Hardening components

Abstract

The present disclosure relates to a curable composition comprising at least a first, a second, and a third polymer. The first polymer comprises a first monomer unit and a second monomer unit different from the first monomer unit, the first monomer unit having a structure according to formula (I) as defined herein, and the second monomer unit having a structure according to formula (II) as defined herein. The second polymer comprises at least about 60% by weight of styrene monomer units, and the third polymer comprises at most about 60% by weight of styrene monomer units. The present disclosure also relates to using the composition to form a free-standing film, laminate, prepreg, and / or printed circuit board.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 312,415, filed February 22, 2022, the contents of which are incorporated herein by reference in their entirety.

[0002] Technical Field The present disclosure relates to curable compositions, and related methods, laminates, prepregs, and circuit boards. [Background technology]

[0003] In order to meet the demand for high frequency transmission, the requirements of high frequency transmission systems and wireless communication devices in the industry are constantly increasing. Generally, a circuit assembly includes a conductive metal layer and a dielectric substrate layer. To meet the demand for high frequency transmission, the dielectric substrate layer needs to have a low dissipation factor (Df) (e.g., at most 0.0020). Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure is based on the unexpected discovery that certain curable compositions comprising styrene-containing polymers can exhibit superior electrical properties (e.g., low Dk and Df), improved stability, improved mechanical properties (interlayer bond strength), and improved adhesion properties to other materials (e.g., peel strength). [Means for solving the problem]

[0005] In one aspect, the present disclosure features a curable composition (e.g., a curable resin composition) that includes: (1) at least one first polymer that includes a first monomer unit and a second monomer unit different from the first monomer unit; (2) at least one second polymer that includes at least about 60% by weight of styrene monomer units; and (3) at least one third polymer that includes at most about 60% by weight of styrene monomer units. The first monomer unit is represented by Formula (I):

[0006] [ka]

[0007] wherein each of R1, R2, R3, R4, and R5 is independently H, halo, C1-C6 alkyl, or C2-C6 alkenyl, and the second monomer unit has a structure represented by formula (II):

[0008] [ka]

[0009] (Wherein, Z is arylene, and R6, R7, R8, R9, R 10 , and R 11 each of which is independently H or C1-C6 alkyl.

[0010] In another aspect, the disclosure features a coating (eg, a free-standing or supported coating) prepared from the curable composition described herein.

[0011] In another aspect, the disclosure features a prepreg product including a woven or nonwoven substrate impregnated with a curable composition described herein.

[0012] In another aspect, the disclosure features a laminate including at least one layer prepared from the prepreg product described herein.

[0013] In another aspect, the disclosure features a circuit board (eg, a printed circuit board) for use in an electronic product that includes a laminate described herein.

[0014] In yet another aspect, the disclosure features a method that includes impregnating a woven or nonwoven substrate with a curable composition described herein and curing the composition to form a prepreg product.

[0015] The details of one or more embodiments of the disclosed compositions and methods are set forth in the description that follows. Other features, objects, and advantages of the disclosed compositions and methods will be apparent from the description and from the claims. DETAILED DESCRIPTION OF THE INVENTION

[0016] As defined herein, unless otherwise specified, all expressed percentages should be understood to be percentages by weight of the total weight of the curable composition, i.e., weight percent. Unless otherwise specified, ambient temperature referred to herein refers to 25°C.

[0017] In general, the present disclosure is directed to curable compositions comprising at least one (e.g., two or more) first polymer, at least one (e.g., two or more) second polymer, and at least one (e.g., two or more) third polymer. The first, second, and third polymers are different from one another. In some embodiments, the polymers described herein can be homopolymers or copolymers (e.g., random copolymers, graft copolymers, alternating copolymers, or block copolymers) unless otherwise specified. In some embodiments, the curable compositions described herein do not include any polymers other than the first, second, and third polymers described herein.

[0018] In some embodiments, the first polymer described herein comprises at least one The polymer comprises at least one (e.g., two or more) first monomeric units and at least one (e.g., two or more) second monomeric unit different from the first monomeric units. The term "monomer unit" referred to herein refers to a group within a polymer formed from a monomer and is used interchangeably with the term "monomer repeat unit" as known in the art. In some embodiments, the first polymer comprises only the first and second monomeric units, and does not comprise any other monomeric units. In some embodiments, the first monomer unit has formula (I):

[0019] [ka]

[0020] wherein each of R1, R2, R3, R4, and R5 is independently H, halo (e.g., F, Cl, Br, or I), C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl), or C2-C6 alkenyl (e.g., vinyl, propenyl, or allyl).

