Thermosetting composition and curing composition, prepreg and laminated board based on thermosetting composition

Abstract

The present disclosure relates to thermosetting compositions suitable for use in the manufacture of electronic materials (e.g., circuit board substrates), as well as cured compositions, prepregs, and laminates based on such thermosetting compositions. One aspect of the present disclosure is a thermoset composition comprising: a poly (1, 4-phenylene ether) component having a phenylene ether content of at least 80%, the poly (1, 4-phenylene ether) component being a poly (1, 4-phenylene ether) bis (meth) acrylate component, a bis (vinyl) poly (1, 4-phenylene ether) component, or a bis (meth) allyl) poly (1, 4-phenylene ether) component; a 1, 4-phenylene ether) component, or a combination of two or more; the weight-average molecular weight of the aromatic crosslinking component is not greater than 700 g / mol, and each molecule has 1.75-3.5 crosslinkable vinyl, (methyl) allyl and / or (methyl) acrylate groups on average; a butadiene / styrene copolymer rubber component; microparticulate silica; a halogen-free organic flame retardant component; and an effective amount of a thermal radical initiator component.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 509,663, filed June 22, 2023, the entire contents of which are incorporated herein by reference. Technical Field 1. Technical Field

[0004] This disclosure relates to thermosetting compositions suitable for manufacturing electronic materials (e.g., circuit board substrates), and cured compositions, prepregs, and laminates based on such thermosetting compositions. 2. Background Technology

[0006] Various polymer materials have been developed for use as substrates in electronic products. To provide ideal high transmission speeds, desirable properties include low dielectric constant and low loss factor (especially at high frequencies), as well as high glass transition temperature, low coefficient of thermal expansion, and high-temperature stability.

[0007] These materials are typically laminated with a copper foil layer. The peel strength between the copper foil and the polymer material is a crucial characteristic of these materials. During device fabrication, these materials are subjected to high temperatures (e.g., through soldering), and insufficient adhesion between the copper and the polymer can lead to problems in the device, such as trace lifting, pad lifting, and large-scale delamination. Adhesion is typically measured by "peel strength," which quantifies the force required to peel the copper layer from the material.

[0008] However, while peel strength is important, electronic and thermal properties are also crucial. What is needed are new materials that not only possess high peel strength with copper, but also good dielectric properties (especially at high frequencies) and good thermal properties. Summary of the Invention

[0009] One aspect of this disclosure is a thermosetting composition comprising: A poly(1,4-phenylene ether) component having a content of at least 80% phenylene ether, wherein the poly(1,4-phenylene ether) component is a poly(1,4-phenylene ether) bis(meth)acrylate component, a bis(vinyl)poly(1,4-phenylene ether) component, or a bis((meth)allyl)poly(1,4-phenylene ether) component, or a combination of two or more thereof, and the amount thereof is 20-35 wt%. The aromatic crosslinked component has a weight-average molecular weight of not more than 700 g / mol and each molecule has an average of 1.75-3.5 crosslinkable vinyl, (meth)allyl and / or (meth)acrylate groups, in an amount of 2-15 wt%. The butadiene / styrene copolymer rubber component, in an amount of 5-25 wt%; Microparticles of silica, in an amount of 15-50 wt%; Halogen-free organic flame retardant components, in an amount of 15-35 wt%; and Effective amount of thermal free radical initiator component.

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

[0011] Another aspect of this disclosure is a method for curing the thermosetting composition 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 a plurality of prepregs described herein. Attached Figure Description

[0014] Figure 1 This is a schematic cross-sectional view of a prepreg according to one embodiment of the present disclosure.

[0015] Figure 2 This is a schematic cross-sectional view of a laminate according to one embodiment of the present disclosure. Invention Details

[0017] The inventors of this invention have developed specific thermosetting compositions that not only provide good peel strength to copper, but also excellent dielectric properties and good thermal properties at high frequencies.

[0018] One aspect of this disclosure is a thermosetting composition comprising: A poly(1,4-phenylene ether) component having a content of at least 80% phenylene ether, wherein the poly(1,4-phenylene ether) component is a poly(1,4-phenylene ether) bis(meth)acrylate component, a bis(vinyl)poly(1,4-phenylene ether) component, or a bis((meth)allyl)poly(1,4-phenylene ether) component, or a combination of two or more thereof, and the amount thereof is 20-35 wt%. The aromatic crosslinked component has a weight-average molecular weight of not more than 700 g / mol and each molecule has an average of 1.75-3.5 crosslinkable vinyl, (meth)allyl and / or (meth)acrylate groups, in an amount of 2-15 wt%. The butadiene / styrene copolymer rubber component, in an amount of 5-25 wt%; Microparticles of silica, in an amount of 15-50 wt%; Halogen-free organic flame retardant components, in an amount of 15-35 wt%; and Effective amount of thermal free radical initiator component.

[0019] As used herein, a thermosetting composition is a substantially liquid composition that solidifies from a liquid state to a solid state under the influence of heat. Various particularly desirable thermosetting compositions are those that are “B-stage,” meaning they can be partially cured into a workable solid under a first heat treatment and then fully cured under a second heat treatment. Partially cured materials may, for example, be in what is called the “B-stage” and can be further cured into what is called the “C-stage.” Those skilled in the art of electronic materials are familiar with using thermosetting compositions as described herein to produce a variety of products, such as prepregs, resin films, resin-coated copper, laminates, and printed circuit boards.

[0020] One component of the thermosetting composition disclosed herein is a poly(1,4-phenylene ether) component, which is a poly(1,4-phenylene ether) bis(meth)acrylate component, a bis(vinyl)poly(1,4-phenylene ether) component, or a bis((meth)allyl)poly(1,4-phenylene ether) component, or a combination of two or more thereof, having a phenylene ether content of at least 80 wt%, in an amount of 20-35 wt%. The poly(1,4-phenylene ether) component may consist of a single poly(1,4-phenylene ether) bis(meth)acrylate, bis(vinyl) or bis((meth)allyl) polymer (which itself is typically a series of molecules with different degrees of polymerization), or a blend of multiple poly(1,4-phenylene ether) bis(meth)acrylate, bis(vinyl) or bis((meth)allyl) polymer samples.

[0021] The poly(1,4-phenylene ether) component has a phenylene ether content of at least 80 wt%. This means that at least 80 wt% of the component consists of -O- (optionally substituted phenylene) groups. In various embodiments, the mass of the -O- (optionally substituted phenylene) groups in the poly(1,4-phenylene ether) component consists of at least 50% phenyl carbon and phenyl hydrogen.

[0022] In various preferred embodiments, the poly(1,4-phenylene ether) component is a poly(1,4-phenylene ether) dimethacrylate component, i.e., having at least 75 wt%, for example, at least 90 wt% of poly(1,4-phenylene ether) dimethacrylate.

[0023] In various embodiments, the poly(1,4-phenylene ether) component is a bis(vinyl)poly(1,4-phenylene ether) component, i.e., having at least 75 wt%, for example at least 90 wt% of bis(vinyl)poly(1,4-phenylene ether).

[0024] In various embodiments, the poly(1,4-phenylene ether) component is a bis(allyl)poly(1,4-phenylene ether) component, i.e., having at least 75 wt%, for example at least 90 wt% of bis(allyl)poly(1,4-phenylene ether).

[0025] In various embodiments, the poly(1,4-phenylene ether) component is a bis(methylallyl)poly(1,4-phenylene ether) component, i.e., having at least 75 wt%, for example at least 90 wt% of bis(methylallyl)poly(1,4-phenylene ether).

[0026] In various embodiments, the poly(1,4-phenylene ether) component has the following structural formula:

[0027] Where A is a bond, -CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -C(O)-, S(O) or S(O)2; each R 1 Independently, it is methacrylate, acrylate, vinyl, allyl, or methallyl; each R 2 Independently methyl or hydrogen; and each R 3 Independently methyl or hydrogen. Within this definition, cases with different A and R... 1 and R 2 A mixture of molecules. As will be understood by those skilled in the art, the values ​​of x and y will vary depending on the molecular weight of the material.

[0028] For example, in various embodiments, A is -CH2-, -CH(CH3)-, or -C(CH3)2-. In various embodiments, A is -C(CH3)2-.

[0029] Four-R 2 - The structure of the replaced portion can vary. For example, in various embodiments, at least 75% In the part, there are two Rs 2 It is a methyl group, with two Rs. 2 It is H. For example, in various implementation schemes, in at least 90% of In the part, there are two Rs 2 It is a methyl group, with two Rs. 2 It is H. In various implementation schemes, in at least 98% of In the part, there are two Rs2 It is a methyl group, with two Rs. 2 It is H.

