent in the resin composition will partially or completely volatilize.

[0096] There is no particular limitation on the solvent of the present invention. Exemplarily, it includes but is not limited to: ketones such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; aromatic hydrocarbons such as toluene, xylene, mesitylene; esters such as ethoxyethyl acetate, ethyl acetate; nitrogen-containing solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone. The above solvents can be used alone or in combination of two or more. Preferably, it is any one or a combination of at least two of toluene, xylene, mesitylene, acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone.

[0097] During the process of dissolving or dispersing the resin composition in the solvent as described above, an emulsifier can be added. By dispersing with the emulsifier, fillers, etc. can be uniformly dispersed in the glue solution.

[0098] The resin composition provided by the present invention is prepared by the following method. The preparation method includes: mixing and uniformly dispersing each component in the resin composition to obtain the resin composition.

[0099] 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.

[0100] Preferably, the resin film is prepared by coating the resin composition on a release material and drying and / or semi-curing.

[0101] In a third aspect, the present invention provides a resin-coated copper foil, which 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.

[0102] Preferably, the resin-coated copper foil is prepared by coating the resin composition on a copper foil and drying and / or semi-curing.

[0103] Fourth aspect, the present invention provides a prepreg, which prepreg comprises a reinforcing material and a resin composition as described in the first aspect attached to the reinforcing material.

[0104] Preferably, the resin composition is attached to the reinforcing material after impregnation and drying.

[0105] Preferably, the raw material of the reinforcing material includes any one or at least two combinations of natural fiber, organic synthetic fiber, inorganic fiber, and organic fabric; such as fiberglass cloth, quartz fiberglass blended cloth, non-woven fabric, etc.; low-dielectric reinforcing materials can also be selected according to needs, such as NE fiberglass cloth, Q quartz cloth, QL cloth, etc.

[0106] 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.

[0107] Preferably, the drying temperature 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.

[0108] Preferably, the drying time 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.

[0109] On the other hand, the present invention provides a laminate, which laminate comprises at least 1 sheet of prepreg as described in the fourth aspect.

[0110] Fifth aspect, the present invention provides a metal-clad laminate, which metal-clad laminate 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.

[0111] Preferably, the metal foil in the metal-clad laminate includes any one or at least two combinations of copper foil, aluminum foil, nickel foil, and alloy foil, and copper foil is further preferred.

[0112] Preferably, the metal foil is copper foil, and the metal-clad laminate is a copper-clad laminate.

[0113] Preferably, the number of prepregs in the metal-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 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 values included in the above range.

[0114] Exemplarily, the method for preparing the metal-clad laminate includes: laminating a metal foil on one side or both sides of a prepreg and curing to obtain the metal-clad laminate; or, stacking at least two prepregs into a laminate, then laminating a metal foil on one side or both sides of the laminate and curing to obtain the metal-clad laminate.

[0115] Preferably, the curing is carried out in a press.

[0116] 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 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 values included in the above range. Further preferably, it is 200 - 220 °C.

[0117] 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 / cm 2 , as well as the specific 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 values included in the above range.

[0118] Preferably, the curing time is 60 - 300 min, for example, 80 min, 100 min, 120 min, 150 min, 180 min, 200 min, 220 min, 240 min, 260 min, or 280 min, as well as the specific 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 values included in the above range.

[0119] Sixth aspect, the present invention provides a printed circuit board, which includes 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.

[0120] Compared with the prior art, the present invention has the following beneficial effects:

[0121] (1) In the resin composition provided by the present invention, through the component design of maleimide compound, epoxy resin, benzoxazine compound, double-bonded phosphazene, and filler, and the mutual compounding between the components, a highly crosslinked system with interpenetrating molecules of different structures can be cured, so that the resin composition and the metal-clad laminate containing it have the characteristics of high glass transition temperature, high adhesion, high peel strength, low coefficient of thermal expansion, and low dielectric loss, good flame retardancy, and greatly improve the reliability of the substrate material and electronic products.

[0122] (2) Through the component design and optimization of the resin composition, the T of the copper-clad laminate using it g ≥230 °C, the peel strength ≥ 0.9 N / mm, Df at 10 GHz ≤ 0.007, Z-CTE ≤ 1.6%, and it can achieve V-0 level flame retardancy, and has both high T g , low coefficient of thermal expansion, high adhesion, low dielectric loss, and excellent dielectric properties. Specific Embodiments

[0123] The technical solutions 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 to the present invention.

