Thermosetting compositions, cured compositions based on thermosetting compositions, prepregs and laminates

Abstract

The present disclosure relates to thermoset compositions suitable for use in the manufacture of electronic materials, such as circuit board substrates, as well as cured compositions, prepregs, and laminates based on such thermoset compositions. One aspect of the present disclosure is a thermoset composition comprising: an aromatic epoxy resin component; a poly(styrene-co-maleic anhydride) component; an oligomer component bearing maleimides; the oligomer component bearing maleimides having a number average of at least 4 maleimides per molecule, by number average, and a softening point of no higher than 100 °C; a benzoxazine / maleimide component that is a bis(benzoxazine) subcomponent and a bis(maleimide) subcomponent and / or reaction products thereof; an aromatic primary diamine component; a microparticulate silica; an organic, halogen-free flame retardant component; an effective amount of one or more catalysts.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 588,417, filed October 6, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to thermosetting compositions suitable for manufacturing electronic materials (such as circuit board substrates), and cured compositions, prepregs, and laminates based on such thermosetting compositions. Background Technology

[0004] Prepreg and copper-clad laminate are planar materials commonly used in the manufacture of printed circuit boards. Prepreg and laminate are typically composite structures that include reinforcing materials (such as woven glass fiber, nonwoven glass fiber, paper or other fibrous and non-fibrous materials) and a polymer resin (a material applied to or used to impregnate the reinforcing material) as a matrix material.

[0005] As the operating frequencies of electronic devices continue to increase, careful control of the electrical properties of prepregs and laminates is becoming increasingly important. The electrical properties of circuit boards involve a variety of parameters, including dielectric constant (Dk), dielectric loss tangent (Df), insulation resistance, surface resistance, volume resistivity, arc resistance, CTI or relative tracking index, and electrical strength.

[0006] However, electrical properties are not the only necessary performance criteria. Instead, various other properties are also required. These include resistance to chemical reagents, thermal properties (such as glass transition temperature, dimensional stability, and Z-axis coefficient of thermal expansion); mechanical properties (such as strength and dimensional stability); and adhesion to copper foil (measured by peel strength).

[0007] Furthermore, fire resistance is a highly desirable property for these materials. Many conventional flame retardants are halogenated compounds. However, it is highly desirable to offer flame retardancy without using halogenated compounds in the market.

[0008] What people need now is new materials that not only have good dielectric properties (especially at high frequencies), but also perform well in a variety of other properties. Summary of the Invention

[0009] One aspect of this disclosure is a thermosetting composition comprising: Aromatic epoxy resin components are present in a total amount ranging from 5 to 25 wt%. The poly(styrene-co-maleic anhydride) component is present in an amount ranging from 8 to 30 wt%. The oligomer component containing maleimide, in an amount ranging from 2 to 10 wt%, has a number average of at least 3 maleimides per molecule, and a softening point not higher than 100 °C. The benzoxazine / maleimide component, which is a bis(benzoxazine) sub-component and a bis(maleimide) sub-component and / or its reaction product, exists in an amount ranging from 2 to 20 wt%. The aromatic primary diamine component, in an amount of 0.1-2 wt%; Microparticles of silica, in the range of 15-50 wt%; Organic halogen-free flame retardant component, in an amount of 3-25 wt%; and An effective amount of one or more catalysts.

[0010] Another aspect of this disclosure is the cured (e.g., partially cured or substantially fully cured) product of the thermosetting composition as described herein.

[0011] Another aspect of this disclosure is a method for curing a thermosetting composition as described herein, the method comprising heating the thermosetting composition at a temperature of 150-250 °C.

[0012] Another aspect of this disclosure is a prepreg comprising a mesh substrate at least partially embedded in the cured product described herein.

[0013] Another aspect of this disclosure is laminates of various prepregs as described herein.

[0014] Brief description of the attached figures

[0015] Figure 1 This is a schematic cross-sectional view of a prepreg according to one embodiment of the present disclosure.

[0016] Figure 2 This is a schematic cross-sectional view of a laminate according to one embodiment of the present disclosure. Invention Details

[0018] The inventors have developed specific thermosetting compositions that can provide excellent high-frequency dielectric properties, as well as good thermal properties and peel strength properties.

[0019] One aspect of this disclosure is a thermosetting composition comprising: Aromatic epoxy resin components are present in a total amount of 5-25 wt%; The poly(styrene-co-maleic anhydride) component is present in an amount ranging from 8 to 30 wt%. The oligomer component containing maleimide, in an amount ranging from 2 to 10 wt%, has a number average of at least 3 maleimides per molecule, and a softening point not higher than 100 °C. The benzoxazine / maleimide component, which is a bis(benzoxazine) sub-component and a bis(maleimide) sub-component and / or its reaction product, exists in an amount ranging from 2 to 20 wt%. The aromatic primary diamine component, in an amount of 0.1-2 wt%; Microparticles of silica, in the range of 15-50 wt%; Organic halogen-free flame retardant component, in an amount of 3-25 wt%; and An effective amount of one or more catalysts.

[0020] As used herein, thermosetting compositions are essentially liquid compositions that solidify from a liquid state to a solid state under the influence of heat. Various particularly desirable thermosetting compositions are those that are “B-stageable,” meaning they can be partially cured into a workable solid under a first heat treatment, and then fully cured under a subsequent second heat treatment. Partially cured materials may, for example, be in the so-called “B-stage” and can be further cured to the so-called “C-stage.” Those skilled in the art of electronic materials are familiar with the use of thermosetting compositions as described herein in the production of various products, such as prepregs, resin films, resin-coated copper foils, laminates, and printed circuit boards.

[0021] One component of the thermosetting composition disclosed herein is an aromatic epoxy resin component, present in a total amount ranging from 5 to 25 wt%. As used herein, the aromatic epoxy resin component comprises one or more aromatic epoxy resin sub-components, which, on a number-average basis, each molecule of these sub-components carries at least two epoxy groups. The aromatic epoxy resin component is ideally liquid at 25 °C. The inventors have noted that the aromatic epoxy resin component can provide a variety of advantageous properties to materials, including sufficiently rapid curing (together with other components of the composition), flame retardancy and self-extinguishing properties, thermal stability, chemical resistance, and adhesive strength (e.g., for glass and metallic materials).

[0022] Based on the description herein, those skilled in the art can determine an appropriate amount of the aromatic epoxy resin component in the range of 5-25 wt%. For example, in various embodiments of the thermosetting compositions as further described herein, the amount of the aromatic epoxy resin component is in the range of 5-20 wt%, or 5-17 wt%, or 5-15 wt%, or 7-25 wt%, or 7-17 wt%, or 7-15 wt%, or 10-25 wt%, or 10-20 wt%, or 10-17 wt%, or 10-15 wt%.

[0023] Ideally, the aromatic epoxy resin component has a high aromatic fraction. This contributes to providing high thermal stability and flame retardancy, especially when the aromatic epoxy resin component is substantially halogen-free (e.g., no more than 1 wt% halogen, or no more than 0.5 wt% halogen). As used herein, the “aromatic carbon fraction” of a material is the percentage of aromatic carbon atoms in the material. For example, anthracene has an aromatic carbon fraction of 100%, while tetramethylbenzene has an aromatic carbon fraction of 60%. In various embodiments further described herein, the aromatic carbon fraction of the aromatic epoxy resin component is at least 60%, for example, at least 65%. In various embodiments further described herein, the aromatic carbon fraction of the aromatic epoxy resin component is at least 70%, for example, at least 75%. However, it is ideal to have some non-aromatic properties to provide a degree of molecular flexibility and to be responsible for the epoxy carbon that constitutes the material. Therefore, in various embodiments, the aromatic carbon content of the aromatic epoxy resin component is in the range of 60-85%, for example 65-85%, or 60-82%, or 65-82%, or 60-80%, or 65-80%, or 60-75%, or 65-75%. In various embodiments, the aromatic carbon content of the aromatic epoxy resin component is in the range of 70-85%, for example 75-85%, or 70-82%, or 75-82%, or 70-80%, or 75-80%.

[0024] The inventors point out that a variety of aromatic epoxy resins can be used in the compositions disclosed herein. For example, in various embodiments as further described herein, the aromatic epoxy resin component comprises one or more of the following: phenolic epoxy resins (e.g., biphenyl phenolic epoxy resins, phenolic epoxy resins, cresol phenolic epoxy resins), bisphenol epoxy resins (e.g., bisphenol A epoxy resins, bisphenol F epoxy resins, and bisphenol S epoxy resins), biphenyl epoxy resins, xylene epoxy resins, arylalkylene epoxy resins (e.g., phenol aralkyl epoxy resins, biphenyl aralkyl epoxy resins, biphenyl phenolic epoxy resins, biphenyl dimethyl epoxy resins, triphenol methane phenolic epoxy resins, and tetramethylbiphenyl epoxy resins); and naphthalene epoxy resins.

[0025] Those skilled in the art will understand that in phenolic epoxy resins (such as bisphenol type epoxy resins or phenolic type epoxy resins) as described herein, some minor degree of phenolic properties may be retained (e.g., no more than 5% of phenolic oxygen groups are not substituted by epoxy-containing substituents), while the resin is still represented by the general formula provided herein.

[0026] Particularly suitable are the NC-3000 and NC-2000 series resins from Nippon Kayaku; KES-7370 is available from Kolon Industries; and resins from Chang Chun Petrochemical (Chang Chun Petrochemical A) are also suitable. l PNE series materials (e.g., PNE-177) obtained from PNE.

[0027] In various preferred embodiments, the aromatic epoxy resin component comprises at least one biphenyl-type phenolic epoxy resin (e.g., biphenyl aralkyl epoxy resin). In various embodiments, said at least one biphenyl-type phenolic epoxy resin comprises (or is) a resin having the following general structure:

[0028] Each R1 and R2 is independently an alkyl group having 1 to 4 carbon atoms; a is in the range of 0 to 3, b is in the range of 0 to 4; and the numerical mean of n is in the range of 1 to 6 (e.g., 2-6, or 3-6, or 1-5, or 2-5, or 3-5). In various embodiments, each R1 and R2 is independently methyl or ethyl, and each a and b is independently 0, 1, or 2. In various embodiments, each a and b is 0. In various embodiments, the at least one biphenyl-type phenolic epoxy resin comprises (or is) a resin having the following general structure:

[0029] The mean value of n is in the range of 1-6 (e.g., 2-6, or 3-6, or 1-5, or 2-5, or 3-5). The inventors have noted that such materials can enhance the thermal stability, flame retardancy, and self-extinguishing properties of materials made from this thermosetting composition, while providing good reactivity and network formation.