[0030] In various implementation schemes, at least 75% In the part, there are two Rs 2 The methyl group is substituted in a meta position; and both R groups are... 2 It is H. For example, in various implementation schemes, in at least 90% of In the part, there are two Rs 2 The methyl group is substituted in a meta position; and both R groups are substituted. 2 It is H. In various implementation schemes, in at least 98% of In the part, there are two Rs 2 The methyl group is substituted in a meta position; and both R groups are... 2 It is H.

[0031] In various implementation schemes, at least 75% In the part, there are two Rs 2 The methyl group is substituted in a meta-position distant from the A moiety; and the two R groups are... 2 It is H. For example, in various implementation schemes, in at least 90% of In the part, there are two Rs 2 The methyl group is substituted in a meta-position distant from the A moiety; and the two R groups are... 2 It is H. In various implementation schemes, in at least 98% of In the part, there are two Rs 2 The methyl group is substituted in a meta-position distant from the A moiety; and the two R groups are... 2 It is H.

[0032] Four-R 3 - The structure of the replaced portion can also vary. For example, in various embodiments, at least 75% In the part, there are two Rs 3 It is methyl and has two Rs 3 It is H. For example, in various implementation schemes, in at least 90% of In the part, there are two Rs 3 It is methyl and has two Rs 3 It is H. In various implementation schemes, in at least 98% of In the part, there are two Rs 3 It is methyl and has two Rs 3 It is H.

[0033] In various implementation schemes, at least 75% In the part, there are two Rs 3 The methyl group is substituted in a meta position; and both... R 3It is H. For example, in various implementation schemes, in at least 90% of In the part, two R 3 The methyl group is substituted in a meta position; and both R groups are... 3 It is H. In various implementation schemes, in at least 98% of In the part, two R 3 It is a methyl group that is meta-substituted and two R 3 It is H.

[0034] In various implementation schemes, at least 75% In the part, there are two Rs 3 The methyl group is substituted in a meta-position far from the A moiety, and both R groups are... 3 It is H. For example, in various implementation schemes, in at least 90% of In the part, there are two Rs 3 The methyl group is substituted in a meta-position distant from the A moiety; and the two R groups are... 3 It is H. In various implementation schemes, in at least 98% of In the part, there are two Rs 3 The methyl group is substituted in a meta-position distant from the A moiety; and the two R groups are... 3 It is H.

[0035] As mentioned above, R 1 It can be one or more of methacrylate, acrylate, vinyl, allyl, and methylallyl. In various embodiments, at least 75% of the R... 1 It is a methacrylate, for example, at least 90%, or at least 95%. In various embodiments, at least 75% of R... 1 It is vinyl, for example, at least 90%, or at least 95%. In various embodiments, at least 75% of R 1 It is allyl, for example, at least 90%, or at least 95%. In various embodiments, at least 75% of R 1 It is methylallyl, for example, at least 90%, or at least 95%. In various embodiments, at least 75% of R 1 It is methacrylate, vinyl, allyl or methylallyl, for example at least 90%, or at least 95%.

[0036] In various specific embodiments, at least 75 wt% of the poly(1,4-phenylene ether) component has the following formula:

[0037] In various such embodiments, at least 90 wt% of the poly(1,4-phenylene ether) component has this formula. In various such embodiments, at least 95 wt% of the poly(1,4-phenylene ether) component has this formula.

[0038] The poly(1,4-phenylene ether) component can have a variety of molecular weights. Those skilled in the art will select a suitable molecular weight to provide the desired properties of the thermosetting composition, such as a suitable viscosity for processing into prepregs or other cured articles. For example, in various embodiments, the number-average molecular weight of the poly(1,4-phenylene ether) component is in the range of 1000-4000 g / mol, such as 1000-3500 g / mol, 1000-3000 g / mol, 1000-2500 g / mol, 1500-4000 g / mol, 1500-3500 g / mol, or 1500-2500 g / mol.

[0039] As described above, the values ​​of x and y will vary depending on the molecular weight of the material. In various embodiments, the number mean of the sum of x and y of the poly(1,4-phenylene ether) component is in the range of 3-30, for example 3-25, or 3-20, or 3-15, or 5-30, or 5-25, or 5-20, or 5-15, or 7-30, or 7-25, or 7-20, or 7-15, or 10-30, or 10-25, or 10-20, or 10-15.

[0040] Examples of suitable materials include NORYL SA-9000 from SABIC; Kolon KPU-6000 from Kolon Industries; and SP7-160 from SilverAge Engineering Plastics Co Ltd.

[0041] As described above, the poly(1,4-phenylene ether) component is present in the thermosetting composition in an amount of 20-35 wt%. Those skilled in the art can vary this amount generally within this range. For example, in various embodiments, the poly(1,4-phenylene ether) component is present in an amount of 22-35 wt%, such as 22-32 wt%, or 22-30 wt%. In various embodiments, the poly(1,4-phenylene ether) component is present in an amount of 25-35 wt%, such as 25-32 wt%, or 25-30 wt%.

[0042] As described above, the thermosetting composition further includes an aromatic crosslinking component with a weight-average molecular weight of not more than 700 g / mol and an average of 1.75-3.5 crosslinkable vinyl, (meth)allyl and / or (meth)acrylate groups per molecule, in an amount of 2-15 wt%.

[0043] Those skilled in the art will understand that a variety of such aromatic crosslinking components can be used, alone or in combination. For example, in various preferred embodiments, the aromatic crosslinking component includes / or a cyanurate component. In various embodiments, the aromatic crosslinking component includes / or a cyanurate component, which is triallyl cyanurate, triallyl isocyanurate, or a combination of triallyl cyanurate and triallyl isocyanurate. For example, in some embodiments, the aromatic crosslinking component includes / or triallyl cyanurate. In some embodiments, the aromatic crosslinking component includes / or triallyl isocyanurate. In some embodiments, the aromatic crosslinking component includes / or a combination of triallyl cyanurate and triallyl isocyanurate. In some embodiments, the aromatic crosslinking component includes / or trimethylallyl isocyanurate.

[0044] However, those skilled in the art will understand that other aromatic crosslinking agents can be used in addition to or in place of the cyanurate materials described above. For example, in various embodiments, the aromatic crosslinking component includes (or) divinylbenzene.

[0045] In various embodiments, the aromatic crosslinking component includes (or) triallyl cyanurate, triallyl isocyanurate, trimethylallyl isocyanurate, divinylbenzene, or any combination thereof.

[0046] Aromatic crosslinking components, such as those mentioned above, are widely available from various suppliers.

[0047] The thermosetting compositions described herein may contain various amounts of aromatic crosslinking components. For example, in various embodiments, the aromatic crosslinking component is present in an amount of 2-11 wt%, such as 2-9 wt%, or 2-7 wt%. In various embodiments, the aromatic crosslinking component is present in an amount of 3-15 wt%, such as 3-11 wt%, or 3-9 wt%, or 3-7 wt%. In various embodiments, the aromatic crosslinking component is present in an amount of 4-15 wt%, such as 4-11 wt%, or 4-9 wt%, or 4-7 wt%. Those skilled in the art can adjust the amount of aromatic crosslinking component to provide the desired properties of the cured material.

[0048] The thermosetting composition further includes a butadiene / styrene copolymer rubber component in an amount of 5-25 wt%. As used herein, the butadiene / styrene copolymer rubber is a polymer formed from at least 80 wt% butadiene and styrene residues, and has a glass transition temperature not exceeding 5°C as measured by DSC. The corresponding components of the thermosetting composition may contain one or more such rubber samples.

[0049] In various embodiments, the total content of butadiene and styrene residues in the butadiene / styrene copolymer rubber component is at least 90 wt%, for example at least 95 wt%, at least 97 wt%, at least 98 wt%, or at least 99 wt%.

[0050] However, in various embodiments, the butadiene / styrene copolymer rubber component contains a significant number of other residues. For example, in some embodiments, the butadiene / styrene copolymer rubber component contains divinylbenzene residues, for example, grafted onto the butadiene / styrene backbone. In various embodiments, the butadiene / styrene copolymer rubber component contains up to 5 wt% of divinylbenzene residues, for example, 0.5-5 wt%, or 0.5-3 wt%, or 1-5 wt%, or 1-3 wt%.

[0051] In various embodiments further described herein, the butadiene / styrene copolymer rubber component has butadiene and styrene arranged in a substantially random pattern. Those skilled in the art will understand that such materials can be manufactured by copolymerizing butadiene and styrene in a single process. However, in alternative embodiments, copolymers with significant block copolymer characteristics can be used.

[0052] In various embodiments, the number average molecular weight of the butadiene / styrene copolymer rubber component is in the range of 1500-7000 g / mol, for example 1500-5000 g / mol, or 2500-7000 g / mol, or 2500-5000 g / mol.