[0021] Examples of monomers that can be used to form the first monomer unit include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-propylstyrene, m-propylstyrene, p- Propylstyrene, o-butylstyrene, m-butylstyrene, p-butylstyrene, o-isobutylstyrene, m-isobutylstyrene, p-isobutylstyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, on-pentylstyrene, mn-pentylstyrene, pn-pentylstyrene, o-2-methylbutylstyrene, m-2-methylbutylstyrene, p-2-methylbutylstyrene, o-3-methylbutylstyrene, m-3-methylbutylstyrene, p-3-methylbutylstyrene, ot-pentylstyrene, mt-pentylstyrene, pt-pentylstyrene, on-hexylstyrene, mn-hexylstyrene, pn-hexylstyrene, o-2-methylpentylstyrene, m-2-methylpentylstyrene, p-2-methylpentylstyrene, o-3-methylpentylstyrene, m-3-methylpentylstyrene p-3-methylpentylstyrene, o-1-methylpentylstyrene, m-1-methylpentylstyrene, p-1-methylpentylstyrene, o-2,2-dimethylbutylstyrene, m-2,2-dimethylbutylstyrene, p-2,2-dimethylbutylstyrene, o-2,3-dimethylbutylstyrene, m-2,3-dimethylbutylstyrene, p-2,3-dimethylbutylstyrene, o-2,4-dimethylbutylstyrene, m-2,4-dimethylbutylstyrene, p-2,4-dimethylbutylstyrene, o-3,3-dimethylbutylstyrene, m-3,3-dimethylbutylstyrene, p-3,3-dimethylbutylstyrene, o-3,4-dimethylbutylstyrene, m-3,4-dimethylbutylstyrene, p-3,4-dimethylbutylstyrene, o-4,4-dimethylbutylstyrene, m-4,4-dimethylbutylstyrene, p-4,Examples include 4-dimethylbutylstyrene, o-2-ethylbutylstyrene, m-2-ethylbutylstyrene, p-2-ethylbutylstyrene, o-1-ethylbutylstyrene, m-1-ethylbutylstyrene, and p-1-ethylbutylstyrene.

[0022] In some embodiments, the second monomer unit has formula (II): [ka]

[0023] (wherein Z is an arylene (e.g., a phenylene or naphthalene group), and R, R, R, R, R 10 , and R 11 is independently H or C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl). As used herein, the term "arylene" encompasses unsubstituted arylene and substituted arylene, such as arylene substituted with one or more (e.g., two or three or more) C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl).

[0024] Examples of monomers that can be used to form the second monomer unit include o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 1,4-divinylnaphthalene, 1,5-divinylnaphthalene, 2,3-divinylnaphthalene, 2,7-divinylnaphthalene, 2,6-divinylnaphthalene, 1,2-divinyl-3,4-dimethylbenzene, and 1,3-divinyl-4,5,8-tributylnaphthalene.

[0025] In some embodiments, the first polymer may optionally further include at least one (e.g., two or more) third monomer unit different from the first and second monomer units. In some embodiments, the third monomer unit includes a structure represented by Formula (I), a norbornene group, a (meth)acrylate group, or an indane group. As used herein, norbornene, (meth)acrylate, and indane groups each include unsubstituted groups and groups substituted with one or more (e.g., two, three, or more) C1-C6 alkyls (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl). Additionally, as used herein, the term "(meth)acrylate" includes both acrylate and methacrylate. In some embodiments, the third monomer unit includes an unsaturated group (e.g., an unsaturated hydrocarbon group).