[0030] The at least one biphenyl-type phenolic resin may be present in the thermosetting composition in various amounts, for example in the range of 5-25 wt%, or in the range of 5-20 wt%, or 5-17 wt%, or 5-15 wt%, or 7-25 wt%, or 7-17 wt%, or 7-15 wt%, or 10-25 wt%, or 10-20 wt%, or 10-17 wt%, or 10-15 wt%.

[0031] In various preferred embodiments, the aromatic epoxy resin component comprises at least one phenolic epoxy resin. In various embodiments, said at least one phenolic epoxy resin has the following common structure:

[0032] Each R1 is independently an alkyl group having 1 to 4 carbon atoms; a is in the range of 0 to 3, and the number mean of n is in the range of 1 to 6 (e.g., 2-6, or 3-6, or 1-5, or 2-5, or 3-5). In various embodiments, each R 1 The a is independently methyl or ethyl, and each a is independently 0, 1, or 2. In various embodiments, each a is 0. One example of such a resin (where each a is 0) is available from Changchun Petrochemical under the designation PNE-177, and has an epoxy equivalent (g / eq) of 172-182 in its pure state and a viscosity of 20,000-80,000 cps at 52 °C; materials with added solvents (e.g., acetone, MEK, or xylene) with lower viscosity are also available. The inventors note that such materials can enhance the adhesion and chemical resistance of materials made from this thermosetting composition.

[0033] The at least one phenolic resin can be present in the thermosetting composition in various amounts, such as 5-25 wt%, 5-20 wt%, 5-17 wt%, 5-15 wt%, 7-25 wt%, 7-17 wt%, 7-15 wt%, 10-25 wt%, 10-20 wt%, 10-17 wt%, or 10-15 wt%. However, the inventors have noted that at higher levels, the flame retardancy may decrease. Therefore, in various preferred embodiments, the amount of phenolic epoxy resin is in the range of 1-10 wt%, such as 1-7 wt%, 1-5 wt%, 2-10 wt%, 2-7 wt%, 2-5 wt%, 3-10 wt%, 3-7 wt%, or 3-5 wt%.

[0034] In various desirable embodiments, the aromatic epoxy resin component comprises both biphenyl-type phenolic epoxy resin and phenolic epoxy resin. For example, in various such embodiments, the weight ratio of biphenyl-type phenolic epoxy resin to phenolic epoxy resin is in the range of 1:1 to 15:1, such as 2:1 to 10:1, or 2:1 to 5:1, or 2:1 to 3:1. The inventors point out that using such a ratio can provide a good balance between adhesive strength and chemical resistance and flame retardancy and thermal stability.

[0035] Aromatic epoxy resin components can have various epoxy equivalent values, for example, in the range of 150 g / eq to 350 g / eq.

[0036] The inventors note that non-aromatic epoxy resins may be present in some embodiments of the thermosetting compositions as generally described herein. However, it should be noted that this is not necessary, and when such materials are included in high amounts, it may be detrimental to the various desirable properties of materials made from the thermosetting compositions of this disclosure. Therefore, in the various embodiments further described herein, the amount of any non-aromatic epoxy resin does not exceed 10 wt%, for example, not more than 5 wt%, or not more than 2 wt%, or not more than 1 wt%.

[0037] As described above, the thermosetting compositions of this disclosure also include a poly(styrene-co-maleic anhydride) component. The inventors have noted that such materials contribute to enhancing the heat resistance and dielectric properties (e.g., Dk and Df) of materials made using the thermosetting compositions of this disclosure.

[0038] Based on the description herein, those skilled in the art can determine an appropriate amount of the poly(styrene-co-maleic anhydride) component in the range of 8-30 wt%. For example, in various embodiments, the amount of the poly(styrene-co-maleic anhydride) component is in the range of 8-25 wt%, or 8-22 wt%, or 8-20 wt%, or 8-18 wt%, or 10-30 wt%, or 10-25 wt%, or 10-22 wt%, or 10-20 wt%, or 10-18 wt%. In various embodiments, the amount of the poly(styrene-co-maleic anhydride) component is in the range of 12-30 wt%, for example, 12-25 wt%, or 12-22 wt%, or 12-20 wt%, or 12-18 wt%, or 14-30 wt%, or 14-25 wt%, or 14-22 wt%, or 14-20 wt%, or 14-18 wt%.

[0039] Those skilled in the art will understand that various poly(styrene-co-maleic anhydride) products with different molar ratios of styrene / maleic anhydride residues are available, such as 8:1, 6:1, 4:1, and 3:1. Ideally, the poly(styrene-co-maleic anhydride) component contains no more than 5 wt% of non-styrene residues or maleic anhydride residues (i.e., analogs of their acids), for example, no more than 2 wt% or no more than 1 wt%.

[0040] The inventors have noted that the styrene / maleic anhydride residue ratio of the poly(styrene-co-maleic anhydride) component can be selected to provide a desired set of properties to materials made from the thermosetting composition. For example, a relatively higher number of maleic anhydride residues can benefit better electrical properties, while a relatively higher number of styrene residues can provide an increased glass transition temperature. In various examples, the styrene / maleic anhydride residue ratio of the poly(styrene-co-maleic anhydride) component is in the range of 2:1 to 6:1, for example, 2:1 to 5:1, or 2:1 to 4:1, or 2.5:1 to 6:1, or 2.5:1 to 5:1, or 2.5:1 to 4:1, or 3:1 to 6:1, or 3:1 to 5:1, or 3:1 to 4:1.

[0041] The inventors point out that a ratio in the range of 3:1 to 4:1 can provide a particularly desirable balance of performance. This can be provided by a poly(styrene-co-maleic anhydride) component comprising (or being) a blend of a first poly(styrene-co-maleic anhydride) polymer with a styrene / maleic anhydride residue ratio in the range of 2.8:1 to 3.2:1 and a second poly(styrene-co-maleic anhydride) polymer with a styrene / maleic anhydride residue ratio in the range of 3.8:1 to 4.2:1. XIRAN® EF30 and XIRAN® EF40, available from Polyscope, are examples of products suitable for use in ratios of 3:1 and 4:1.

[0042] As described above, the thermosetting compositions of this disclosure also include oligomer components containing maleimide. As used herein, the oligomer components containing maleimide have at least three maleimide molecules per molecule on a number-average basis, and a softening point not exceeding 100 °C as measured in a ring and ball softening test (e.g., according to ISO 18280 or JIS K7234). The inventors have noted that the use of such materials can enhance the toughness and thermal reliability of materials made from thermosetting compositions and reduce warping. Furthermore, they generally contribute to improving the solubility of the components within the thermosetting composition.

[0043] Those skilled in the art can determine, based on the description herein, an appropriate amount of maleimide-containing oligomer component for use in thermosetting compositions, ranging from 2 to 10 wt%. For example, in various embodiments further described herein, the amount of maleimide-containing oligomer component is in the range of 2-9 wt%, or 2-7 wt%, or 3-10 wt%, or 3-9 wt%, or 3-7 wt%, or 5-10 wt%, or 5-9 wt%, or 5-7 wt%.

[0044] In various embodiments, on an average basis, each molecule of the maleimide-containing oligomer component has at least 4 maleimides, for example, at least 5 or at least 6. In various embodiments, on an average basis, each molecule of the maleimide-containing oligomer component has 3-10 maleimides, for example, in the range of 4-10, 5-10, 6-10, 3-9, 4-9, 5-9, or 6-9. In various embodiments, on an average basis, each molecule of the maleimide-containing oligomer component has 3-8 maleimides, for example, in the range of 4-8, 5-8, 6-8, 3-7, 4-7, or 5-7.

[0045] Maleimide-containing oligomers ideally have a relatively high aromatic carbon content to improve thermal stability and various other properties. In various embodiments further described herein, the aromatic carbon fraction of the maleimide-containing oligomer component is at least 80%, for example at least 84% or at least 88%.

[0046] In various embodiments, the softening point of the maleimide-containing component, as determined in a ring and ball softening test (e.g., according to ISO 18280 or JIS K7234), is not higher than 95 °C, for example, not higher than 90 °C. In various embodiments, the softening point of the maleimide-containing component, as determined in a ring and ball softening test (e.g., according to ISO 18280 or JIS K7234), is in the range of 70-100 °C, for example, 75-100 °C, or 80-100 °C, or 70-95 °C, or 75-95 °C, or 80-95 °C, or 70-90 °C, or 75-90 °C, or 80-85 °C, or 75-85 °C. In various embodiments, the softening point of the oligomer component containing maleimide, as determined in a ring and ball softening test (e.g., according to ISO 18280 or JIS K7234), is in the range of 80-95 °C, or 70-90 °C, or 75-90 °C, or 80-90 °C, or 70-85 °C, or 75-85 °C, or 80-85 °C.

[0047] Various oligomers containing maleimide are suitable for use in the thermosetting compositions of this disclosure. In various embodiments further described herein, the oligomers containing maleimide have the following general formula:

[0048] Where n is chosen to provide the ideal number of maleimide residues per molecule as described elsewhere.

[0049] As described above, the thermosetting composition further includes a benzoxazine / maleimide component, which is a bis(benzoxazine) sub-component and a bis(maleimide) sub-component and / or their reaction products, in an amount ranging from 2 to 20 wt%. The inventors have found that the use of such components (whether as individual components or as prepolymers of their reaction products) can enhance flame retardancy, improve electrical properties (such as Dk and Df), and provide good dimensional stability to materials made from the thermosetting composition.

[0050] As used herein, a bis(benzoxazine) subcomponent is a monomeric subcomponent having two reactive benzoxazine moieties, which may themselves be N-substituted (e.g., substituted with alkyl or phenyl groups). Similarly, a bis(maleimide) subcomponent is a monomeric subcomponent having two reactive maleimide moieties.

[0051] Those skilled in the art can provide suitable amounts of the benzoxazine / maleimide component in the range of 2-20 wt% based on the disclosure herein. For example, in various embodiments as further described herein, the amount of the benzoxazine / maleimide component is in the range of 2-17 wt%, or 2-15 wt%, or 2-12 wt%, or 2-9 wt%, or 4-20 wt%, or 4-17 wt%, or 4-15 wt%, or 4-12 wt%, or 4-9 wt%, or 6-20 wt%, or 6-17 wt%, or 6-15 wt%, or 6-12 wt%, or 6-9 wt%.