[0053] The amount of the 1,2-vinyl moiety in the butadiene / styrene substantially random copolymer rubber component can vary. In various embodiments, the molar fraction of the 1,2-vinyl moiety of butadiene residues in the butadiene / styrene copolymer rubber component is in the range of 15-80 mol%, for example 15-70%, or 15-60%, or 20-80 mol%, or 20-70 mol%, or 20-60 mol%. In various embodiments, the molar fraction of the 1,2-vinyl moiety of butadiene residues in the butadiene / styrene copolymer rubber component is 25-80 mol%, for example 25-70%, or 25-60%, or 30-80 mol%, or 30-70 mol%, or 30-60 mol%. In various embodiments, the molar fraction of the 1,2-vinyl portion of the butadiene residues in the butadiene / styrene copolymer rubber component is 35-80 mol%, for example 35-70%, or 35-60%, or 40-80 mol%, or 40-70 mol%, or 40-60 mol%. In various embodiments, the molar fraction of the 1,2-vinyl portion of the butadiene residues in the butadiene / styrene copolymer rubber component is 20-60 mol%, for example, 20-55 mol%, or 20-50 mol%, or 20-45 mol%, or 25-60 mol%, or 25-55 mol%, or 25-50 mol%, or 25-45 mol%, or 30-60 mol%, or 30-55 mol%, or 30-50 mol%, or 30-45 mol%, or 35-60 mol%, or 35-55 mol%, or 35-50 mol%, or 35-45 mol%.

[0054] The amount of styrene residues in the butadiene / styrene copolymer rubber component can also vary. In various embodiments, the butadiene / styrene substantially random copolymer rubber component has 15-40 wt% styrene residues, for example 15-35 wt% or 15-30 wt%. In various embodiments, the butadiene / styrene copolymer rubber component has 20-40 wt% styrene residues, for example 20-35 wt% or 20-30 wt%. In various embodiments, the butadiene / styrene copolymer rubber component has 23-40 wt% styrene residues, for example 23-35 wt% or 23-30 wt%.

[0055] While the butadiene / styrene copolymer rubber component can consist essentially of a single butadiene / styrene copolymer rubber sample, blends may be used in certain cases. For example, in various embodiments, the butadiene / styrene copolymer rubber component comprises a first butadiene / styrene substantially random copolymer rubber sub-component and a second butadiene / styrene substantially random copolymer rubber sub-component, the first sub-component having 17-27 wt% styrene residues, and wherein the molar fraction of the 1,2-vinyl portion of the butadiene residues is 60-80 mol; the second sub-component having 20-30 wt% styrene residues, and wherein the molar fraction of the 1,2-vinyl portion of the butadiene residues is 20-40 mol. In various such embodiments, the weight ratio of the first butadiene / styrene substantially random copolymer rubber sub-component to the second butadiene / styrene substantially random copolymer rubber sub-component is in the range of 1:1.2 to 1:2.3, for example 1:1.5 to 1:2.3, or 1:1.2 to 1:2, or 1:1.5 to 1:2.

[0056] Butadiene / styrene basic random copolymer rubber materials are available from a variety of suppliers, including Cray Valley (e.g., Ricon 100, Ricon 181, Ricon 184, Ricon 257) and Kuraray Co., Ltd. (L-SBR grades, including L-SBR-870, L-SBR-822, and L-SBR-841). Block copolymer materials are also widely available.

[0057] The amount of the butadiene / styrene copolymer rubber component in the thermosetting composition can vary. For example, in various embodiments, the butadiene / styrene copolymer rubber component is present in an amount of 5-20 wt%, or 5-18 wt%, or 5-15 wt%. In various embodiments, the butadiene / styrene copolymer rubber component is present in an amount of 7-25 wt%, for example 7-20 wt%, or 7-18 wt%, or 7-15 wt%. In various embodiments, the butadiene / styrene substantially random copolymer rubber component is present in an amount of 9-25 wt%, for example 9-20 wt%, or 9-18 wt%, or 9-15 wt%.

[0058] The thermosetting composition further includes microparticle silica in an amount of 15-50 wt%. As used herein, microparticle silica is a particulate material having at least 95 wt% SiO2, and d 50 The particle size ranges from 0.1 to 100 micrometers. In various embodiments, the d... 50The 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 d of the microparticles of silica... 90 The particle size 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. In various embodiments, the d of the microparticles of silica... 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. In various embodiments, the microparticles of silica have at least 99 wt% SiO2, for example at least 99.5 wt% SiO2.

[0059] The microparticles of silica are ideally substantially spherical. Those skilled in the art can verify the sphericity using a microscope.

[0060] 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.

[0061] The amount of microparticle silica can vary. For example, in various embodiments, the microparticle silica is present in an amount of 15-45 wt%, or 15-40 wt%, or 15-35 wt%. In various specific embodiments, the microparticle silica is present in an amount of 20-50 wt%, for example, 20-45 wt%, or 20-40 wt%, or 20-35 wt%. In various specific embodiments, the microparticle silica is present in an amount of 25-50 wt%, for example, 25-45 wt%, or 25-40 wt%, or 25-35 wt%.

[0062] The thermosetting composition further includes an organic halogen-free flame retardant component in an amount of 15-35 wt%. In various embodiments, the organic halogen-free flame retardant comprises phosphorus.

[0063] It is worth noting that the inventors of this invention have discovered that certain flame retardants described in U.S. Patents 8,536,256, 9,012,546, 9,522,927, and 9,562,063 can provide particularly good performance in the thermosetting compositions described herein. Therefore, the entire contents of these patents are incorporated herein by reference, and their text is reproduced below; this disclosure contemplates the use of any flame retardant generally 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 comprises (or) 6H-dibenzo[c,e][1,2]oxaphosphacyclohexane, 6,6'-(1,4-ethanediyl)bis-, 6,6'-dioxide; 6H-dibenzo[c,e][1,2]oxaphosphacyclohexane, 6,6'-(1,4-butanediyl)bis-, 6,6'-dioxide; or 6H-dibenzo[c,e][1,2]oxaphosphacyclohexane, 6,6'-(p-xylyl)bis-, 6,6'-dioxide; or any combination thereof. In various embodiments, the flame retardant component comprises (or) 6H-dibenzo[c,e][1,2]oxaphosphacyclohexane, 6,6'-(1,4-ethanediyl)bis-, 6,6'-dioxide. In various embodiments, the flame retardant component comprises (or) compounds having the following structures: .

[0064] In various embodiments, the flame-retardant component comprises / or includes a composition containing a high-melting-point isomer of formula IIa:

[0065] and low-melting-point isomers having the following formulas IIb and IIc:

[0066] 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 For the area of ​​the high-melting-point isomer peak, A l This represents the area of ​​the low-melting-point isomer peak.

[0067] However, in other embodiments, other halogen-free flame retardants may be used. In various embodiments, the organic halogen-free flame retardant is a phosphorus-containing flame retardant, such as FRM 6300 (Qingdao) and Mosaflam 615 (UFC).

[0068] The organic halogen-free flame retardant component can be provided in various amounts within a wider range of 15-35 wt% in the thermosetting composition. For example, in various embodiments, the organic halogen-free flame retardant component is present in an amount of 15-30 wt%, such as 15-25 wt%. In various embodiments, the organic halogen-free flame retardant component is present in an amount of 20-35 wt%, such as 20-30 wt%. In various embodiments, the organic halogen-free flame retardant component is present in an amount of 25-35 wt%, such as 25-30 wt%.

[0069] As described above, the thermosetting composition further includes an effective amount of a thermal free radical initiator component. Those skilled in the art will determine the ideal thermal free radical initiator or combination thereof, and the ideal amount, to initially polymerize the thermosetting composition into a B-stage composition, and further polymerize the B-stage composition into a fundamentally polymerized composition, such as in laminate form. Suitable initiators include, but are not limited to: benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide, tert-butylbenzene hydroperoxide, acetyl isobutyryl peroxide, diacetyl peroxide, tert-butylperoctanoate, α,α'-bis(tert-butylperoxy-m-isopropyl)benzene, 2,3-dimethyl-2,3-diphenylbutane, bis(trimethylsilane)peroxide, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexane, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)-hex-3-yne, di-tert-butylperoxide The initiator components include tert-butylisopropylphenyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl peroxide, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)octane, 2-trimethylsilylphenyltriphenylsilyl peroxide, 2,3-trimethylsilyloxy-2,3-diphenylbutane, di(tert-butylperoxy)isophthalate, azobisisobutyronitrile (AIBN), azobis(2-isopropyl)butyronitrile, 2,2'-azobis(2,4-dimethyl)pentanonitrile (AVBN), (2,4-dichlorobenzoyl)peroxide, (2-dimethylbenzoyl)peroxide, and dodecanoyl peroxide. Those skilled in the art can use a single initiator or a combination of initiators to provide the initiator components. In some embodiments, the one or more initiators may be provided together with a support; those skilled in the art will understand that the mass of the thermal free radical initiator component is calculated as the mass of the initiator compound itself, omitting the mass of any support.