[0026] In some embodiments, the first polymer is present in an amount of at least about 5 wt% (e.g., at least about 6 wt%, at least about 8 wt%, at least about 10 wt%, at least about 12 wt%, at least about 14 wt%, at least about 15 wt%, at least about 16 wt%, at least about 18 wt%, at least about 20 wt%, at least about 25 wt%, or at least about 30 wt%) to at most 60 wt% (e.g., at most 55 wt%, at most 50 wt%, at most 45 wt%, at most 40 wt%, at most 35 wt%, at most 30 wt%, at most 25 wt%, at most 20 wt%, at most 15 wt%, or at most 10 wt%) by weight of the solids of the curable composition described herein. Preferably, the first polymer is present in an amount of about 10 wt% to about 50 wt% by weight of the solids of the curable composition described herein. Without wishing to be bound by theory, it is believed that curable compositions containing the first polymer may have excellent electrical properties (e.g., low Dk or Df) due, at least in part, to the fact that the first polymer is made primarily from hydrocarbon monomers.

[0027] In some embodiments, the second polymer described herein comprises at least about 60% by weight of styrene monomer units (e.g., unsubstituted styrene monomer units, methylstyrene monomer units, t-butylstyrene monomer units, or bromostyrene monomer units). As used herein, the phrase "styrene monomer units" includes both unsubstituted and substituted styrene monomer units (e.g., the first monomer units having the structure shown in Formula (I) described above) and refers to groups formed from unsubstituted or substituted styrene monomers. Suitable substituents for styrene monomer units can include halo (e.g., F, Cl, Br, or I) and C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl). Examples of styrene monomers that can be used to form the styrene monomer units in the second polymer can be similar to those described above for the first monomer units in the first polymer.

[0028] In some embodiments, the styrene monomer units are present in an amount of at least about 60% by weight (e.g., at least about 61%, at least about 62%, at least about 64%, at least about 65%, at least about 66%, at least about 68%, at least about 70%, at least about 72%, at least about 74%, at least about 75%, at least about 76%, at least about 78%, or at least about 80% by weight) to at most 100% by weight (e.g., at most 99%, at most 98%, at most 96%, at most 95%, at most 94%, at most 92%, at most 90%, at most 85%, at most 80%, at most 75%, or at most 70% by weight) of the second polymer. In some embodiments, the styrene monomer units are present in an amount of from about 65% to about 80% by weight of the second polymer. Without wishing to be bound by theory, it is believed that including a second polymer having at least about 60 wt% (e.g., about 65 wt% to about 80 wt%) styrene monomer units significantly improves the compatibility of the first and third polymers in the curable compositions described herein, thereby improving the uniformity, stability, and shelf life of the curable composition before curing, reducing phase separation in laminates formed with the curable composition, and improving the uniformity and processability of prepregs and circuit boards formed from the curable composition. In contrast, without wishing to be bound by theory, it is believed that if the second polymer has less than about 60 wt% styrene monomer units, the second polymer may not be sufficiently compatible with the first polymer. In some embodiments, without wishing to be bound by theory, it is believed that a second polymer having more than about 80% by weight of styrene monomer units may be more brittle than a second polymer having about 65% to about 80% by weight of styrene monomer units and may be less compatible with the third polymers described herein, even though the third polymers described herein may be suitable for the intended purposes of the present disclosure.

[0029] In some embodiments, the second polymer described herein may optionally further comprise ethylene monomer units, propylene monomer units, butylene monomer units, isobutylene monomer units, butadiene monomer units, isoprene monomer units, or cyclohexene monomer units.

[0030] Examples of suitable second polymers include styrene isoprene styrene (SIS) block copolymers, styrene isoprene propylene styrene (SIPS) block copolymers, styrene isoprene butylene styrene (SIBS) block copolymers, styrene butylene styrene (SBS) block copolymers, styrene propylene styrene (SPS) block copolymers, and the like. Examples of block copolymers include styrene butylene block copolymers, styrene butadiene block copolymers, styrene ethylene propylene styrene (SEPS) block copolymers, and styrene ethylene butylene styrene (SEBS) block copolymers. In some embodiments, the second polymer can be a random copolymer containing the monomer units described herein.