[0052] Various bis(benzoxazine) sub-components are suitable for use with benzoxazine / maleimide components. For example, in various embodiments, the bis(benzoxazine) sub-component comprises (or is) one or more of the following:

[0053] Each of X1 and X2 is independently an arylene (e.g., phenylene, biphenylene, naphthylene); a C1-C3 alkylene (ideally substituted on the same carbon, e.g., -C(CH3)2-, CH(CH3), CH2) or S(O). 0-2 For example, in various embodiments, the bis(benzoxazine) sub-component comprises (or is) one or more of the following:

[0054] For example, in various preferred embodiments, the bis(benzoxazine) sub-component comprises (or is) bisphenol F benzoxazine.

[0055] Various bis(maleimide) sub-components are suitable for use with benzoxazine / maleimide components. For example, in various embodiments, the bis(maleimide) sub-component comprises (or is) one or more of the following: 4,4'-dimaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane, 2,2-bis[4-(4-maleimide-phenoxy)phenyl]propane, m-phenylene dimaleimide, 4-methyl-1,3-phenylene dimaleimide, and N,N'-1,4-phenylene dimaleimide. For example, in various embodiments, the bis(maleimide) sub-component comprises (or is) 4,4'-dimaleimide diphenylmethane.

[0056] In various embodiments as further described herein, the benzoxazine / maleimide component is provided as a prepolymer of a bis(benzoxazine) subcomponent and a bismaleimide subcomponent (e.g., bisphenol F benzoxazine / 4,4'-dimaleimide diphenylmethane prepolymer). This prepolymer can be further derivatized, for example, to reduce the OH content. A suitable prepolymer material is LZ-8298, available from Huntsman.

[0057] The ratio of the bis(benzoxazine) subcomponent to the bis(maleimide) subcomponent can vary. Each of the benzoxazine and maleimide can react with itself and with the other components of the thermosetting composition, so the subcomponents do not need to be molar equal. In various embodiments, the molar ratio of the bis(benzoxazine) subcomponent to the bis(maleimide) subcomponent is in the range of 2:1 to 1:2, for example, in the range of 1.5:1 to 1:2, or 1.25:1 to 1:2, or 1:1 to 1:2, or 2:1 to 1:1.5, or 1.5:1 to 1:1.5, or 1.25:1 to 1:1.5, or 1:1 to 1:1.5, or 2:1 to 1:1.25, or 1.5:1 to 1:1.25, or 1.25:1 to 1:1.25, or 1:1 to 1:1.25, or 2:1 to 1:1, or 1.5:1 to 1:1, or 1.25:1 to 1:1. In other embodiments, the molar ratio of the bis(benzoxazine) subcomponent to the bis(maleimide) subcomponent is in the range of 9:1 to 2:1, for example, 7:1 to 2:1, or 5:1 to 2:1, or 4:1 to 2:1. In other embodiments, the molar ratio of the bis(benzoxazine) subcomponent to the bis(maleimide) subcomponent is in the range of 1:9 to 1:2, for example, 1:7 to 1:2, or 1:5 to 1:2, or 1:4 to 1:2.

[0058] The benzoxazine / maleimide component ideally has a high aromatic content. For example, in various embodiments, the aromatic carbon content of the benzoxazine / maleimide component is at least 60%, such as at least 65%, or at least 67%, or at least 70%. Of course, those skilled in the art will understand that the oxazine carbon is not aromatic, and the residues derived from maleimide in the prepolymer may also not be aromatic.

[0059] As described above, the thermosetting compositions of this disclosure also include an aromatic primary diamine component. The inventors have noted that the use of an aromatic primary diamine can increase the crosslinking density of the system, thereby improving many properties.

[0060] Based on this disclosure, those skilled in the art can determine an appropriate amount of the aromatic primary diamine component within the range of 0.05-2 wt%. For example, in various embodiments, the amount of the aromatic primary diamine component is 0.05-1.5 wt%, or 0.05-1 wt%, or 0.05-0.7 wt%, or 0.1-2 wt%, or 0.1-1.5 wt%, or 0.1-1 wt%, or 0.1-0.7 wt%.

[0061] Various aromatic primary diamines are suitable for use in the thermosetting compositions of this disclosure. In various embodiments, the aromatic primary diamine component comprises (or is) 4,4'-(diaminodiphenyl) sulfone, 4,4'-diaminodiphenyl (ether), or 4,4'-diaminodiphenyl (methane). In various embodiments, the aromatic primary diamine component comprises (or is) 4,4'-(diaminodiphenyl) sulfone.

[0062] The aromatic primary diamine component ideally has a high aromatic content. For example, in various embodiments, the aromatic primary diamine component has an aromatic carbon content of at least 90%, such as at least 95%, at least 98%, or at least 99%.

[0063] The thermosetting composition also includes microparticles of silica in an amount ranging from 15 to 50 wt%. As used herein, the microparticles of silica are at least 95 wt% SiO2 and d 50 Particulate materials with a particle size ranging from 0.1 to 100 micrometers. In various embodiments, the d... 50 The particle size is in the range of 0.5-10 micrometers, for example 0.5-7 micrometers, or 0.5-5 micrometers, or 1-10 micrometers, or 1-7 micrometers, or 1-5 micrometers. In various embodiments, the d90 particle size of the micro-particle silica is in the range of 1-20 micrometers, for example 1-14 micrometers, or 1-8 micrometers, or 3-20 micrometers, or 3-14 micrometers, or 3-8 ... 10The particle size is in the range of 0.1-5 micrometers, for example 0.1-3 micrometers, or 0.1-2 micrometers, or 0.5-5 micrometers, or 0.5-3 micrometers, or 0.5-2 micrometers. In various embodiments, the microparticles of silica have at least 99 wt% SiO2, for example at least 99.5 wt% SiO2.

[0064] Microcrystalline silica particles are ideally substantially spherical. Those skilled in the art can verify sphericity using a microscope.

[0065] Suitable micro-particle silica is available from a variety of suppliers, including DQ-1028L from Novoray; SS-15V from Sibelco; and FB-3SDC and FB-3SDX from Denka Co. Ltd.

[0066] The amount of microparticle silica can vary. For example, in various embodiments, the amount of microparticle silica is in the range of 15-45 wt%, or 15-40 wt%, or 15-35 wt%. In various specific embodiments, the amount of microparticle silica is in the range of 20-50 wt%, for example, 20-45 wt%, or 20-40 wt%, or 20-35 wt%. In various specific embodiments, the amount of microparticle silica is in the range of 20-50 wt%, for example, 25-45 wt%, or 25-40 wt%, or 25-35 wt%.

[0067] The thermosetting composition also includes an organic halogen-free flame retardant component in an amount of 3-25 wt%. In various embodiments, the organic halogen-free flame retardant comprises phosphorus.

[0068] Certain flame retardants described in U.S. Patents 8,536,256, 9,012,546, 9,522,927, and 9,562,063 are suitable for use in the thermosetting compositions described herein. Therefore, these patents are incorporated herein by reference in their entirety, the text of which is reproduced below; this disclosure contemplates the use of any flame retardant generalized or specifically described in any of these patents as part of the organic halogen-free flame retardant component of the thermosetting compositions of this disclosure, alone or in combination. For example, in various embodiments, the organic halogen-free flame retardant component includes (or is) 6H-dibenzo[c,e][1,2]oxophosphacyclohexane, 6,6′-(1,4-ethylenediyl)bis-,6,6′-dioxide; 6H-dibenzo[c,e][1,2]oxophosphacyclohexane, 6,6′-(1,4-butadiyl)bis-,6,6′-dioxide; or 6H-dibenzo[c,e][1,2]oxophosphacyclohexane, 6,6′-(p-xylyldiyl)bis-,6,6′-dioxide; or any combination thereof. In various embodiments, the flame retardant component includes (or is) 6H-dibenzo[c,e][1,2]oxophosphacyclohexane, 6,6′-(1,4-ethylenediyl)bis-,6,6′-dioxide. In various embodiments, the flame retardant component comprises (or is) a compound having the following structure:

[0069] In various embodiments, the flame retardant component comprises (or is) a composition containing a high-melting-point isomer of formula IIa:

[0070] And low-melting-point isomers having the following formulas IIb and IIc:

[0071] The isomer ratio of the composition, as determined by 31P NMR, is greater than about 0.5, and the isomer ratio = A h / (A h +A l ), where A h : Peak area of ​​high melting point isomer, A l : Peak area of ​​low melting point isomers.

[0072] Another particularly suitable phosphorus-based flame retardant is a diarylphosphine oxide-based flame retardant. Therefore, in various embodiments as further described herein, the organic halogen-free flame retardant component comprises (or is) a diarylphosphine oxide-based flame retardant, such as a diphenylphosphine oxide-based flame retardant. In various embodiments, the organic halogen-free flame retardant component comprises (or is) a compound having the following structural formula:

[0073] R1 is selected from covalent bonds, -CH2-,

[0074] Where R 11 R 12 R 13 and R 14 Independently H, alkyl or

[0075] For example, in various embodiments, the halogen-free flame retardant comprises (or is) xylyldiphenylphosphine oxide represented by the following formula: .

[0076] However, those skilled in the art will understand that other halogen-free flame retardants may be used in addition to, or even in place of, those mentioned above. Examples include phosphorus-containing flame retardants such as ammonium polyphosphate, hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenyl phosphate), tris(2-carboxyethyl)phosphine (TCEP), tri(chloroisopropyl) phosphate, trimethyl phosphate (TMP), dimethyl methylphosphonate (DMMP), bis(dimethylbenzyl) isophthalate (RDXP, such as commercially available PX-200, PX-201 and PX-202), phosphazenes (such as commercially available SPB-100, SPH-100 and SPV-100), melamine polyphosphate, DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and its derivatives or resins, DPPO (diphenylphosphine oxide) and its derivatives or resins, and aluminum phosphonate (e.g., commercially available OP-930 and OP-935).

[0077] The organic halogen-free flame retardant component can be provided in the thermosetting composition in a wide range of amounts, from 3 to 25 wt%. For example, in various embodiments, the amount of the organic halogen-free flame retardant component is 3 to 20 wt%, such as 3 to 15 wt%. In various embodiments, the amount of the organic halogen-free flame retardant component is 4 to 25 wt%, such as 4 to 20 wt% or 4 to 15 wt%. In various embodiments, the amount of the organic halogen-free flame retardant component is 5 to 25 wt%, such as 5 to 20 wt% or 5 to 15 wt%.

[0078] As described above, the thermosetting composition also includes an effective amount of one or more catalysts. These catalysts work together to effectively cure the thermosetting composition. Those skilled in the art are familiar with a variety of catalysts that effectively cure the epoxy systems described herein, and one or more of these catalysts can be selected to provide, in desired amounts, the initial polymerization of the thermosetting composition into a B-stage composition, and further to polymerize the B-stage composition into a substantially polymerized composition (e.g., in laminate form).