[0070] Those skilled in the art will determine the effective amount of the thermal free radical initiator component. For example, in various embodiments, the thermal free radical initiator component is present in an amount of 0.05-4 wt%, such as 0.05-2 wt%, 0.05-1 wt%, or 0.05-0.7 wt%. In various embodiments, the thermal free radical initiator component is present in an amount of 0.07-4 wt%, such as 0.07-2 wt%, 0.07-1 wt%, or 0.07-0.7 wt%. In various embodiments, the thermal free radical initiator component is present in an amount of 0.1-4 wt%, such as 0.1-2 wt%, 0.1-1 wt%, or 0.1-0.7 wt%. In various embodiments, the thermal free radical initiator component is present in an amount of 0.2-4 wt%, such as 0.2-2 wt%, 0.2-1 wt%, or 0.2-0.7 wt%.

[0071] In addition to the components described above, other components may be present in certain embodiments. For example, in various embodiments, the thermosetting composition may further include a silane coupling agent, for instance, to provide adhesion to microparticle silica fillers and / or glass materials used in the manufacture of prepregs or laminates. Silane coupling agents are familiar to those skilled in the art, and suitable coupling agents can be selected based on the description herein. For example, in some embodiments, the silane coupling agent may be selected from one or more (meth)acryloyl-functionalized silanes (e.g., 3-(meth)acryloyloxypropyltrimethoxysilane), vinyl-functionalized silanes (e.g., vinyltriethoxysilane), allyl-functionalized silanes (e.g., allyltrimethoxysilane), and other silanes with reactive carbon-carbon double bonds (e.g., styryltrimethoxysilane, 3-butenyltriethoxysilane, 7-octenyltriethoxysilane). The silane coupling agent may be present, for example, in an amount up to 5 wt%, for example, in the range of 0.1-5 wt%. However, the inventors of this invention have noted that in many embodiments, the silane coupling agent is not necessary for good performance, and therefore in various embodiments, the amount of silane coupling agent present does not exceed 0.01 wt%.

[0072] The amounts of each component in the thermosetting compositions described herein are calculated on a dry solids basis, i.e., 100 wt% is the total amount of the non-volatile (i.e., boiling point below 200°C at atmospheric pressure) components of the composition. In various embodiments, the thermosetting compositions are provided in a substantially non-volatile form, i.e., free of significant amounts of solvent. The inventors of the present invention have noted that the thermosetting compositions described herein can provide desirable viscosity in many embodiments without the use of significant amounts of solvent. Therefore, in various embodiments, the thermosetting compositions described herein can provide no more than 10 wt% of material with a boiling point below 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 of which are calculated on a non-volatile content basis of 100 wt%.

[0073] However, the inventors of this invention have noted that solvents can help provide materials with lower viscosity for processing, particularly 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 below 200°C at atmospheric pressure. Those skilled in the art will understand that a variety of solvents can be used, alone or in combination, and suitable solvents for the various components of the suspension composition can be determined. Possible examples include γ-butyrolactone, cyclohexanone, butanone, methyl isobutyl ketone, N,N-dimethylformamide, propylene glycol monomethyl ether, N,N-dimethylacetamide, ethylene glycol monomethyl ether, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, 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., totaling 100 wt%).

[0074] Another aspect of this disclosure is the cured product of the thermosetting compositions described herein. As will be understood by those skilled in the art, the cured product may, in some embodiments, be only partially cured, for example, cured into a solid form, making it workable but capable of being cured more completely by further processing. This partial curing may reach what is known as "stage B," or less or more. In other embodiments, the cured product may be substantially fully cured, and therefore substantially stable to further processing. A variety of curing conditions may 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.

[0075] Another aspect of this disclosure is a prepreg comprising a mesh substrate at least partially embedded in a cured product of this disclosure, ideally a partially cured product that can subsequently be further cured by further heating. One embodiment is... Figure 1 The diagram is shown in a schematic cross-sectional view. Here, the prepreg 100 includes a mesh substrate 110 embedded in the cured product 120 of this disclosure.

[0076] Various mesh substrates can be used by those skilled in the art. For example, in various embodiments, the mesh substrate is a fabric (woven or non-woven), such as made of glass fiber, carbon fiber, or various polymer fibers (such as aramid fiber, for example, a material provided 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 of (as oxides) 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%). Examples of suitable 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 will be understood by those skilled in the art, prepregs can have various total thicknesses, but in some embodiments, the thickness of the prepreg 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 thickness of the prepreg 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 thickness of the prepreg is in the range of 50-300 micrometers, for example 50-200 micrometers, or 50-150 micrometers. The prepreg ideally contains at least 30 wt% of the cured product of this disclosure, for example at least 50 wt%.

[0077] Those skilled in the art are familiar with methods for manufacturing prepregs and will adapt these methods for use with the thermosetting compositions of this disclosure. The thermosetting composition can be contacted with a mesh substrate, dried as needed to remove any volatiles, and cured by heat to at least partially cure the thermosetting composition to provide a prepreg.

[0078] Another aspect of this disclosure is laminates of various prepregs disclosed herein. One example is... Figure 2The diagram is shown in a schematic perspective view. Here, laminate 230 comprises laminates of a plurality of prepregs 200. The laminate can be manufactured by hot-pressing a plurality of prepregs described herein to cause softening and further curing of the partially cured material of the prepregs, 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 substantially completely cure the material. As used herein, substantially complete curing can be determined using a ΔTg measurement, wherein the material is run in a differential scanning calorimeter to 250°C and a first Tg is determined. The sample is then cooled to room temperature and the Tg measurement is repeated to 250°C to provide a second Tg. If the difference between the first Tg and the second Tg does not exceed 10°C, the material is said to be substantially completely cured. Techniques for forming laminates from prepregs are also familiar to those skilled in the art and will be adapted for use with the prepregs of this disclosure.

[0079] The laminate disclosed herein may comprise one or more layers of metal, such as copper. The one or more layers of metal may be disposed, for example, 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, circuit board laminates may be constructed in multiple steps, for example, by providing a first laminate having metal on one or both sides, then forming circuitry from that metal, and then further laminating the first laminate thus treated with additional prepreg layers and metal layers to form a multilayer laminate.

[0080] The inventors of this invention have discovered that the material described herein provides good peel strength even when used with thin, low-roughness copper. Such copper is available under the designation "BF-NN". In various embodiments, 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. In various embodiments, each of the one or more copper layers has an outer surface away from the surface laminated with the prepreg, which has 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, for example, 0.15-0.25 micrometers. In various embodiments, each of the one or more copper layers has an inner surface that contacts one of the prepregs, the inner 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), all measured by a non-contact method, ISO 25178.

[0081] The inventors of this invention have discovered that the material described herein possesses a variety of desirable properties, including a low Df value, good peel strength, and a high glass transition temperature. For example, in various embodiments, the laminate has a Df value in the range of 0.0015 to 0.003, e.g., 0.0015 to 0.0025, as measured by IPC-TM-650 2.5.5.5. In various embodiments, the laminate has a peel strength of at least 2.5 lb / in as measured by IPC-TM-650 2.4.8 (e.g., in the range of 2.5-5 lb / in, or 2.5-4.5 lb / in, or 2.5-4 lb / in, or 3-5 lb / in, or 3-4.5 lb / in, or 3-4 lb / in). In various embodiments, the laminate has a Tg measured by DSC 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.

[0082] Various aspects and implementations of this disclosure are further provided through the following non-limiting examples.

[0083] Example 1

[0084] Various aspects and implementations of this disclosure are further provided through the following non-limiting examples.

[0085] Various specific example formulations include the following components, based on solids:

[0086] The PPO methacrylate is a poly(phenylene ether) dimethacrylate supplied under the trade name NORYL 900, having the following nominal structural formula:

[0087] The styrene-butadiene rubber (70% 1,2-vinyl, 17-27 wt% styrene) is supplied under the trade name RICON® 100. The styrene-butadiene rubber (20-40% 1,2-vinyl, 20-30 wt% styrene) is supplied under the trade name RICON® 181. The styrene-butadiene rubber (30% 1,2-vinyl, 28% styrene) is supplied under the trade name RICON® 184. The microparticle silica is DQ-1028L from Novoray. The halogen-free flame retardant is a composition containing a high-melting-point isomer of formula IIa:

[0088] The low-melting-point isomers of formulas IIb and IIc have the following formula:

[0089] 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 Area of ​​the high-melting-point isomer peak; A l Area of ​​the low-melting-point isomer peak.

[0090] The thermosetting composition was fabricated into a 6-layer laminate. The thermosetting composition was added to an impregnation tank, and woven glass fabric (2116, low Dk glass, 0.10 mm thickness, 105 g / m²) was then applied. 2 The glass fabric is pulled through an impregnation tank and then through rollers with a gap thickness of 0.012. The resin-coated glass fabric is then dried in an oven to substantially remove the solvent (i.e., less than 1% residual solvent). This provides a prepreg material on the glass with 57% resin and a thickness of approximately 0.005 inches.