[0031] In some embodiments, the second polymer is present in an amount of at least about 0.1 wt.% (e.g., at least about 0.2 wt.%, at least about 0.4 wt.%, at least about 0.5 wt.%, at least about 0.6 wt.%, at least about 0.8 wt.%, at least about 1 wt.%, at least about 2 wt.%, at least about 4 wt.%, at least about 5 wt.%, at least about 6 wt.%, at least about 8 wt.%, or at least about 10 wt.%) to at most 25 wt.% (e.g., at most 24 wt.%, at most 22 wt.%, at most 20 wt.%, at most 18 wt.%, at most 16 wt.%, at most 15 wt.%, at most 14 wt.%, at most 12 wt.%, at most 10 wt.%, at most 8 wt.%, at most 6 wt.%, or at most 5 wt.%) of the solids of the curable compositions described herein. Preferably, the second polymer is present in an amount of about 1 wt.% to about 10 wt.% of the solids of the curable compositions described herein.

[0032] In some embodiments, the third polymer described herein comprises at most about 60% by weight of styrene monomer units (e.g., unsubstituted styrene monomer units, methylstyrene monomer units, t-butylstyrene monomer units, or bromostyrene monomer units). Examples of monomers that can be used to form the styrene monomer units in the third polymer can be similar to those described above with respect to the first monomer units in the first polymer.

[0033] In some embodiments, the styrene monomer units comprise at least about 10% by weight (e.g., at least about 12%, at least about 14%, at least about 15%, at least about 16%, It is present in an amount of at least about 18% by weight, at least about 20% by weight, at least about 22% by weight, at least about 24% by weight, at least about 25% by weight, at least about 26% by weight, at least about 28% by weight, at least about 30% by weight, at least about 32% by weight, at least about 34% by weight, at least about 35% by weight, at least about 36% by weight, at least about 38% by weight, or at least about 40% by weight) to at most 60% by weight (e.g., at most 58% by weight, at most 56% by weight, at most 55% by weight, at most 54% by weight, at most 52% by weight, at most 50% by weight, at most 48% by weight, at most 46% by weight, at most 45% by weight, at most 44% by weight, at most 42% by weight, at most 40% by weight, at most 38% by weight, at most 36% by weight, at most 35% by weight, at most 34% by weight, at most 32% by weight, or at most 30% by weight). Without wishing to be bound by theory, it is believed that including a polymer having at most 60% by weight of styrene monomer units may significantly improve the mechanical properties (e.g., interlayer bond strength and / or toughness) of the curable compositions described herein and the adhesive properties (e.g., peel strength) between the curable compositions and a metal substrate (e.g., copper or aluminum foil). In contrast, without wishing to be bound by theory, it is believed that if the styrene monomer units in the third polymer are less than about 10% by weight, the third polymer may not have sufficient compatibility with the first and second polymers. In addition, without wishing to be bound by theory, it is believed that if the styrene monomer units in the third polymer are more than about 60% by weight, the curable compositions described herein may not have sufficient mechanical properties.

[0034] In some embodiments, the third polymer described herein optionally further comprises ethylene monomer units, propylene monomer units, butylene monomer units, isobutylene monomer units, butadiene monomer units, isoprene monomer units, or cyclohexene monomer units. It may contain .omeric units.

[0035] In some embodiments, the third polymer may further include a functional group that improves adhesion. Generally, the functional group in the third polymer may be a group capable of reacting with other components (e.g., the first and second polymers) in the curable compositions described herein. For example, the functional group in the third polymer may be an oxygen-containing group (e.g., a succinic anhydride group) or a nitrogen-containing group (e.g., an amine group). In some embodiments, the functional group in the third polymer may be a terminal group or end group. For example, the third polymer may include a polymer modified with maleic anhydride or a polymer containing an amine end group.

[0036] Examples of suitable third polymers include maleic anhydride modified styrene ethylene butylene styrene block copolymers, styrene ethylene butylene styrene block copolymers containing amine end groups, styrene 4-methylstyrene isoprene butylene block copolymers, 4-methylstyrene butylene block copolymers, and styrene butadiene styrene block copolymers.

[0037] In some embodiments, the third polymer is present in an amount of at least about 0.1 wt.% (e.g., at least about 0.2 wt.%, at least about 0.4 wt.%, at least about 0.5 wt.%, at least about 0.6 wt.%, at least about 0.8 wt.%, at least about 1 wt.%, at least about 2 wt.%, at least about 4 wt.%, at least about 5 wt.%, at least about 6 wt.%, at least about 8 wt.%, or at least about 10 wt.%) to at most 25 wt.% (e.g., at most 24 wt.%, at most 22 wt.%, at most 20 wt.%, at most 18 wt.%, at most 16 wt.%, at most 15 wt.%, at most 14 wt.%, at most 12 wt.%, at most 10 wt.%, at most 8 wt.%, at most 6 wt.%, or at most 5 wt.%) of the solids of the curable compositions described herein. Preferably, the third polymer is present in an amount of about 1 wt.% to about 10 wt.% of the solids of the curable compositions described herein.