[0079] For example, in various embodiments, the one or more catalysts comprise tertiary amine catalysts, such as N-substituted imidazole catalysts, like 2-phenylimidazole, 2-methylimidazole, or 2-ethylimidazole. Tertiary amines are well-known epoxy curing agents, and those skilled in the art can select from these and other catalysts to provide the desired catalytic activity.

[0080] In various embodiments, the one or more catalysts include phase transfer catalysts (e.g., used with or without tertiary amines). Examples include quaternary phosphonium salts or quaternary ammonium salts, such as tetraalkylphosphonium salts (e.g., tetrabutylacetate); tetraalkylammonium salts or benzyltrialkylammonium salts. Phase transfer catalysts are also well known in the curing of epoxy systems, and those skilled in the art can select from these and other catalysts to provide the desired catalytic activity.

[0081] Those skilled in the art can determine the effective amount of the one or more catalysts. For example, in various embodiments, the effective amount of the one or more catalysts is in the range of 0.005-1 wt%, such as 0.005-0.5 wt%, or 0.005-0.2 wt%, or 0.005-0.1 wt%, or 0.01-1 wt%, or 0.01-0.5 wt%, or 0.01-0.2 wt%, or 0.01-0.1 wt%.

[0082] In some embodiments, the one or more catalysts may be provided together with a support; those skilled in the art will understand that the mass of the catalyst component is calculated based on the mass of the catalyst compound itself, omitting the mass of any support.

[0083] In some embodiments, additional components besides those described above may be present. For example, in various embodiments, the thermosetting composition may also include a phosphorus-modified phenolic resin in an amount of up to 15 wt%, such as up to 10 wt% or up to 8 wt%. Using a phosphorus-modified phenolic resin can help further improve fire resistance while providing good mechanical properties. One such example has the following structure:

[0084] Each R is independently one of the structures on the right side of the figure, and m is, for example, in the range of 1-100. One such material is available from Kolon Industries under the designation KIH-G800.

[0085] Furthermore, in various embodiments, the thermosetting composition may also include a silane coupling agent, for example, to provide bonding with microparticle silica fillers and / or glass materials used in the manufacture of prepregs or laminates. Those skilled in the art are familiar with silane coupling agents and can select a suitable silane coupling agent based on the description herein. For example, in some embodiments, the silane coupling agent may be selected from one or more epoxy-functionalized silanes and amine-functionalized silanes. In various embodiments, the epoxy-functionalized or amine-functionalized silane is a C1-C3 alkoxysilane, such as a methoxysilane or an ethoxysilane, such as a trimethoxysilane or a triethoxysilane. In various embodiments, the epoxy-functionalized or amine-functionalized silane comprises (or is) an epoxy-functionalized silane, such as (3-glycidoxypropyl)trimethoxysilane or (3-glycidoxypropyl)triethoxysilane. In various embodiments, the epoxy-functional or amine-functional silane comprises (or is) an amino-functional silane, such as (3-aminopropyl)trimethoxysilane or (3-aminopropyl)triethoxysilane.

[0086] The amount of silane coupling agent present can be, for example, up to 2 wt%, or up to 1 wt%. In various embodiments, the amount of silane coupling agent is in the range of 0.1-2 wt%, for example, in the range of 0.1-1.5 wt%, or 0.1-1 wt%, or 0.2-2 wt%, or 0.2-1.5 wt%, or 0.2-1 wt%.

[0087] The amounts of the components in the thermosetting compositions described herein are based on dry solids, i.e., the total amount of non-volatile components (i.e., boiling points less than 200 °C at atmospheric pressure) in the composition is taken as 100 wt%. In various embodiments, the thermosetting compositions are provided in a substantially non-volatile form, i.e., free of significant amounts of solvent. The inventors have noted that in many embodiments, the thermosetting compositions described herein can provide desirable viscosity without the use of significant amounts of solvent. Therefore, in various embodiments, the thermosetting compositions described herein can be provided containing no more than 10 wt% of material with a boiling point less than 200 °C at atmospheric pressure, for example, no more than 5 wt%, or no more than 3 wt%, or no more than 1 wt%, all calculations being performed with the aforementioned non-volatile content taken as 100 wt%.

[0088] However, the inventors note that solvents can be useful for providing a lower processing viscosity to the material, especially when impregnating glass or polymer fabrics used in the manufacture of prepregs. Therefore, in various embodiments, the thermosetting composition further includes a solvent with a boiling point of less than 200 °C at atmospheric pressure. Those skilled in the art will understand that multiple solvents can be used alone or in combination, and suitable solvents will be determined to suspend the various components of the composition therein. Potential examples include γ-butyrolactone, cyclohexanone, butanone, methyl isobutyl ketone, N,N-dimethylformamide, propylene glycol monomethyl ether, N,N-dimethylacetamide, ethylene glycol monomethyl ether, ethyl methoxy, ethyl ethoxy, ethyl propoxy, diisobutyl ketone (DIBK), N-methylpyrrolidone, xylene, ethyl acetate, toluene, trichloroethane, dibutyl ether, methyl ethyl ketone, and acetone. Similarly, those skilled in the art will understand that the amount of solvent can be varied to provide the desired viscosity; in various embodiments, the amount of solvent is up to 60 wt%, for example in the range of 20-60 wt%, exceeding the non-volatile components of the thermosetting composition (i.e., a total of 100 wt%).

[0089] Another aspect of this disclosure is the cured product of the thermosetting compositions described herein. As those skilled in the art will understand, in some embodiments, the cured product may only be partially cured, for example, to the extent that it forms a solid form and is operable, but can be cured more completely by further processing. This partial curing may be a so-called “B-stage”, or may reach a smaller or greater extent. In other embodiments, the cured product may be substantially fully cured, thus being substantially stable to further processing. A variety of curing conditions can be used, but typically the curing temperature is in the range of 100-250 °C, sustained for a sufficient time to achieve the desired degree of curing.

[0090] Another aspect of this disclosure is a prepreg comprising a mesh substrate at least partially embedded in the cured product of this disclosure, ideally a partially cured product that can be further cured at a later time by further heating. One embodiment is shown in Figure 1 The schematic cross-sectional view shows that the prepreg 100 includes a mesh substrate 110 embedded in the cured product 120 of this disclosure.

[0091] A variety of mesh substrates can be used by those skilled in the art. For example, in various embodiments, the mesh substrate is a fabric (woven or nonwoven), such as made of glass fiber, carbon fiber, or various polymer fibers (such as aramid fibers, as is available under the trade name KEVLAR). In a particularly desirable embodiment, the substrate is a borosilicate glass fabric. In some such embodiments, the glass is formed by SiO2 (50-80 wt%), B2O3 (5-25 wt%), and optional components including, but not limited to, CaO (up to 30 wt%), Al2O3 (up to 20 wt%), and MgO (up to 5 wt%). Suitable examples of glass fabrics include electronic-grade E-glass fabric, NE-glass fabric, D-glass fabric, and S-glass fabric. In various embodiments, the mesh substrate is substantially embedded in the cured product. As those skilled in the art will understand, prepregs can be made in various total thicknesses, but in some embodiments, the prepreg thickness is in the range of 10-300 micrometers, for example 10-200 micrometers, or 10-150 micrometers, or 10-100 micrometers. In some embodiments, the prepreg thickness is in the range of 25-300 micrometers, for example 25-200 micrometers, or 25-150 micrometers, or 25-100 micrometers. In some embodiments, the prepreg thickness is in the range of 50-300 micrometers, for example 50-200 micrometers, or 50-150 micrometers. The prepreg ideally comprises at least 30 wt% of the cured product of this disclosure, for example at least 50 wt%.

[0092] Those skilled in the art are familiar with methods for manufacturing prepregs and will adapt such methods to the thermosetting compositions of this disclosure. The thermosetting composition may be contacted with a mesh substrate, dried as needed to remove any volatiles, and cured by heating to at least partially cure the thermosetting composition to provide a prepreg.

[0093] Another aspect of this disclosure is a laminate of various prepregs. An example is shown in... Figure 2The schematic perspective view shows that laminate 230 comprises a plurality of prepregs 200. The laminate can be manufactured by hot-pressing a plurality of prepregs as described herein, causing partially cured materials of the prepregs to soften and further cure, thereby fusing them together to form a laminate structure. Hot-pressing conditions can vary but are typically in the range of 150–250 °C and 1–10 MPa. In many embodiments, further curing can result in substantially complete curing of the material. Substantially complete curing can be determined using a delta Tg measurement, as used herein, where the material is run to 250 °C in a differential scanning calorimeter and a first Tg is determined. The sample is then cooled to room temperature, and the Tg measurement to 250 °C is repeated to provide a second Tg. If the difference between the first and second Tg does not exceed 10 °C, the material is considered substantially complete curing. Techniques for forming laminates from prepregs are also familiar to those skilled in the art and will be adapted to the prepregs of this disclosure.

[0094] The laminate disclosed herein may comprise one or more layers of metal, such as copper. The one or more layers of metal may, for example, be disposed on one or both main surfaces of the laminate and / or laminated between prepreg layers. Each metal layer may be substantially homogeneous or may be provided in the form of circuitry, for example, by etching. As will be understood by those skilled in the art, the circuit board laminate may be constructed in multiple steps, for example, by providing a first laminate having metal on one or both surfaces, then forming circuitry from that metal, followed by further laminating the first laminate, thus treated, with additional prepreg layers and metal to form a multilayer laminate. The thickness may vary; in various embodiments, the surface average thickness of the metal layers (e.g., copper layers) is in the range of 10-500 micrometers, for example 10-250 micrometers, or 10-100 micrometers, or 20-500 micrometers, or 20-250 micrometers, or 20-100 micrometers.

[0095] The inventors have discovered that the materials described herein possess a variety of desirable properties, including low Df and Dk values, good peel strength, and a high glass transition temperature. For example, in various embodiments, the laminate has a Dk value measured according to IPC-TM-650 2.5.5.9 in the range of 3.5 to 4.5, such as 3.65-4.5, or 3.8-4.5, or 3.65-4.35. In various embodiments, the laminate has a Df value measured according to IPC-TM-650 2.5.5.9 in the range of 0.003 to 0.009, such as 0.004 to 0.009, or 0.005-0.009. In various implementations, the laminate has a peel strength (1 / 2 oz very low profile copper foil) of at least 2.5 lb / in, as measured according to IPC-TM-6502.4.8 (e.g., at least 3 lb / in, or at least 3.5 lb / in, e.g., in the range of 2.5-6 lb / in, or 2.5-5 lb / in, or 2.5-4.5 lb / in, or 3-6 lb / in, or 3-5 lb / in, or 3-4.5 lb / in, or 3.5-6 lb / in, or 3.5-5 lb / in, or 3.5-4.5 lb / in). In various implementations, the Tg of the laminate, as measured by DMA, is in the range of 180-240 °C, for example, 180-230 °C, or 180-220 °C, or 190-240 °C, or 190-230 °C, or 190-220 °C.