[0091] Six layers of this prepreg are laminated between two sheets of copper (BF-NN grade, ultra-flat profile, "1 oz", nominal thickness 35 microns), with the treated copper surface in contact with the prepreg material. The assembly is then placed between two stainless steel 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 raised to the curing temperature (210°C) at a specified heating rate (2.5°C / min) and held at that temperature for a specified time (120 minutes). The press is then cooled at approximately 5°C / min until the resulting laminate is cooled to a temperature suitable for removal.

[0092] The data for the two example formulations are shown in the table below:

[0093] Using thin, highly flat copper is particularly challenging in terms of peel strength. This paper demonstrates that the formulation described herein provides good peel strength even with BF-NN grade copper.

[0094] Various aspects of this disclosure are illustrated by the following enumerated embodiments, which can be combined in any number and in any technically or logically consistent manner: Implementation Scheme 1. A thermosetting composition comprising: A poly(1,4-phenylene ether) component having a content of at least 80% phenylene ether, wherein the poly(1,4-phenylene ether) component is a poly(1,4-phenylene ether) bis(meth)acrylate component, a bis(vinyl)poly(1,4-phenylene ether) component, or a bis((meth)allyl)poly(1,4-phenylene ether) component, or a combination of two or more thereof, and its amount is 20-35 wt%. The aromatic crosslinked component has a weight-average molecular weight of not more than 700 g / mol and each molecule has an average of 1.75-3.5 crosslinkable vinyl, (meth)allyl and / or (meth)acrylate groups, in an amount of 2-15 wt%. The butadiene / styrene copolymer rubber component, in an amount of 5-25 wt%; Microparticles of silica, in an amount of 15-50 wt%; Organic halogen-free flame retardant components, in an amount of 15-35 wt%; and The thermal free radical initiator component is present in an amount of 0.1-3 wt%.

[0095] Implementation Scheme 2. The thermosetting composition according to Implementation Scheme 1, wherein the mass of the (optionally substituted phenylene) groups in the -O- (optionally substituted phenylene) content of the poly(1,4-phenylene ether) component consists of at least 50% phenyl carbon and phenyl hydrogen.

[0096] Implementation Scheme 3. The thermosetting composition according to Implementation Scheme 1 or Implementation Scheme 2, wherein the poly(1,4-phenylene ether) bis(meth)acrylate component is a poly(1,4-phenylene ether) dimethacrylate component, i.e., having at least 75 wt%, for example at least 90 wt% of poly(1,4-phenylene ether) dimethacrylate.

[0097] Implementation Scheme 4. The thermosetting composition according to Implementation Scheme 1 or Implementation Scheme 2, wherein the poly(1,4-phenylene ether) component is a bis(vinyl)poly(1,4-phenylene ether) component, i.e., having at least 75 wt%, for example at least 90 wt% of bis(vinyl)poly(1,4-phenylene ether).

[0098] Implementation Scheme 5. The thermosetting composition according to Implementation Scheme 1 or Implementation Scheme 2, wherein the poly(1,4-phenylene ether) component is a bis(allyl)poly(1,4-phenylene ether) component, i.e., having at least 75 wt%, for example at least 90 wt% of bis(allyl)poly(1,4-phenylene ether).

[0099] Implementation Scheme 6. The thermosetting composition according to Implementation Scheme 1 or Implementation Scheme 2, wherein the poly(1,4-phenylene ether) component is a bis(methylallyl)poly(1,4-phenylene ether) component, i.e., having at least 75 wt%, for example at least 90 wt% of bis(methylallyl)poly(1,4-phenylene ether).

[0100] Implementation Scheme 7. The thermosetting composition according to any one of Implementation Schemes 1-6, wherein the poly(1,4-phenylene ether) component has the following formula:

[0101] Where A is a bond, -CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -C(O)-, -S(O)-, or -S(O)2-; each R 1 Independently, it is methacrylate, acrylate, vinyl, allyl, or methallyl; each R 2 Independently methyl or hydrogen; and each R 3 It can be methyl or hydrogen on its own.

[0102] Implementation Scheme 8. The thermosetting composition according to Implementation Scheme 7, wherein A is -CH2-, -CH(CH3)- or -C(CH3)2-.

[0103] Implementation Scheme 9. The thermosetting composition according to Implementation Scheme 7, wherein A is -C(CH3)2-.

[0104] Implementation Scheme 10. The thermosetting composition according to any one of Implementation Schemes 7-9, wherein at least 75% of the content of the thermosetting composition is in the form of a thermosetting composition. In some parts (e.g., at least 90% or at least 98%), two Rs 2 It is methyl and has two Rs 2 It is H.

[0105] Implementation Scheme 11. The thermosetting composition according to any one of Implementation Schemes 7-9, wherein at least 75% of the content of the thermosetting composition is... In some parts (e.g., at least 90% or at least 98%), two Rs 2 It is a methyl group that is meta-substituted and both R groups are present. 2 It is H.

[0106] Implementation Scheme 12. The thermosetting composition according to any one of Implementation Schemes 7-9, wherein at least 75% of the content of the thermosetting composition is in the form of a thermosetting composition. In some parts (e.g., at least 90% or at least 98%), two Rs 2 It is a methyl group and is substituted in a meta position away from the A moiety, and both R groups are... 2 It is H.

[0107] Implementation Scheme 13. The thermosetting composition according to any one of Implementation Schemes 7-12, wherein at least 75% of the content of the thermosetting composition is... In some parts (e.g., at least 90% or at least 98%), two Rs 3 It is methyl and has two Rs 3 It is H.

[0108] Implementation Scheme 14. The thermosetting composition according to any one of Implementation Schemes 7-13, wherein at least 75% of the content of the thermosetting composition is... In some parts (e.g., at least 90% or at least 98%), two Rs 3 It is a methyl group that is meta-substituted and both R groups are present. 3 It is H.

[0109] Implementation Scheme 15. The thermosetting composition according to any one of Implementation Schemes 7-14, wherein at least 75% of the content of the thermosetting composition is... In some parts (e.g., at least 90% or at least 98%), two Rs 3 It is a methyl group and is substituted in a meta position away from the A moiety, and both R groups are... 3 It is H.

[0110] Implementation Scheme 16. The thermosetting composition according to any one of Implementation Schemes 7-15, wherein at least 75% of R 1 It is a methacrylate, for example, at least 90%, or at least 95%.

[0111] Implementation Scheme 17. The thermosetting composition according to any one of Implementation Schemes 4-15, wherein at least 75% of R 1 It is vinyl, for example, at least 90%, or at least 95%.

[0112] Implementation Scheme 18. The thermosetting composition according to any one of Implementation Schemes 4-15, wherein at least 75% of R 1 It is allyl, for example, at least 90%, or at least 95%.

[0113] Implementation Scheme 19. The thermosetting composition according to any one of Implementation Schemes 4-15, wherein at least 75% of R1 is methylallyl, for example at least 90%, or at least 95%.

[0114] Implementation Scheme 20. The thermosetting composition according to any one of Implementation Schemes 4-15, wherein at least 75% of R 1 It is methacrylate, vinyl, allyl or methylallyl, for example at least 90%, or at least 95%.

[0115] Implementation Scheme 21. The thermosetting composition according to any one of Implementation Schemes 7-20, wherein the poly(1,4-phenylene ether) component comprises at least 75% by weight, for example at least 90% by weight or at least 95% by weight, having the following formula: .

[0116] Implementation Scheme 22. The thermosetting composition according to any one of Implementation Schemes 7-21, wherein the number mean of the sum of x+y of the poly(1,4-phenylene ether) component is in the range of 3-30, for example 3-25, or 3-20, or 3-15, or 5-30, or 5-25, or 5-20, or 5-15, or 7-30, or 7-25, or 7-20, or 7-15, or 10-30, or 10-25, or 10-20, or 10-15.

[0117] Implementation Scheme 23. The thermosetting composition according to any one of Implementation Schemes 1-22, wherein the number average molecular weight of the poly(1,4-phenylene ether) component is in the range of 1000-4000 g / mol, for example 1000-3500 g / mol or 1000-3000 g / mol, or 1000-2500 g / mol, or 1500-4000 g / mol, or 1500-3500 g / mol, or 1500-2500 g / mol.

[0118] Implementation Scheme 24. The thermosetting composition according to any one of Implementation Schemes 1-23, wherein the poly(1,4-phenylene ether) component is present in an amount of 22-35% by weight, for example 22-32% by weight, or 22-30% by weight.