[0038] In some embodiments, the curable compositions described herein can optionally further comprise at least one (e.g., two or more) additional polymers different from the first, second, and third polymers described above. Examples of such additional polymers include polyphenylene ethers, polybutadienes, polystyrenes (e.g., those made from unsubstituted styrene or substituted styrene monomers such as those described herein), polysiloxanes (e.g., polyvinylsiloxanes, polyallylsiloxanes, and copolymers thereof), and polysilsesquioxanes (e.g., open- or closed-cage polysilsesquioxanes). Without wishing to be bound by theory, it is believed that these additional polymers can reduce the cost of the curable compositions described herein and / or improve processability (e.g., by reducing viscosity or improving flow), adhesive properties (e.g., peel strength), mechanical properties (e.g., interlayer bond strength), and flammability.

[0039] In some embodiments, the additional polymer is present in an amount of at least about 0.1 wt.% (e.g., at least about 0.2 wt.%, at least about 0.4 wt.%, at least about 0.5 wt.%, at least about 0.6 wt.%, at least about 0.8 wt.%, at least about 1 wt.%, at least about 2 wt.%, at least about 4 wt.%, at least about 5 wt.%, at least about 6 wt.%, at least about 8 wt.%, or at least about 10 wt.%) to at most 30 wt.% (e.g., at most 28 wt.%, at most 26 wt.%, at most 25 wt.%, at most 24 wt.%, at most 22 wt.%, at most 20 wt.%, at most 18 wt.%, at most 16 wt.%, at most 15 wt.%, at most 14 wt.%, at most 12 wt.%, at most 10 wt.%, at most 8 wt.%, at most 6 wt.%, or at most 5 wt.%) of the solids of the curable compositions described herein. The additional polymer is preferably present in an amount of from about 1% to about 20% by weight of the solids of the curable compositions described herein.

[0040] In some embodiments, the curable compositions described herein can optionally further comprise at least one (e.g., two or more) filler. In some embodiments, the filler can include silica (e.g., hollow silica), boron nitride, barium titanate, barium strontium titanate, titanium oxide, glass (e.g., hollow glass), fluorine-containing polymers (e.g., polytetrafluoroethylene), or silicone. In some embodiments, the filler can be in the form of particles or powder. Preferably, the curable compositions described herein include silica as a filler. Without wishing to be bound by theory, it is believed that the filler can improve the mechanical properties, thermal conductivity, and electrical properties of the curable compositions described herein, and / or reduce the coefficient of thermal expansion (CTE) and cost.

[0041] In some embodiments, the filler is present in an amount of at least about 1 wt. % (e.g., at least about 2 wt. %, at least about 4 wt. %, at least about 5 wt. %, at least about 6 wt. %, at least about 8 wt. %, at least about 10 wt. %, at least about 15 wt. %, at least about 20 wt. %, at least about 25 wt. %, at least about 30 wt. %, at least about 35 wt. %, or at least about 40 wt. %) to at most 80 wt. % (e.g., at most 75 wt. %, at most 70 wt. %, at most 65 wt. %, at most 60 wt. %, at most 55 wt. %, at most 50 wt. %, at most 45 wt. %, at most 40 wt. %, at most 35 wt. %, at most 30 wt. %, at most 25 wt. %, at most 20 wt. %, at most 15 wt. %, at most 10 wt. %, or at most 5 wt. %) of the solids of the curable compositions described herein. The filler is preferably present in an amount of from about 5% to about 50% by weight of the solids of the curable compositions described herein.

[0042] In some embodiments, the curable compositions described herein can optionally further comprise at least one (e.g., two or more) radical initiator. In some embodiments, the radical initiator can include a peroxide (e.g., di-(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(t-butylperoxy)hexane, or dicumyl peroxide), an aromatic hydrocarbon (e.g., 3,4-dimethyl-3,4-diphenylhexane or 2,3-dimethyl-2,3-diphenylbutane), or an azo compound. Without wishing to be bound by theory, it is believed that the radical initiator can facilitate curing of the curable composition when the composition is used to form a prepreg product or laminate. In embodiments where the curable compositions described herein do not include a radical initiator, the composition can be cured by heating.