[0096] Various aspects and implementations of this disclosure are further provided by the following non-limiting examples.

[0097] Example 1

[0098] Various aspects and implementations of this disclosure are further provided by the following non-limiting examples.

[0099] The three example formulations (AC) comprise the following components (based on solids):

[0100] The biphenyl-type epoxy resin, KES-7370, is available from Kolon Industries and has the following general structure:

[0101] The mean of n is approximately 3.7.

[0102] The phenolic epoxy resin, PNE-177 (Changchun Petrochemical), has the following general structure, an epoxy equivalent (g / eq) of 172-182, and a viscosity of 20,000-80,000 cps in its pure state at 52 °C: .

[0103] Maleimide oligomers have a universal structure:

[0104] On average, n is approximately 6. These products are available from Sichuan EM Technology Co., Ltd. under the code DFE-950.

[0105] The aromatic primary diamine is 4,4'-diaminodiphenyl sulfone.

[0106] Two styrene-maleic anhydride copolymers, XIRAN® EF30 and XIRAN® EF40, available from Polyscope, were used, with styrene:maleic anhydride molar ratios of 3:1 and 4:1, respectively.

[0107] The benzoxazine prepolymer, LZ-8298, is available from Huntsman.

[0108] The phosphorus-modified phenolic resin is KIG-G800 from Kolon Industries.

[0109] The halogen-free flame retardant is xylyl diphenylphosphine oxide.

[0110] The micro-particle spherical silica is DQ-1028L and is available from Novoray.

[0111] The silane coupling agent is (3-glycidoxypropyl)trimethoxysilane.

[0112] The catalysts are 2-phenylimidazolium and tetrabutylacetic acid phosphonium.

[0113] The thermosetting composition was made into a 6-layer laminate. The thermosetting composition was placed in an impregnation tank, and a glass fiber cloth (2116, E-glass, 0.8 mm thick, 105 g / m²) was then applied. 2 The glass fiber fabric coated with resin is pulled through an impregnation tank and then passed between rollers with a gap thickness of 0.012. The resin-coated glass fiber fabric is dried in an oven to substantially remove the solvent (i.e., less than 1% of the solvent remains). This provides a prepreg material with a resin content of 57% on the glass and a thickness of approximately 0.005.

[0114] Six layers of the prepreg are laminated between two copper foils (Very Low Profile, VLP grade, ultra-flat profile, “0.5 oz”, nominal thickness 17 microns), with the treated side of the copper foil in contact with the prepreg material. The assembly is then placed between two stainless steel pressure plates and loaded into a hot oil vacuum press. Pressure (200-500 psi) and vacuum (2-5 mbar) are applied, and the load temperature is increased to the curing temperature (210 °C) at a defined heating rate (2.5 °C / min) and held for a defined time (120 min). The press is then allowed to cool at a rate of approximately 5 °C / min until the resulting laminate is cooled sufficiently for removal.

[0115] The data is provided in the table below:

[0116] The Nokia MRT-6 test carrier printed circuit board, manufactured using a lamination based on formulation A, passed a 1000-hour conductive anolyte test at 65 °C and 87% relative humidity, 100 V, for both 16 mil and 20 mil via pitches. It also passed a 2000-cycle interconnect stress test at 150 °C. After six reflow soldering cycles and six thermal stress cycles, the test carrier passed thermal reliability tests for both 0.65 mm and 0.80 mm pitches, demonstrating excellent reliability.

[0117] The various aspects and implementations of this disclosure are further provided by the following non-limiting embodiments, which can be combined in any number and in any combination that is technically or logically incompatible.

[0118] Implementation Scheme 1. A thermosetting composition comprising: Aromatic epoxy resin components are present in a total amount ranging from 5 to 25 wt%. The poly(styrene-co-maleic anhydride) component is present in an amount ranging from 8 to 30 wt%. The oligomer component containing maleimide, in an amount ranging from 2 to 10 wt%, has a number average of at least 3 maleimide per molecule and a softening point not higher than 100 °C. The benzoxazine / maleimide component, which is a bis(benzoxazine) sub-component and a bis(maleimide) sub-component and / or its reaction product, exists in an amount ranging from 2 to 20 wt%. The aromatic primary diamine component, in an amount of 0.1-2 wt%; Microparticles of silica, in the range of 15-50 wt%; Organic halogen-free flame retardant component, in an amount of 3-25 wt%; and An effective amount of one or more catalysts.

[0119] Implementation Scheme 2. The thermosetting composition as described in Implementation Scheme 1, wherein the amount of the aromatic epoxy resin component is in the range of 5-20 wt%, or 5-17 wt%, or 5-15 wt%, or 7-25 wt%, or 7-17 wt%, or 7-15 wt%, or 10-25 wt%, or 10-20 wt%, or 10-17 wt%, or 10-15 wt%.

[0120] Implementation Scheme 3. The thermosetting composition as described in Implementation Scheme 1 or Implementation Scheme 2, wherein the aromatic epoxy resin component is substantially free of halogens (e.g., halogens not exceeding 1 wt% or not exceeding 0.5 wt%).

[0121] Implementation Scheme 4. The thermosetting composition as described in any one of Implementation Schemes 1-3, wherein the aromatic carbon fraction of the aromatic epoxy resin component is at least 60%, for example at least 65%.

[0122] Implementation Scheme 5. The thermosetting composition as described in any one of Implementation Schemes 1-3, wherein the aromatic carbon fraction of the aromatic epoxy resin component is at least 70%, for example at least 75%.

[0123] Implementation Scheme 6. The thermosetting composition of any one of Implementation Schemes 1-3, wherein the aromatic carbon fraction of the aromatic epoxy resin component is in the range of 60-85%, for example 65-85%, or 60-82%, or 65-82%, or 60-80%, or 65-80%, or 60-75%, or 65-75%.

[0124] Implementation Scheme 7. The thermosetting composition as described in any one of Implementation Schemes 1-3, wherein the aromatic carbon fraction of the aromatic epoxy resin component is in the range of 70-85%, for example 75-85%, or 70-82%, or 75-82%, or 70-80%, or 75-80%.

[0125] Implementation Scheme 8. The thermosetting composition of any one of Implementation Schemes 1-7, wherein the aromatic epoxy resin component comprises one or more of the following: phenolic epoxy resins (e.g., biphenyl phenolic epoxy resins, phenolic epoxy resins, cresol phenolic epoxy resins), bisphenol epoxy resins (e.g., bisphenol A epoxy resins, bisphenol F epoxy resins, and bisphenol S epoxy resins), biphenyl epoxy resins, xylyl epoxy resins, arylalkylene epoxy resins (e.g., phenol aralkyl epoxy resins, biphenyl aralkyl epoxy resins, biphenyl phenolic epoxy resins, biphenyl dimethylene epoxy resins, triphenol methane phenolic epoxy resins, and tetramethyl biphenyl epoxy resins); and naphthalene epoxy resins.

[0126] Implementation Scheme 9. The thermosetting composition of any one of Implementation Schemes 1-8, wherein the aromatic epoxy resin component comprises biphenylphenolic epoxy resin.

[0127] Implementation Scheme 10. The thermosetting composition as described in Implementation Scheme 9, wherein the biphenylphenolic epoxy resin has the following structure:

[0128] Each R1 and R2 is independently an alkyl group having 1 to 4 carbon atoms; a is in the range of 0 to 3, b is in the range of 0 to 4; and the numerical mean of n is in the range of 1 to 6.

[0129] Implementation Scheme 11. The thermosetting composition as described in Implementation Scheme 10, wherein the numerical mean of n is in the range of 2-6, or 3-6, or 1-5, or 2-5, or 3-5.

[0130] Implementation Scheme 12. The thermosetting composition as described in Implementation Scheme 10 or Implementation Scheme 11, wherein each R1 and R2 is independently methyl or ethyl, and each a and b is independently 0, 1 or 2.

[0131] Implementation Scheme 13. The thermosetting composition as described in Implementation Scheme 10 or Implementation Scheme 11, wherein each of a and b is 0.

[0132] Implementation Scheme 14. The thermosetting composition as described in Implementation Scheme 10 or Implementation Scheme 11, wherein the biphenylphenolic epoxy resin has the following structure: .

[0133] Implementation Scheme 15. The thermosetting composition of any one of Implementation Schemes 9-14, wherein the amount of the at least one biphenylphenolic epoxy resin is in the range of 5-25 wt%, for example 5-20 wt%, or 5-17 wt%, or 5-15 wt%, or 7-25 wt%, or 7-17 wt%, or 7-15 wt%, or 10-25 wt%, or 10-20 wt%, or 10-17 wt%, or 10-15 wt%.

[0134] Implementation Scheme 16. The thermosetting composition of any one of Implementation Schemes 1-15, wherein the aromatic epoxy resin component comprises a phenolic epoxy resin.

[0135] Implementation Scheme 17. The thermosetting composition as described in Implementation Scheme 16, wherein the phenolic epoxy resin has the following structure:

[0136] Each R1 is independently an alkyl group having 1 to 4 carbon atoms; a is in the range of 0 to 3, and the number mean of n is in the range of 1 to 6.

[0137] Implementation Scheme 18. The thermosetting composition as described in Implementation Scheme 17, wherein n is 2-6, or 3-6, or 1-5, or 2-5, or 3-5.

[0138] Implementation Scheme 19. The thermosetting composition as described in Implementation Scheme 17 or Implementation Scheme 18, wherein each R1 is independently methyl or ethyl, and each a is independently 0, 1 or 2.

[0139] Implementation Scheme 20. The thermosetting composition as described in Implementation Scheme 17 or Implementation Scheme 18, wherein each a is 0.

[0140] Implementation Scheme 21. The thermosetting composition as described in any one of Implementation Schemes 16-20, wherein the amount of phenolic epoxy resin is in the range of 5-25 wt%, for example 5-20 wt%, or 5-17 wt%, or 5-15 wt%, or 7-25 wt%, or 7-17 wt%, or 7-15 wt%, or 10-25 wt%, or 10-20 wt%, or 10-17 wt%, or 10-15 wt%.