[0119] Implementation Scheme 25. The thermosetting composition according to any one of Implementation Schemes 1-24, wherein the poly(1,4-phenylene ether) component is present in an amount of 25-35% by weight, for example 25-32% by weight, or 25-30% by weight.

[0120] Implementation Scheme 26. The thermosetting composition according to any one of Implementation Schemes 1-25, wherein the aromatic crosslinking component comprises (or) a cyanurate component.

[0121] Implementation Scheme 27. The thermosetting composition according to any one of Implementation Schemes 1-26, wherein the aromatic crosslinking component is a cyanurate component, which is triallyl cyanurate, triallyl isocyanurate, or a combination of triallyl cyanurate and triallyl isocyanurate.

[0122] Implementation Scheme 28. The thermosetting composition according to any one of Implementation Schemes 1-27, wherein the aromatic crosslinking component comprises (or) triallyl cyanurate.

[0123] Implementation Scheme 29. The thermosetting composition according to any one of Implementation Schemes 1-28, wherein the aromatic crosslinking component comprises (or) triallyl isocyanurate.

[0124] Implementation Scheme 30. The thermosetting composition according to any one of Implementation Schemes 1-29, wherein the aromatic crosslinking component comprises (or) a combination of triallyl cyanurate and triallyl isocyanurate.

[0125] Implementation Scheme 31. The thermosetting composition according to any one of Implementation Schemes 1-30, wherein the aromatic crosslinking component comprises (or) trimethylallyl isocyanurate.

[0126] Implementation Scheme 32. The thermosetting composition according to any one of Implementation Schemes 1-30, wherein the aromatic crosslinking component comprises (or) divinylbenzene.

[0127] Implementation Scheme 33. The thermosetting composition according to any one of Implementation Schemes 1-30, wherein the aromatic crosslinking component comprises (or) triallyl cyanurate, triallyl isocyanurate, trimethylallyl isocyanurate, divinylbenzene, or any combination thereof.

[0128] Implementation Scheme 34. The thermosetting composition according to any one of Implementation Schemes 1-33, wherein the aromatic crosslinking component is present in an amount of 2-11% by weight, for example 2-9% by weight, or 2-7% by weight.

[0129] Implementation Scheme 35. The thermosetting composition according to any one of Implementation Schemes 1-33, wherein the aromatic crosslinking component is present in an amount of 3-15% by weight, for example 3-11% by weight, or 3-9% by weight, or 3-7% by weight.

[0130] Implementation Scheme 36. The thermosetting composition according to any one of Implementation Schemes 1-33, wherein the aromatic crosslinking component is present in an amount of 4-15% by weight, for example 4-11% by weight, or 4-9% by weight, or 4-7% by weight.

[0131] Implementation Scheme 37. The thermosetting composition according to any one of Implementation Schemes 1-36, wherein the total content of butadiene and styrene residues of the butadiene / styrene copolymer rubber component is at least 90% by weight, for example at least 95% by weight, at least 97% by weight, at least 98% by weight, or at least 99% by weight.

[0132] Implementation Scheme 38. The thermosetting composition according to any one of Implementation Schemes 1-37, wherein the butadiene / styrene copolymer rubber component comprises up to 5% by weight of divinylbenzene residues, for example in the range of 0.5-5% by weight, or 0.5-3% by weight, or 1-5% by weight, or 1-3% by weight.

[0133] Implementation Scheme 39. The thermosetting composition according to any one of Implementation Schemes 1-38, wherein the butadiene / styrene copolymer rubber component has butadiene and styrene arranged in a substantially random manner.

[0134] Implementation Scheme 40. The thermosetting composition according to any one of Implementation Schemes 1-39, wherein the number average molecular weight of the butadiene / styrene copolymer rubber component is in the range of 1500-7000 g / mol, for example 1500-5000 g / mol, or 2500-7000 g / mol, or 2500-5000 g / mol.

[0135] Implementation Scheme 41. The thermosetting composition according to any one of Implementation Schemes 1-40, wherein the molar fraction of the 1,2-vinyl portion of the butadiene residues of the butadiene / styrene copolymer rubber component is in the range of 15-80 mol%, for example 15-70%, or 15-60%, or 20-80 mol%, or 20-70 mol%.

[0136] Implementation Scheme 42. The thermosetting composition according to any one of Implementation Schemes 1-40, wherein the molar fraction of the 1,2-vinyl portion of the butadiene residues of the butadiene / styrene copolymer rubber component is 25-80 mol%, for example 25-70 mol%, or 25-60%, or 30-80 mol%, or 30-70 mol%.

[0137] Implementation Scheme 43. The thermosetting composition according to any one of Implementation Schemes 1-40, wherein the molar fraction of the 1,2-vinyl portion of the butadiene residues of the butadiene / styrene copolymer rubber component is 20-60 mol%, for example 20-55 mol%, or 20-50 mol%, or 20-45 mol%, or 25-60 mol%, or 25-55 mol%, or 25-50 mol%, or 25-45 mol%, or 30-60 mol%, or 30-55 mol%, or 30-50 mol%, or 30-45 mol%, or 35-60 mol%, or 35-55 mol%, or 35-50 mol%, or 35-45 mol%.

[0138] Implementation Scheme 44. The thermosetting composition according to any one of Implementation Schemes 1-43, wherein the butadiene / styrene copolymer rubber component has 15-40% by weight of styrene residues, for example 15-35% by weight or 15-30% by weight.

[0139] Implementation Scheme 45. The thermosetting composition according to any one of Implementation Schemes 1-43, wherein the butadiene / styrene copolymer rubber component has 20-40% by weight of styrene residues, for example 20-35% by weight or 20-30% by weight.

[0140] Implementation Scheme 46. The thermosetting composition according to any one of Implementation Schemes 1-43, wherein the butadiene / styrene copolymer rubber component has 23-40% by weight of styrene residues, for example 23-35% by weight or 23-30% by weight.

[0141] Implementation Scheme 47. The thermosetting composition according to any one of Implementation Schemes 1-46, wherein the butadiene / styrene copolymer rubber component comprises a first butadiene / styrene substantially random copolymer rubber sub-component and a second butadiene / styrene substantially random copolymer rubber sub-component, the first sub-component having 17-27% by weight of styrene residues, and wherein the molar fraction of the 1,2-vinyl portion of the butadiene residues is 60-80 mol; the second sub-component having 20-30% by weight of styrene residues, and wherein the molar fraction of the 1,2-vinyl portion of the butadiene residues is 20-40 mol.

[0142] Implementation Scheme 48. The thermosetting composition according to Implementation Scheme 47, wherein the weight ratio of the first butadiene / styrene substantially random copolymer rubber sub-component to the second butadiene / styrene substantially random copolymer rubber sub-component is in the range of 1:1.2-1:2.3, for example 1:1.5-1:2.3, or 1:1.2-1:2, or 1:1.5-1:2.

[0143] Implementation Scheme 49. The thermosetting composition according to any one of Implementation Schemes 1-48, wherein the butadiene / styrene copolymer rubber component is present in an amount of 5-20% by weight, or 5-18% by weight, or 5-15% by weight.

[0144] Implementation Scheme 50. The thermosetting composition according to any one of Implementation Schemes 1-48, wherein the butadiene / styrene copolymer rubber component is present in an amount of 7-25% by weight, for example 7-20% by weight, or 7-18% by weight, or 7-15% by weight.

[0145] Implementation Scheme 51. The thermosetting composition according to any one of Implementation Schemes 1-48, wherein the butadiene / styrene copolymer rubber component is present in an amount of 9-25% by weight, for example 9-20% by weight, or 9-18% by weight, or 9-15% by weight.

[0146] Implementation Scheme 52. The thermosetting composition according to any one of Implementation Schemes 1-51, wherein the microparticles of silica have a 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.

[0147] Implementation Scheme 53. The thermosetting composition according to any one of Implementation Schemes 1-52, wherein the microparticle silica has a d 90 The particle size 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.

[0148] Implementation Scheme 54. The thermosetting composition according to any one of Implementation Schemes 1-53, wherein the microparticle silica has a 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.

[0149] Implementation Scheme 55. The thermosetting composition according to any one of Implementation Schemes 1-54, wherein the microparticles of silica are substantially spherical.

[0150] Implementation Scheme 56. The thermosetting composition according to any one of Implementation Schemes 1-55, wherein the microparticle silica has at least 99% by weight SiO2, for example at least 99.5% by weight SiO2.

[0151] Implementation Scheme 57. The thermosetting composition according to any one of Implementation Schemes 1-56, wherein the microparticle silica is present in an amount of 15-45% by weight, or 15-40% by weight, or 15-35% by weight.

[0152] Implementation Scheme 58. The thermosetting composition according to any one of Implementation Schemes 1-57, wherein the microparticle silica is present in an amount of 20-50% by weight, for example 20-45% by weight, or 20-40% by weight, or 20-35% by weight.