[0124] 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:

[0125]

[0126]

[0127] The resin composition and the metal-clad laminate of the present invention will be described in detail below with multiple embodiments as examples, but the resin composition and the metal-clad laminate are not limited to these embodiments.

[0128] Examples 1-5, Comparative Examples 1-8

[0129] A resin composition, the types and dosages of each component are shown in Table 1 and Table 2, and the dosage unit of each component is "part" (mass part).

[0130] A prepreg and a copper clad laminate comprising the resin composition are prepared as follows:

[0131] (1) Charge each component of the resin composition according to the formulation amount, add 90 parts of methyl ethyl ketone, and mechanically stir for 4 h to dissolve and cure to prepare a glue solution;

[0132] (2) Immerse 2116E-glass fiber cloth in the glue solution obtained in step (1), remove part of the liquid resin through the nip rolls of rolling, 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 145 °C for 4.5 min to obtain a prepreg with a thickness of 0.125 mm;

[0133] (3) Prepare an electrolytic copper foil with a thickness of 18 μm, stack 4 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 stacked sheets, put them into a laminator and laminate according to the following conditions:

[0134] 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 220 °C, and keep it for 120 min for curing to obtain the copper clad laminate.

[0135] Perform performance tests on the copper clad laminate, and the specific method is as follows:

[0136] (1) Glass transition temperature (T g ): Use dynamic thermomechanical analysis (DMA) and measure according to the DMA method specified in IPC-TM-650 2.4.24.4;

[0137] (2) Peel strength (PS): Test the peel strength of the metal cover layer according to the "after thermal stress" experimental conditions in the method of IPC-TM-650 2.4.8;

[0138] (3) Dielectric constant Dk and dielectric loss factor Df: Measure according to the method specified in IPC-TM-650 2.5.5.13 using the split dielectric post resonator method (SPDR) at 10 GHz;

[0139] (4) Flame retardancy: Test and classify according to the material flammability method specified in UL-94;

[0140] (5) Thermal expansion coefficient Z-CTE: Test the thermal expansion rate of the sheet in the Z-axis direction from 50 to 260 °C according to the method specified in IPC-TM-650 2.4.24;

[0141] The performance test data are shown in Table 1 and Table 2.

[0142] Table 1

[0143]

[0144]

[0145] Table 2

[0146]

[0147]

[0148] According to the performance data in Table 1, it can be seen that the present invention forms a highly crosslinked system with interpenetrating molecules of different structures in the cured product through the design of maleimide compounds containing indane structures, epoxy resins, benzoxazine compounds, double-bonded phosphazenes, fillers and the mutual compounding of each component, enabling the resin composition and the copper-clad laminate containing the same to achieve the characteristics of high glass transition temperature, high peel strength, low coefficient of thermal expansion, and low dielectric loss. Specifically, for the copper-clad laminates of Examples 1-5, T g ≥230 °C, peel strength ≥ 0.9 N / mm, Df at 10 GHz ≤ 0.0068, Z-CTE ≤ 1.6%, and can achieve V-0 level flame retardancy.

[0149] Comparing Table 1 and Table 2, it can be seen that the maleimide compound in Comparative Example 1 does not contain an indane structure, and in Comparative Example 2, the content of the maleimide resin containing an indane structure is too low, resulting in deterioration of T g , peel strength and Z-CTE. In Comparative Example 3, the dosage of the epoxy resin is too high while the dosage of the maleimide compound is insufficient, resulting in deterioration of T g , dielectric properties and Z-CTE. In Comparative Example 4, the dosage of benzoxazine is too low, resulting in deterioration of T g and Z-CTE. In Comparative Example 5, the dosage of the double-bonded phosphazene is too small, resulting in poor flame retardancy. In Comparative Example 6, a non-reactive phosphazene without double bonds is used, resulting in deterioration of T g and peel strength. In Comparative Example 7, the dosage of benzoxazine is too high, resulting in poor dielectric loss. In Comparative Example 8, the dosage of the double-bonded phosphazene is too high, resulting in deterioration of T g and Z-CTE.