[0141] Implementation Scheme 22. The thermosetting composition of any one of Implementation Schemes 16-20, wherein the amount of phenolic epoxy resin is in the range of 1-10 wt%, for example 1-7 wt%, or 1-5 wt%, or 2-10 wt%, or 2-7 wt%, or 2-5 wt%, or 3-10 wt%, or 3-7 wt%, or 3-5 wt%.

[0142] Implementation Scheme 23. The thermosetting composition of any one of Implementation Schemes 1-22, wherein the aromatic epoxy resin component comprises the biphenyl-type phenolic epoxy resin of any one of Implementation Schemes 9-12 and the phenolic epoxy resin of any one of Implementation Schemes 13-16.

[0143] Implementation Scheme 24. The thermosetting composition as described in Implementation Scheme 23, wherein the weight ratio of biphenyl phenolic epoxy resin to phenolic epoxy resin is in the range of 1:1 to 15:1, for example 2:1 to 10:1, or 2:1 to 5:1, or 2:1 to 3:1.

[0144] Implementation Scheme 25. The thermosetting composition of any one of Implementation Schemes 1-24, wherein the aromatic epoxy resin component has an epoxy equivalent value in the range of 150 g / eq to 350 g / eq.

[0145] Implementation Scheme 26. The thermosetting composition according to any one of Implementation Schemes 1-25, wherein the amount of any non-aromatic epoxy resin does not exceed 10 wt%, for example, not more than 5 wt%, or not more than 2 wt%, or not more than 1 wt%.

[0146] Implementation Scheme 27. The thermosetting composition according to any one of Implementation Schemes 1-26, wherein the amount of the poly(styrene-co-maleic anhydride) component is in the range of 8-25 wt%, or 8-22 wt%, or 8-20 wt%, or 8-18 wt%, or 10-30 wt%, or 10-25 wt%, or 10-22 wt%, or 10-20 wt%, or 10-18 wt%.

[0147] Implementation Scheme 28. The thermosetting composition according to any one of Implementation Schemes 1-26, wherein the amount of the poly(styrene-co-maleic anhydride) component is in the range of 12-30 wt%, for example 12-25 wt%, or 12-22 wt%, or 12-20 wt%, or 12-18 wt%, or 14-30 wt%, or 14-25 wt%, or 14-22 wt%, or 14-20 wt%, or 14-18 wt%.

[0148] Implementation Scheme 29. The thermosetting composition according to any one of Implementation Schemes 1-28, wherein the non-styrene residues or maleic anhydride residues in the poly(styrene-co-maleic anhydride) component do not exceed 5 wt%, for example, not more than 2 wt% or not more than 1 wt%.

[0149] Implementation Scheme 30. The thermosetting composition according to any one of Implementation Schemes 1-29, wherein the ratio of styrene / maleic anhydride residues in the poly(styrene-co-maleic anhydride) component is in the range of 2:1 to 6:1, for example 2:1 to 5:1, or 2:1 to 4:1, or 2.5:1 to 6:1, or 2.5:1 to 5:1, or 2.5:1 to 4:1, or 3:1 to 6:1, or 3:1 to 5:1, or 3:1 to 4:1.

[0150] Implementation Scheme 31. The thermosetting composition according to any one of Implementation Schemes 1-29, wherein the ratio of styrene / maleic anhydride residues in the poly(styrene-co-maleic anhydride) component is in the range of 3:1 to 4:1.

[0151] Implementation Scheme 32. The thermosetting composition according to any one of Implementation Schemes 1-31, wherein the poly(styrene-co-maleic anhydride) component comprises (or is) a blend of a first poly(styrene-co-maleic anhydride) polymer with a styrene / maleic anhydride residue ratio in the range of 2.8:1 to 3.2:1 and a second poly(styrene-co-maleic anhydride) polymer with a styrene / maleic anhydride residue ratio in the range of 3.8:1 to 4.2:1.

[0152] Implementation Scheme 33. The thermosetting composition according to any one of Implementation Schemes 1-32, wherein the amount of the oligomer component containing maleimide is in the range of 2-9 wt%, or 2-7 wt%, or 3-10 wt%, or 3-9 wt%, or 3-7 wt%, or 5-10 wt%, or 5-9 wt%, or 5-7 wt%.

[0153] Implementation Scheme 34. A thermosetting composition according to any one of Implementation Schemes 1-33, wherein, on a number basis, each molecule of the oligomer component containing maleimide has at least 4 maleimides, for example at least 5 or at least 6.

[0154] Implementation Scheme 35. The thermosetting composition according to any one of Implementation Schemes 1-33, wherein the oligomer component containing maleimide has 3-10 maleimide molecules per molecule, for example in the range of 4-10, or 5-10, or 6-10, or 3-9, or 4-9, or 5-9, or 6-9.

[0155] Implementation Scheme 36. The thermosetting composition according to any one of Implementation Schemes 1-33, wherein the oligomer component containing maleimide has 3-8 maleimide molecules per molecule on an average basis, for example in the range of 4-8, or 5-8, or 6-8, or 3-7, or 4-7, or 5-7.

[0156] Implementation Scheme 37. The thermosetting composition according to any one of Implementation Schemes 1-36, wherein the softening point of the oligomer component containing maleimide is not higher than 95 °C, for example not higher than 90 °C.

[0157] Implementation Scheme 38. The thermosetting composition according to any one of Implementation Schemes 1-36, wherein the softening point of the oligomer component containing maleimide is in the range of 70-100 °C, for example 75-100 °C, or 80-100 °C, or 70-95 °C, or 75-95 °C, or 80-95 °C, or 70-90 °C, or 75-90 °C, or 80-90 °C, or 70-85 °C, or 75-85 °C, or 80-85 °C.

[0158] Implementation Scheme 39. The thermosetting composition according to any one of Implementation Schemes 1-38, wherein the aromatic carbon fraction of the oligomer component containing maleimide is at least 80%, for example at least 84% or at least 88%.

[0159] Implementation Scheme 40. The thermosetting composition according to any one of Implementation Schemes 1-39, wherein the oligomer component containing maleimide has the following structure: .

[0160] Implementation Scheme 41. The thermosetting composition according to any one of Implementation Schemes 1-40, wherein the amount of the benzoxazine / maleimide component is in the range of 2-17 wt%, or 2-15 wt%, or 2-12 wt%, or 2-9 wt%, or 4-20 wt%, or 4-17 wt%, or 4-15 wt%, or 4-12 wt%, or 4-9 wt%, or 6-20 wt%, or 6-17 wt%, or 6-15 wt%, or 6-12 wt%, or 6-9 wt%.

[0161] Implementation Scheme 42. The thermosetting composition according to any one of Implementation Schemes 1-41, wherein the bis(benzoxazine) sub-component comprises (or is) one or more of the following:

[0162] Each of X1 and X2 is independently an arylene (e.g., phenylene, biphenylene, naphthylene); a C1-C3 alkylene (ideally substituted on the same carbon, e.g., -C(CH3)2-, -CH(CH3)-, -CH2-) or S(O). 0-2 .

[0163] Implementation Scheme 43. The thermosetting composition according to any one of Implementation Schemes 1-42, wherein the bis(benzoxazine) sub-component of the benzoxazine / maleimide component comprises (or is) one or more of the following:

[0164] Implementation Scheme 44. The thermosetting composition according to any one of Implementation Schemes 1-42, wherein the bis(benzoxazine) sub-component comprises (or is) bisphenol F benzoxazine.

[0165] Implementation Scheme 45. The thermosetting composition according to any one of Implementation Schemes 1-44, wherein the bis(maleimide) sub-component comprises (or is) one or more of the following: 4,4'-dimaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimide phenyl)methane, 2,2-bis[4-(4-maleimide phenoxy)phenyl]propane, m-phenylene dimaleimide, 4-methyl-1,3-phenylene dimaleimide, and N,N'-1,4-phenylene dimaleimide.

[0166] Implementation Scheme 46. The thermosetting composition according to any one of Implementation Schemes 1-45, wherein the bis(maleimide) sub-component comprises (or is) 4,4'-dimaleimide diphenylmethane.

[0167] Implementation Scheme 47. The thermosetting composition according to any one of Implementation Schemes 1-46, wherein the benzoxazine / maleimide component is provided in the form of a prepolymer of a bis(benzoxazine) sub-component and a bismaleimide sub-component (e.g., bisphenol F benzoxazine / 4,4'-dimaleimide diphenylmethane prepolymer).

[0168] Implementation Scheme 48. The thermosetting composition according to any one of Implementation Schemes 1-47, wherein the molar ratio of the bis(benzoxazine) subcomponent to the bis(maleimide) subcomponent is in the range of 2:1 to 1:2, for example in the range of 1.5:1 to 1:2, or 1.25:1 to 1:2, or 1:1 to 1:2, or 2:1 to 1:1.5, or 1.5:1 to 1:1.5, or 1.25:1 to 1:1.5, or 1:1 to 1:1.5, or 2:1 to 1:1.25, or 1.5:1 to 1:1.25, or 1.25:1 to 1:1.25, or 1:1 to 1:1.25, or 2:1 to 1:1, or 1.5:1 to 1:1, or 1.25:1 to 1:1.

[0169] Implementation Scheme 49. The thermosetting composition according to any one of Implementation Schemes 1-47, wherein the molar ratio of the bis(benzoxazine) subcomponent to the bis(maleimide) subcomponent is in the range of 9:1 to 2:1, for example 7:1 to 2:1, or 5:1 to 2:1, or 4:1 to 2:1.

[0170] Implementation Scheme 50. The thermosetting composition according to any one of Implementation Schemes 1-47, wherein the molar ratio of the bis(benzoxazine) subcomponent to the bis(maleimide) subcomponent is in the range of 1:9 to 1:2, for example 1:7 to 1:2, or 1:5 to 1:2, or 1:4 to 1:2.

[0171] Implementation Scheme 51. The thermosetting composition according to any one of Implementation Schemes 1-50, wherein the aromatic carbon content of the benzoxazine / maleimide component is at least 60%, for example at least 65%, or at least 67%, or at least 70%.

[0172] Implementation Scheme 52. The thermosetting composition according to any one of Implementation Schemes 1-51, wherein the amount of the aromatic primary diamine component is 0.1-1.5 wt%, or 0.1-1 wt%, or 0.1-0.7 wt%, or 0.2-2 wt%, or 0.2-1.5 wt%, or 0.2-1 wt%, or 0.2-0.7 wt%.

[0173] Implementation Scheme 53. The thermosetting composition according to any one of Implementation Schemes 1-52, wherein the aromatic primary diamine component comprises (or is) 4,4'-(diaminodiphenyl) sulfone, 4,4'-diaminodiphenyl (ether) or 4,4'-diaminodiphenyl (methane).