[0153] Implementation Scheme 59. The thermosetting composition according to any one of Implementation Schemes 1-58, wherein the microparticle silica is present in an amount of 25-50% by weight, for example 25-45% by weight, or 25-40% by weight, or 25-35% by weight.

[0154] Implementation Scheme 60. The thermosetting composition according to any one of Implementation Schemes 1-59, wherein the organic halogen-free flame retardant component is a flame retardant according to any one of U.S. Patent Nos. 8,536,256, 9,012,546, 9,522,927, and 9,562,063.

[0155] Implementation Scheme 61. The thermosetting composition according to any one of Implementation Schemes 1-59, wherein the organic halogen-free flame retardant component comprises (or) 6H-dibenzo[c,e][1,2]oxaphosphacyclohexane, 6,6'-(1,4-ethanediyl)bis-, 6,6'-dioxide; 6H-dibenzo[c,e][1,2]oxaphosphacyclohexane, 6,6'-(1,4-butanediyl)bis-, 6,6'-dioxide; or 6H-dibenzo[c,e][1,2]oxaphosphacyclohexane, 6,6'-(p-xylenediyl)bis-, 6,6'-dioxide; or any combination thereof.

[0156] Implementation Scheme 62. The thermosetting composition according to any one of Implementation Schemes 1-59, wherein the organic halogen-free flame retardant component comprises (or) 6H-dibenzo[c,e][1,2]oxaphosphacyclohexane, 6,6'-(1,4-ethanediyl)bis-,6,6'-dioxide.

[0157] Implementation Scheme 63. The thermosetting composition according to any one of Implementation Schemes 1-59, wherein the organic halogen-free flame retardant component comprises / or a compound having the following structure: .

[0158] Implementation Scheme 64. A thermosetting composition according to any one of embodiments 1-59, wherein the organic halogen-free flame retardant component comprises / or a composition containing a high-melting-point isomer of formula IIa:

[0159] Low-melting-point isomers of formulas IIb and IIc:

[0160] 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 ​​the high-melting-point isomer; A l Peak area of ​​the low-melting-point isomer.

[0161] Implementation Scheme 65. The thermosetting composition according to any one of Implementation Schemes 1-64, wherein the organic halogen-free flame retardant component is present in an amount of 15-30% by weight, for example 15-25% by weight.

[0162] Implementation Scheme 66. The thermosetting composition according to any one of Implementation Schemes 1-64, wherein the organic halogen-free flame retardant component is present in an amount of 20-35% by weight, for example 20-30% by weight or 20-25% by weight.

[0163] Implementation Scheme 67. The thermosetting composition according to any one of Implementation Schemes 1-64, wherein the organic halogen-free flame retardant component is present in an amount of 25-35% by weight, for example 25-30% by weight.

[0164] Implementation Scheme 68. A thermosetting composition according to any one of Implementation Schemes 1-67, wherein the thermal free radical initiator component is one or more of the following: benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide, tert-butylbenzene hydroperoxide, acetyl isobutyryl peroxide, diacetyl peroxide, tert-butyl peroctanoate, α,α'-bis(tert-butylperoxy-m-isopropyl)benzene, 2,3-dimethyl-2,3-diphenylbutane, bis(trimethylsilane)peroxide, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexane, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy-m-isopropyl)benzene, etc. (Oxy)-hex-3-yne, di-tert-butyl peroxide, tert-butylisopropylphenyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)octane, 2-trimethylsilylphenyltriphenylsilyl peroxide, 2,3-trimethylsiloxy-2,3-diphenylbutane, di(tert-butylperoxy)isophthalate, azobisisobutyronitrile (AIBN), azobis(2-isopropyl)butyronitrile, 2,2'-azobis(2,4-dimethyl)valerate (AVBN), (2,4-dichlorobenzoyl)peroxide, (2-dimethylbenzoyl)peroxide, and dodecanoyl peroxide.

[0165] Implementation Scheme 69. The thermosetting composition according to any one of Implementation Schemes 1-68, wherein the thermal free radical initiator component is present in an amount of 0.05-4% by weight, for example 0.05-2% by weight, or 0.05-1% by weight, or 0.05-0.7% by weight.

[0166] Implementation Scheme 70. The thermosetting composition according to any one of Implementation Schemes 1-68, wherein the thermal free radical initiator component is present in an amount of 0.07-4% by weight, for example 0.07-2% by weight, or 0.07-1% by weight, or 0.07-0.7% by weight.

[0167] Implementation Scheme 71. The thermosetting composition according to any one of Implementation Schemes 1-68, wherein the thermal free radical initiator component is present in an amount of 0.1-4% by weight, for example 0.1-2% by weight, or 0.1-1% by weight, or 0.1-0.7% by weight.

[0168] Implementation Scheme 72. The thermosetting composition according to any one of Implementation Schemes 1-68, wherein the thermal free radical initiator component is present in an amount of 0.2-4% by weight, for example 0.2-2% by weight, or 0.2-1% by weight, or 0.2-0.7% by weight.

[0169] Implementation Scheme 73. The thermosetting composition according to any one of Implementation Schemes 1-72 further comprises a silane coupling agent, for example, in an amount up to 5 by weight.

[0170] Implementation Scheme 74. The thermosetting composition according to any one of Implementation Schemes 1-73, comprising not more than 0.01% by weight of a silane coupling agent.

[0171] Implementation Scheme 75. The thermosetting composition according to any one of Implementation Schemes 1-74 is provided in a substantially nonvolatile form, i.e., free of a large amount of solvent.

[0172] Implementation Scheme 76. The thermosetting composition according to any one of Implementation Schemes 1-74 comprises not more than 10% by weight of a material having a boiling point below 200°C at atmospheric pressure, for example not more than 5% by weight, or not more than 3% by weight, or not more than 1% by weight, all calculations being based on a non-volatile content of 100% by weight.

[0173] Implementation Scheme 77. The thermosetting composition according to any one of Implementation Schemes 1-74 further comprises a solvent having a boiling point below 200°C at atmospheric pressure.

[0174] Implementation Scheme 78. The thermosetting composition according to Implementation Scheme 77, 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, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, diisobutyl ketone (DIBK), N-methylpyrrolidone, xylene, ethyl acetate, toluene, trichloroethane, dibutyl ether, methyl ethyl ketone, and acetone.

[0175] Implementation Scheme 79. The thermosetting composition according to Implementation Scheme 77 or Implementation Scheme 78, wherein the amount of solvent is 20-60 wt% in excess of the non-volatile components of the thermosetting composition (i.e., totaling 100 wt%).

[0176] Implementation Scheme 80. A cured product of the thermosetting composition according to any one of Implementation Schemes 1-79.

[0177] Implementation Scheme 81. A method for curing a thermosetting composition according to any one of Implementation Schemes 1-79, comprising heating the thermosetting composition at a temperature of 150-250°C.

[0178] Implementation Scheme 82. A prepreg comprising a mesh substrate, said mesh substrate being at least partially embedded in the cured product of Implementation Scheme 80 or a cured product prepared by the method of Implementation Scheme 81.

[0179] Implementation Scheme 83. The prepreg according to Implementation Scheme 82, wherein the cured product is a partially cured product.

[0180] Implementation Scheme 84. The prepreg according to Implementation Scheme 82 or Implementation Scheme 83, wherein the mesh substrate is a fabric (woven or nonwoven fabric).

[0181] Implementation Scheme 85. The prepreg according to Implementation Scheme 84, wherein the fabric is made of glass fiber, such as borosilicate glass fabric.

[0182] Implementation Scheme 86. The prepreg according to Implementation Scheme 82 or Implementation Scheme 83, wherein the mesh substrate is electronic grade E-glass fabric, NE-glass fabric, D-glass fabric or S-glass fabric.

[0183] Implementation Scheme 87. The prepreg according to any one of Implementation Schemes 82-86 has a thickness in the range of 10-300 micrometers, for example 10-200 micrometers, or 10-150 micrometers, or 10-100 micrometers.

[0184] Implementation Scheme 88. The prepreg according to any one of Implementation Schemes 82-86 has a thickness in the range of 25-300 micrometers, for example 25-200 micrometers, or 25-150 micrometers, or 25-100 micrometers.

[0185] Implementation Scheme 89. The prepreg according to any one of Implementation Schemes 82-86 has a thickness in the range of 50-300 micrometers, for example 50-200 micrometers or 50-150 micrometers.

[0186] Embodiment 90. The prepreg according to any one of embodiments 82-89 comprises at least 30% by weight of the cured product of this disclosure, for example at least 50% by weight.

[0187] Implementation Scheme 91. A plurality of laminates of prepregs according to any one of Implementation Schemes 82-89.

[0188] Implementation Scheme 92. The laminate according to Implementation Scheme 91, wherein the curing product of the prepreg in the laminate is substantially completely cured.