[0150] The applicant declares that the present invention uses the above examples to illustrate the resin composition, metal-clad laminate and printed circuit board of the present invention, but 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 product of the present invention, the addition of auxiliary components, 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 The resin composition comprises the following components in parts by mass: The mass percentage of the maleimide resin containing indane structure in the maleimide compound is ≥50%.

2. The resin composition according to claim 1, characterized in that The indane structure-containing maleimide resin has a structure as shown in Formula I: Wherein, m is selected from an integer of 1-10; R1 and R2 are each independently selected from any one of C1-C5 straight or branched alkyl, C1-C5 alkoxy or phenyl; p1 and p2 are each independently selected from an integer of 0-4; Preferably, the maleimide compound further comprises a second maleimide resin; Preferably, the second maleimide resin has a structure as shown in Formula II: Wherein, L is selected from any one of the following groups: -* indicates the attachment site of the group; R3, R4, and R5 are each independently selected from any one of a C1-C5 straight or branched alkyl group and a phenyl group; n1 is an integer selected from 1 to 10; m1, m2, and m3 are each independently selected from integers of 0-3.

3. The resin composition according to claim 1 or 2, characterized in that The epoxy resins include linear phenolic epoxy resins, cresol phenolic epoxy resins, bisphenol A phenolic epoxy resins, phenol phenolic epoxy resins, trifunctional phenolic epoxy resins, tetrafunctional phenolic epoxy resins, naphthalene epoxy resins, naphthol epoxy resins, naphthol phenolic epoxy resins, anthracene epoxy resins, phenolphthalein epoxy resins, phenoxy epoxy resins, norbornene epoxy resins, adamantane epoxy resins, fluorene epoxy resins, biphenyl epoxy resins, biphenylphenol epoxy resins, tetramethyl Any one of biphenyl epoxy resin, dicyclopentadiene epoxy resin, dicyclopentadiene phenol epoxy resin, dicyclopentadiene novolac epoxy resin, aralkyl epoxy resin, aralkyl novolac epoxy resin, epoxy resin containing arylene ether structure, epoxy resin containing arylene ester structure, alicyclic epoxy resin, polyol epoxy resin, silicon-containing epoxy resin, nitrogen-containing epoxy resin, phosphorus-containing epoxy resin, glycidylamine epoxy resin, glycidylester epoxy resin, or a combination of at least two thereof; Preferably, the epoxy resin comprises a multifunctional epoxy resin containing an aromatic ring and / or a heteroaromatic ring.

4. The resin composition according to any one of claims 1 to 3, characterized in that The benzoxazine compound includes a diamine-type benzoxazine resin and / or a diphenol-type benzoxazine resin; Preferably, the benzoxazine compound comprises any one or a combination of at least two of the compound represented by the structure of Formula III and the compound represented by the structure of Formula IV; Wherein, X1 is selected from any one of the following groups: -* indicates the attachment site of the group; X2 is selected from any one of -CH2-, -O-, -S(O)2- or -C(CH3)2-; R 11 , R 12 Each is independently selected from any one of vinyl, propenyl, allyl or phenyl; R 13 , R 14 Each independently selected from any one of C1-C5 straight or branched alkyl groups; n1 and n2 are each independently selected from integers of 0-4.

5. The resin composition according to any one of claims 1 to 4, characterized in that The double-bond-containing phosphazene includes any one or a combination of at least two of the compounds of formula V and formula VI: Wherein, Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, Ar7, Ar8 are each independently selected from R is selected from any one of vinyl, allyl, acryloyl or methacryloyl; The group in the compound The molar mass is n 11 , group The molar mass is n 12 , n 11 :n 12 is 1:(0.3-3); Preferably, the filler is an inorganic filler and / or an organic filler; Preferably, the inorganic filler includes any one or a combination of at least two of silicon dioxide, hollow glass microspheres, aluminum nitride, boron nitride, silicon carbide, silicon nitride, titanium dioxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide, magnesium oxide, calcium carbonate, zinc oxide, zirconium oxide, mica, boehmite, calcined talc, talc powder, and calcined kaolin; Preferably, the organic filler includes any one of polytetrafluoroethylene, polyphenylene sulfide, and polyether sulfone, or a combination of at least two thereof; Preferably, the average particle size of the filler is 0.01-50 μm; Preferably, the resin composition further comprises 0.001-3 parts by mass of a free radical initiator; Preferably, the free radical initiator comprises an organic peroxide.

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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