[0174] Implementation Scheme 54. The thermosetting composition according to any one of Implementation Schemes 1-53, wherein the aromatic primary diamine component comprises (or is) 4,4'-(diaminodiphenyl) sulfone.

[0175] Implementation Scheme 55. The thermosetting composition according to any one of Implementation Schemes 1-54, wherein the aromatic primary diamine component has an aromatic carbon content of at least 90%, for example at least 95%, at least 98%, or at least 99%.

[0176] Implementation Scheme 56. The thermosetting composition according to any one of Implementation Schemes 1-55, wherein the d of the microparticle silica 50 The particle size is in the range of 0.5-10 micrometers, for example 0.5-7 micrometers, or 0.5-5 micrometers, or 1-10 micrometers, or 1-7 micrometers, or 1-5 micrometers.

[0177] Implementation Scheme 57. The thermosetting composition according to any one of Implementation Schemes 1-56, wherein the d90 particle size of the micro-particle silica is in the range of 1-20 micrometers, for example 1-14 micrometers, or 1-8 micrometers, or 3-20 micrometers, or 3-14 micrometers, or 3-8 micrometers.

[0178] Implementation Scheme 58. The thermosetting composition according to any one of Implementation Schemes 1-57, wherein the microparticles of silica d 10 The particle size is in the range of 0.1-5 micrometers, for example 0.1-3 micrometers, or 0.1-2 micrometers, or 0.5-5 micrometers, or 0.5-3 micrometers, or 0.5-2 micrometers.

[0179] Implementation Scheme 59. The thermosetting composition according to any one of Implementation Schemes 1-58, wherein the microparticles of silica are substantially spherical.

[0180] Implementation Scheme 60. The thermosetting composition according to any one of Implementation Schemes 1-59, wherein the microparticle silica has at least 99 wt% SiO2, for example at least 99.5 wt% SiO2.

[0181] Implementation Scheme 61. The thermosetting composition according to any one of Implementation Schemes 1-60, wherein the amount of microparticle silica is in the range of 15-45 wt%, or 15-40 wt%, or 15-35 wt%.

[0182] Implementation Scheme 62. The thermosetting composition according to any one of Implementation Schemes 1-60, wherein the amount of microparticle silica is in the range of 20-50 wt%, for example 20-45 wt%, or 20-40 wt%, or 20-35 wt%.

[0183] Implementation Scheme 63. The thermosetting composition according to any one of Implementation Schemes 1-60, wherein the amount of microparticle silica is in the range of 20-50 wt%, for example 25-45 wt%, or 25-40 wt%, or 25-35 wt%.

[0184] Implementation Scheme 64. The thermosetting composition according to any one of Implementation Schemes 1-63, wherein the organic halogen-free flame retardant component is a flame retardant as described in any one of U.S. Patent Nos. 8,536,256, 9,012,546, 9,522,927, and 9,562,063.

[0185] Implementation Scheme 65. The thermosetting composition according to any one of Implementation Schemes 1-63, wherein the organic halogen-free flame retardant component comprises (or is) 6H-dibenzo[c,e][1,2]oxophosphacyclohexane, 6,6′-(1,4-ethylenediyl)bis-, 6,6′-dioxide; 6H-dibenzo[c,e][1,2]oxophosphacyclohexane, 6,6′-(1,4-butadiyl)bis-, 6,6′-dioxide; or 6H-dibenzo[c,e][1,2]oxophosphacyclohexane, 6,6′-(p-xylyldiyl)bis-, 6,6′-dioxide; or any combination thereof.

[0186] Implementation Scheme 66. The thermosetting composition according to any one of Implementation Schemes 1-63, wherein the organic halogen-free flame retardant component comprises (or is) 6H-dibenzo[c,e][1,2]oxophosphazenecyclohexane, 6,6′-(1,4-ethylenedimethyl)bis-, 6,6′-dioxide.

[0187] Implementation Scheme 67. A thermosetting composition according to any one of Implementation Schemes 1-63, wherein the organic halogen-free flame retardant component comprises (or is) a compound having the following structure: having the following structure: .

[0188] Implementation Scheme 68. A thermosetting composition according to any one of Implementation Schemes 1-63, wherein the organic halogen-free flame retardant component comprises (or is) a composition containing a high-melting-point isomer of formula IIa:

[0189] And low-melting-point isomers having the following formulas IIb and IIc:

[0190] The isomer ratio of the composition, as determined by 31P NMR, is greater than about 0.5, and the isomer ratio = A h / (A h +A l ), where A h : Peak area of ​​high melting point isomer, A l : Peak area of ​​low melting point isomers.

[0191] Implementation Scheme 69. The thermosetting composition according to any one of Implementation Schemes 1-68, wherein the organic halogen-free flame retardant component comprises (or is) a flame retardant based on diarylphosphine oxide.

[0192] Implementation Scheme 70. The thermosetting composition according to any one of Implementation Schemes 1-68, wherein the organic halogen-free flame retardant component comprises (or is) a flame retardant based on diphenylphosphine oxide.

[0193] Implementation Scheme 71. The thermosetting composition according to any one of Implementation Schemes 1-68, wherein the organic halogen-free flame retardant component comprises (or is) a compound having the following structural formula:

[0194] R1 is selected from covalent bonds, -CH2-,

[0195] Where R 11 R 12 R 13 and R 14 Independently H, alkyl or .

[0196] Implementation Scheme 72. The thermosetting composition according to any one of Implementation Schemes 1-68, wherein the organic halogen-free flame retardant component comprises (or is) a compound having the following structural formula: .

[0197] Implementation Scheme 73. The thermosetting composition according to any one of Implementation Schemes 1-72, wherein the amount of the organic halogen-free flame retardant component is 3-20 wt%, for example 3-15 wt%.

[0198] Implementation Scheme 74. The thermosetting composition according to any one of Implementation Schemes 1-72, wherein the amount of the organic halogen-free flame retardant component is 4-25 wt%, for example 4-20 wt% or 4-15 wt%.

[0199] Implementation Scheme 75. The thermosetting composition according to any one of Implementation Schemes 1-72, wherein the amount of the organic halogen-free flame retardant component is 5-25 wt%, for example 5-20 wt% or 5-15 wt%.

[0200] Implementation Scheme 76. The thermosetting composition according to any one of Implementation Schemes 1-75, wherein the one or more catalysts comprise tertiary amine catalysts, such as N-substituted imidazole catalysts, such as 2-phenylimidazolium, 2-methylimidazolium, or 2-ethylimidazolium.

[0201] Implementation Scheme 77. The thermosetting composition according to any one of Implementation Schemes 1-76, wherein the one or more catalysts comprise a phase transfer catalyst, such as a quaternary phosphonium salt or a quaternary ammonium salt, for example a tetraalkylphosphonium salt (such as tetrabutylacetic acid phosphonium); a tetraalkylammonium salt or a benzyltrialkylammonium salt.

[0202] Implementation Scheme 78. The thermosetting composition according to any one of Implementation Schemes 1-77, wherein the effective amount of said one or more catalysts is in the range of 0.005-1 wt%, for example 0.005-0.5 wt%, or 0.005-0.2 wt%, or 0.005-0.1 wt%, or 0.01-1 wt%, or 0.01-0.5 wt%, or 0.01-0.2 wt%, or 0.01-0.1 wt%.

[0203] Implementation Scheme 79. The thermosetting composition according to any one of Implementation Schemes 1-77 further comprises a phosphorus-modified phenolic resin in an amount of up to 15 wt%, such as up to 10 wt% or up to 8 wt%.

[0204] Implementation Scheme 80. The thermosetting composition according to Implementation Scheme 77, wherein the amount of phosphorus-modified phenolic resin is in the range of 3-15 wt%, for example 3-10 wt%, or 3-8 wt%, or 5-15 wt%, or 5-10 wt%, or 5-8 wt%.

[0205] Implementation Scheme 81. The thermosetting composition according to Implementation Scheme 77 or Implementation Scheme 80, wherein the phosphorus-modified phenolic resin has the following structure:

[0206] Each R is independently one of the structures on the right side of the figure, and m is, for example, in the range of 1-100.

[0207] Implementation Scheme 82. The thermosetting composition according to any one of Implementation Schemes 1-81 further comprises an epoxy-functionalized or amine-functionalized silane in an amount of up to 2 wt%, such as up to 1.5 wt% or up to 1 wt%.

[0208] Implementation Scheme 83. The thermosetting composition according to Implementation Scheme 82, wherein the amount of epoxy-functionalized or amine-functionalized silane is in the range of 0.1-2 wt%, for example 0.1-1.5 wt%, or 0.1-1 wt%, or 0.2-2 wt%, or 0.2-1.5 wt%, or 0.2-1 wt%.

[0209] Implementation Scheme 84. The thermosetting composition according to Implementation Scheme 82 or Implementation Scheme 83, wherein the epoxy-functional or amine-functional silane is a C1-C3 alkoxysilane, such as methoxysilane or ethoxysilane, such as trimethoxysilane or triethoxysilane.

[0210] Implementation Scheme 85. The thermosetting composition according to any one of Implementation Schemes 82-84, wherein the epoxy-functional or amine-functional silane comprises (or is) an epoxy-functional silane, such as (3-glycidoxypropyl)trimethoxysilane or (3-glycidoxypropyl)triethoxysilane.

[0211] Implementation Scheme 86. The thermosetting composition according to any one of Implementation Schemes 82-84, wherein the epoxy-functional or amine-functional silane comprises (or is) an amino-functional silane, such as (3-aminopropyl)trimethoxysilane or (3-aminopropyl)triethoxysilane.

[0212] Implementation Scheme 87. The thermosetting composition according to any one of Implementation Schemes 1-86, which is provided in a substantially non-volatile form, i.e., free of a large amount of solvent.

[0213] Implementation Scheme 88. The thermosetting composition according to any one of Implementation Schemes 1-87, wherein the material contained having a boiling point of less than 200 °C at atmospheric pressure is not more than 10 wt%, for example not more than 5 wt%, or not more than 3 wt%, or not more than 1 wt%, and all calculations are performed with a non-volatile content of 100 wt%.

[0214] Implementation Scheme 89. The thermosetting composition according to any one of Implementation Schemes 1-88 further comprises a solvent having a boiling point of less than 200 °C at atmospheric pressure.