[0189] Implementation Scheme 93. The laminate according to Implementation Scheme 91 or Implementation Scheme 92 further comprises one or more layers of metal, for example on one or two opposing main surfaces of the laminate.

[0190] Implementation Scheme 94. The laminate according to Implementation Scheme 93, wherein one or more metal layers are copper layers.

[0191] Implementation Scheme 95. The laminate according to Implementation Scheme 94, 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.

[0192] Implementation Scheme 96. The laminate according to Implementation Scheme 94 or Implementation Scheme 95, wherein each of the one or more copper layers has an outer surface away from the copper layer laminated with the prepreg, the outer 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, for example 0.15-0.25 micrometers.

[0193] Implementation Scheme 97. A laminate according to any one of embodiments 94-96, wherein each of the one or more copper layers has an inner surface in contact with a prepreg, the inner 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), all measured by a non-contact method ISO 25178.

[0194] Implementation Scheme 98. The laminate according to any one of Implementation Schemes 93-97 has a peel strength of at least 2.5 lb / in as measured by IPC-TM-6502.4.8 (e.g., in the range of 2.5-5 lb / in, or 2.5-4.5 lb / in, or 2.5-4 lb / in, or 3-5 lb / in, or 3-4.5 lb / in, or 3-4 lb / in).

[0195] Implementation Scheme 99. The laminate according to any one of Implementation Schemes 93-98 has a Df value in the range of 0.0015 to 0.003, for example, 0.0015 to 0.0025, as measured by IPC-TM-6502.5.5.5.

[0196] Implementation Scheme 100. The laminate according to any one of Implementation Schemes 93-99 has a Tg measured by DSC 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.

Claims

1. A thermoset composition comprising: 20-35 weight percent of a poly(l,4-phenylene ether) component having a phenylene ether content of at least 80%, the poly(l,4-phenylene ether) component being a poly(l,4-phenylene ether) bis(meth)acrylate component, a bis(vinyl) poly(l,4-phenylene ether) component, or a bis((meth)allyl) poly(l,4-phenylene ether) component, or a combination of two or more thereof; 2-15 weight percent of an aromatic crosslinking component having a weight average molecular weight of no greater than 700 g / mol and, on average, 1.75-3.5 crosslinkable vinyl, (meth)allyl, and / or (meth)acrylate groups per molecule; 5-25 weight percent of a butadiene / styrene copolymer rubber component; 15-50 weight percent of a microparticulate silica; 15-35 weight percent of an organic, halogen-free flame retardant component; and 0.1-3 weight percent of a thermal free radical initiator component.

2. The thermoset composition of claim 1, wherein the mass of the (optionally substituted phenylene) groups of the -0-(optionally substituted phenylene) content of the poly(l,4-phenylene ether) component consists of at least 50% phenyl carbons and phenyl hydrogens.

3. The thermoset composition of claim 1 or 2, wherein the poly(l,4-phenylene ether) bis(meth)acrylate component is a poly(l,4-phenylene ether) bismethacrylate component, i.e., having at least 75 weight percent, such as at least 90 weight percent, of poly(l,4-phenylene ether) bismethacrylate.

4. The thermoset composition of any of claims 1-3, wherein the poly(l,4-phenylene ether) component has the formula: wherein A is a bond, -CH2-, -CH(CH3)-, -C(CH3)2-, -0-, -C(O)-, -S(O)-, or -S(O)2-; each R 1 independently a methacrylate, acrylate, vinyl, allyl, or methallyl group; each R 2 independently a methacrylate, acrylate, vinyl, allyl, or methallyl group; each R 3 independently a methacrylate, acrylate, vinyl, allyl, or methallyl group; each R 5. The thermoset composition of claim 4, wherein at least 75 weight percent, such as at least 90 weight percent or at least 95 weight percent, of the poly(l,4-phenylene ether) component has the formula: 。 6. The thermoset composition of any of claims 1-5, wherein the poly(l,4-phenylene ether) component is present in an amount of 25-35 weight percent.

7. The thermoset composition of any of claims 1-6, wherein the aromatic crosslinking component is a cyanurate component that is triallyl cyanurate, triallyl isocyanurate, or a combination of triallyl cyanurate and triallyl isocyanurate.

8. The thermoset composition of any of claims 1-6, wherein the aromatic crosslinking component comprises (or is) triallyl cyanurate.

9. The thermoset composition of any of claims 1-8, wherein the aromatic crosslinking component is present in an amount of 4-15 weight percent, such as 4-11 weight percent, or 4-9 weight percent, or 4-7 weight percent.

10. The thermoset composition of any of claims 1-9, wherein the total content of butadiene and styrene residues of the butadiene / styrene copolymer rubber component is at least 95 weight percent.

11. The thermoset composition of any of claims 1-10, wherein the butadiene / styrene copolymer rubber component has butadiene and styrene in a substantially random arrangement.

12. The thermoset composition of any of claims 1-11, wherein the butadiene / styrene copolymer rubber component has a number average molecular weight in the range of 1500-7000 g / mol.

13. The thermoset composition of any of claims 1-12, wherein the butadiene / styrene copolymer rubber component has a mole fraction of 1,2-vinyl moieties of butadiene residues in the range of 15-80 mol%.

14. The thermoset composition of any of claims 1-12, wherein the butadiene / styrene copolymer rubber component has a mole fraction of 1,2-vinyl moieties of butadiene residues in the range of 30-60 mol%.

15. The thermoset composition of any of claims 1-13, wherein the butadiene / styrene copolymer rubber component has 23-40 wt% styrene residues.

16. The thermoset composition of any of claims 1-15, wherein the butadiene / styrene copolymer rubber component is comprised of a first butadiene / styrene substantially random copolymer subcomponent having 17-27 wt% styrene residues and wherein the mole fraction of 1,2-vinyl moieties of butadiene residues is 60-80 mol%, and a second butadiene / styrene substantially random copolymer subcomponent having 20-30 wt% styrene residues and wherein the mole fraction of 1,2-vinyl moieties of butadiene residues is 20-40 mol%, wherein the weight ratio of the first butadiene / styrene substantially random copolymer subcomponent to the second butadiene / styrene substantially random copolymer subcomponent is in the range of 1:1.2-1:2.

3.

17. The thermoset composition of any of claims 1-16, wherein the butadiene / styrene copolymer rubber is present in an amount of 9-25 wt%.

18. The thermoset composition of any one of claims 1-17, wherein the microparticulate silica has a d 10 particle size in the range of 0.1-5 microns.

19. The thermoset composition of any of claims 1-18, wherein the microparticulate silica is substantially spherical.

20. The thermoset composition of any of claims 1-19, wherein the microparticulate silica is present in an amount of 20-45 wt%.

21. The thermoset composition of any of claims 1-20, wherein the organic halogen-free flame retardant component comprises (or is) a compound having the following structure: 。 22. The thermoset composition of any of claims 1-21, wherein the organic halogen-free flame retardant component is present in an amount of 20-35 wt%.

23. The thermoset composition of any one of claims 1-22, wherein the thermal radical initiator component is one or more of: benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, t-butyl benzene hydroperoxide, acetyl isobutyl peroxide, diacetyl peroxide, t-butyl peroctoate, a,a'-bis(t-butylperoxy-m-isopropyl)benzene, 2,3-dimethyl-2,3-diphenylbutane, di(trimethylsilyl) peroxide, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexane, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)-hex-3-yne, di-t-butyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butyl benzene peroxalate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2-trimethylsilylphenyl triphenylsilyl peroxide, 2,3-trimethylsiloxy-2,3-diphenylbutane, di(t-butylperoxy) isophthalate, azobisisobutyronitrile (AIBN), azobis(2-isopropyl)butyronitrile, 2,2'-azobis(2,4-dimethyl)pentanenitrile (AVBN), (2,4-dichlorobenzoyl) peroxide, (2-dimethylbenzoyl) peroxide, and dodecanoyl peroxide.

24. The thermoset composition of any one of claims 1-23, wherein the thermal radical initiator component is present in an amount of 0.2-2 wt%.

25. A cured product of the thermoset composition of any one of claims 1-24.

26. A method of curing the thermoset composition of any one of claims 1-24, the method comprising heating the thermoset composition at a temperature of 150-250 °C.

27. A prepreg comprising a webbed substrate at least partially embedded in the cured product of claim 25, or at least partially embedded in the cured product made by the method of claim 26.

28. A laminate of a plurality of prepregs of claim 27.

29. The laminate of claim 28 having a peel strength of at least 2.5 lb / in measured by IPC-TM-650 2.4.8; a Df value in the range of 0.0015 to 0.003 measured by IPC-TM-650 2.5.5.5; and a Tg in the range of 180-240 °C measured by DSC.

30. The laminate of claim 29, wherein the prepreg is a prepreg of claim 27.

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