[0215] Implementation Scheme 90. The thermosetting composition according to Implementation Scheme 89, wherein the solvent is one or more of the following: γ-butyrolactone, cyclohexanone, butanone, methyl isobutyl ketone, N,N-dimethylformamide, propylene glycol monomethyl ether, N,N-dimethylacetamide, ethylene glycol monomethyl ether, ethyl methoxy, ethyl ethoxy, ethyl propoxy, diisobutyl ketone (DIBK), N-methylpyrrolidone, xylene, ethyl acetate, toluene, trichloroethane, dibutyl ether, methyl ethyl ketone, and acetone.

[0216] Implementation Scheme 91. The thermosetting composition according to Implementation Scheme 89 or Implementation Scheme 90, wherein the amount of solvent is in the range of 20-60 wt%, exceeding the non-volatile components of the thermosetting composition (i.e., a total of 100 wt%).

[0217] Implementation Scheme 92. A cured product made from a thermosetting composition according to any one of Implementation Schemes 1-91.

[0218] Implementation Scheme 93. A method for curing a thermosetting composition according to any one of Implementation Schemes 1-91, comprising heating the thermosetting composition at a temperature (e.g., 150-250 °C) that effectively cures the composition at least partially.

[0219] Implementation Scheme 94. A prepreg comprising a mesh substrate at least partially embedded in a cured product of Implementation Scheme 92 or a cured product made by the method of Implementation Scheme 93.

[0220] Implementation Scheme 95. The prepreg according to Implementation Scheme 94, wherein the cured product is a partially cured product.

[0221] Implementation Scheme 96. The prepreg according to Implementation Scheme 94 or Implementation Scheme 95, wherein the mesh substrate is a fabric (woven or nonwoven).

[0222] Implementation Scheme 97. The prepreg according to Implementation Scheme 96, wherein the fabric is made of glass fiber, for example as a borosilicate glass fabric.

[0223] Implementation Scheme 98. The prepreg according to Implementation Scheme 96 or Implementation Scheme 97, wherein the mesh substrate is electronic grade E-glass fabric, NE-glass fabric, D-glass fabric or S-glass fabric.

[0224] Implementation Scheme 99. The prepreg according to any one of Implementation Schemes 94-98 has a thickness in the range of 10-300 micrometers, for example 10-200 micrometers, or 10-150 micrometers, or 10-100 micrometers.

[0225] Implementation Scheme 100. The prepreg according to any one of Implementation Schemes 94-98 has a thickness in the range of 25-300 micrometers, for example 25-200 micrometers, or 25-150 micrometers, or 25-100 micrometers.

[0226] Implementation Scheme 101. The prepreg according to any one of Implementation Schemes 94-98 has a thickness in the range of 50-300 micrometers, for example 50-200 micrometers or 50-150 micrometers.

[0227] Implementation Scheme 102. The prepreg according to any one of Implementation Schemes 94-101, comprising at least 30 wt% of the cured product of this disclosure, for example at least 50 wt%.

[0228] Implementation Scheme 103. A laminate comprising a plurality of prepregs according to any one of Implementation Schemes 94-102.

[0229] Implementation Scheme 104. The laminate according to Implementation Scheme 103, wherein the cured product of the prepreg in the laminate is substantially completely cured.

[0230] Implementation Scheme 105. The laminate according to Implementation Scheme 103 or Implementation Scheme 104 further comprises one or more layers of metal, for example on one or more opposing main surfaces of the laminate.

[0231] Implementation Scheme 106. The laminate according to Implementation Scheme 105, wherein one or more metal layers are copper layers.

[0232] Implementation Scheme 107. The laminate according to Implementation Scheme 106, wherein the thickness of the one or more copper layers is in the range of 15-50 micrometers, for example in the range of 17-37 micrometers.

[0233] Implementation Scheme 108. The laminate according to Implementation Scheme 106 or Implementation Scheme 107, wherein each of the one or more copper layers has an outer surface facing away from the prepreg laminated therewith, the surface having one or more of the following: a surface roughness Ra (measured by contact method, ISO 4287) not exceeding 0.3 micrometers, and / or a surface roughness Sa (measured by non-contact method, ISO 25178) in the range of 0.1-0.3 micrometers (e.g. 0.15-0.25 micrometers).

[0234] Implementation Scheme 109. A laminate according to any one of Implementation Schemes 106-108, wherein each of the one or more copper layers has an inner surface in contact with a prepreg, the surface having one or more of the following: a surface roughness Sa in the range of 0.1-0.4 micrometers (e.g., 0.12-0.3 micrometers); a surface roughness Sz in the range of 1-5 micrometers (e.g., 1.2-4 micrometers); and / or a surface roughness Sdr in the range of 0.5-3 micrometers (e.g., 0.7-2 micrometers), each measured non-contactly according to ISO 25178.

[0235] Implementation Scheme 110. The laminate according to any one of Implementation Schemes 106-109, as measured according to IPC-TM-6502.5.5.9, has a Df value in the range of .003 to 0.009, for example 0.004 to 0.009, or 0.005 to 0.009.

[0236] Implementation Scheme 111. The laminate according to any one of Implementation Schemes 106-110, as measured according to IPC-TM-6502.5.5.9, has a Dk value in the range of 3.5 to 4.5, for example 3.65-4.5, 3.85-4.5, or 3.65-4.35.

[0237] Implementation Scheme 112. The laminate according to any one of Implementation Schemes 106-111 has a Tg measured by DMA in the range of 150-210 °C, for example 150-195 °C, or 160-210 °C, or 160-195 °C, or 170-210 °C, or 170-195 °C.

Claims

1. A thermosetting composition comprising: Aromatic epoxy resin component, which exists in total amount of 5-25 wt%; The poly(styrene-co-maleic anhydride) component is present in an amount ranging from 8 to 30 wt%. The oligomer component containing maleimide, in an amount ranging from 2 to 10 wt%, has a number average of at least 3 maleimide per molecule and a softening point not higher than 100 °C. The benzoxazine / maleimide component, which is a bis(benzoxazine) sub-component and a bis(maleimide) sub-component and / or their reaction products, exists in an amount of 2-20 wt%. The aromatic primary diamine component, in an amount of 0.1-2 wt%; Microparticles of silica, in an amount of 15-50 wt%; Organic halogen-free flame retardant component, in an amount of 3-25 wt%; and An effective amount of one or more catalysts.

2. The thermosetting composition according to claim 1, wherein the amount of the aromatic epoxy resin component is in the range of 5-15 wt%.

3. The thermosetting composition according to claim 1, wherein the aromatic epoxy resin component is substantially halogen-free.

4. The thermosetting composition according to claim 1, wherein the aromatic carbon fraction of the aromatic epoxy resin component is 70-85%.

5. The thermosetting composition according to claim 1, wherein the aromatic epoxy resin component comprises biphenyl-type phenolic epoxy resin and phenolic epoxy resin.

6. The thermosetting composition according to claim 5, wherein the weight ratio of biphenyl-type phenolic epoxy resin to phenolic epoxy resin is in the range of 1:1 to 15:

1.

7. The thermosetting composition according to claim 1, wherein the amount of any non-aromatic epoxy resin does not exceed 10 wt%.

8. The thermosetting composition according to claim 1, wherein the amount of the poly(styrene-co-maleic anhydride) component is in the range of 8-25 wt%.

9. The thermosetting composition according to claim 1, wherein the non-styrene residues or maleic anhydride residues in the poly(styrene-co-maleic anhydride) component do not exceed 5 wt%.

10. The thermosetting composition according to claim 1, wherein the ratio of styrene / maleic anhydride residues in the poly(styrene-co-maleic anhydride) component is in the range of 2:1 to 6:

1.

11. The thermosetting composition according to claim 1, wherein the amount of the oligomer component containing maleimide is in the range of 2-7 wt%.

12. The thermosetting composition according to claim 1, wherein the oligomer component containing maleimide has 3-10 maleimide per molecule on a number-average basis.

13. The thermosetting composition according to claim 1, wherein the fraction of aromatic carbon in the oligomer component containing maleimide is at least 80%.

14. The thermosetting composition according to claim 1, wherein the amount of the benzoxazine / maleimide component is in the range of 4-20 wt%.

15. The thermosetting composition of claim 1, wherein the benzoxazine / maleimide component is provided in the form of a prepolymer of a bis(benzoxazine) sub-component and a bismaleimide sub-component.

16. The thermosetting composition according to claim 1, wherein the molar ratio of the bis(benzoxazine) subcomponent to the bis(maleimide) subcomponent is in the range of 2:1 to 1:

2.

17. The thermosetting composition according to claim 1, wherein the aromatic carbon content of the benzoxazine / maleimide component is at least 60%.

18. The thermosetting composition according to claim 1, wherein the amount of the aromatic primary diamine component is 0.1-1 wt%.

19. The thermosetting composition according to claim 1, wherein the aromatic primary diamine component comprises 4,4'-(diaminodiphenyl) sulfone, 4,4'-diaminodiphenyl (ether) or 4,4'-diaminodiphenyl (methane).

20. The thermosetting composition according to claim 1, wherein the aromatic primary diamine component has an aromatic carbon content of at least 90%.

21. The thermosetting composition according to claim 1, wherein the amount of microparticle silica is in the range of 15-45 wt%.

22. The thermosetting composition of claim 1, wherein the organic halogen-free flame retardant component comprises a flame retardant based on diarylphosphine oxide or a flame retardant based on diphenylphosphine oxide.

23. The thermosetting composition according to claim 1, wherein the amount of the organic halogen-free flame retardant component is 3-20 wt%.

24. The thermosetting composition according to claim 1, wherein the one or more catalysts comprise tertiary amine catalysts, such as N-substituted imidazole catalysts, such as 2-phenylimidazolium, 2-methylimidazolium, or 2-ethylimidazolium; and / or phase transfer catalysts, such as quaternary phosphonium salts or quaternary ammonium salts.

25. The thermosetting composition according to claim 1, wherein the effective amount of the one or more catalysts is in the range of 0.005-1 wt%.

26. The thermosetting composition according to claim 1, further comprising a phosphorus-modified phenolic resin in an amount of up to 15 wt%.

27. The thermosetting composition according to claim 1, further comprising an epoxy-functionalized or amine-functionalized silane in an amount of up to 2 wt%.

28. The thermosetting composition according to claim 1, provided in a substantially non-volatile form.

29. The thermosetting composition according to claim 1, wherein the material comprising a boiling point of less than 200 °C at atmospheric pressure is not more than 10 wt%, and all calculations are based on a non-volatile content of 100 wt%.

30. The thermosetting composition according to claim 1, further comprising a solvent having a boiling point of less than 200 °C at atmospheric pressure.

31. A prepreg comprising a mesh substrate at least partially embedded in a cured product of the thermosetting composition of claim 1.

32. A laminate comprising a plurality of prepregs according to claim 31.

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