[0043] In some embodiments, the radical initiator is present in an amount of at least about 0.01 wt% (e.g., at least about 0.02 wt%, at least about 0.04 wt%, at least about 0.05 wt%, at least about 0.06 wt%, at least about 0.08 wt%, at least about 0.1 wt%, at least about 0.2 wt%, at least about 0.4 wt%, at least about 0.5 wt%, at least about 0.6 wt%, at least about 0.8 wt%, or at least about 1 wt%) to at most 10 wt% (e.g., at most 9 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, at most 4 wt%, at most 3 wt%, at most 2 wt%, or at most 1 wt%) of the solids of the curable compositions described herein. The radical initiator is preferably present in an amount of about 0.1 wt% to about 5 wt% of the solids of the curable compositions described herein.

[0044] In some embodiments, the curable compositions described herein optionally further comprise at least In some embodiments, the crosslinking agent may include at least one (e.g., two or more) crosslinking agents. In some embodiments, the crosslinking agent may be triallyl isocyanurate, triallyl cyanurate, bis(vinylphenyl)ether, bromostyrene (e.g., dibromostyrene), polybutadiene, poly(butadiene-co-styrene) copolymer, divinylbenzene, di(meth)acrylate, maleimide compound (e.g., bismaleimide), dimethylimidazole, dicyclopentadiene, tricyclopentadiene, allylbenzoxazine, allylphosphazene, 2,4-diphenyl-4-methyl-1-pentene, trans-stilbene, 5-vinyl-2-norbornene, acenaphthylene, tricyclopentadiene, dimethicone, methylisocyanurate ... Crosslinking agents may include tano-1H-benzo[f]indene, 1,1-diphenylethylene, 4-benzhydrylstyrene, diisopropenylbenzene, diallyl isophthalate, alpha-methylstyrene, bis(vinylphenyl)ethane compounds (e.g., 1,2-bis(4-vinylphenyl)ethane, 1,2-bis(3-vinylphenyl-4-vinylphenyl)ethane, 1,2-bis(3-vinylphenyl)ethane), silanes (e.g., vinylsilane or allylsilane), siloxanes (e.g., vinylsiloxane or allylsiloxane), or silsesquioxanes (e.g., vinylsilsesquioxane or allylsilsesquioxane). Without wishing to be bound by theory, it is believed that the crosslinking agent may facilitate curing of the curable composition when the composition is used to form a prepreg product or laminate.

[0045] In some embodiments, the crosslinking agent described herein is present in an amount of at least about 0.01 wt% (e.g., at least about 0.02 wt%, at least about 0.04 wt%, at least about 0.05 wt%, at least about 0.06 wt%, at least about 0.08 wt%, at least about 0.1 wt%, at least about 0.2 wt%, at least about 0.4 wt%, at least about 0.5 wt%, at least about 0.6 wt%, at least about 0.8 wt%, or at least about 1 wt%) to at most 10 wt% (e.g., at most 9 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, at most 4 wt%, at most 3 wt%, at most 2 wt%, or at most 1 wt%) of the solids of the curable composition described herein. The crosslinking agent is preferably present in an amount of about 0.1 wt% to about 5 wt% of the solids of the curable composition described herein.

[0046] In some embodiments, the curable compositions described herein may optionally further comprise at least one (e.g., two or more) flame retardant. Suitable flame retardants may include phosphate ester flame retardants, bromobenzene flame retardants, phosphinate flame retardants, and phosphazene flame retardants. In some embodiments, the flame retardant is selected from the group consisting of 1,1'-(ethane-1,2-diyl)bis(pentabromobenzene) (e.g., Saytex 8010 available from Albemarle Corp.), N,N-ethylene-bis(tetrabromophthalimide) (e.g., BT-93 available from Albemarle Corp.), aluminum diethylphosphinate (e.g., Clariant Specialty Examples of suitable flame retardants include OP930 and OP935 available from Nippon Chemists Co., Ltd., allylphosphazene (e.g., SPV-100 available from Otsuka Chemical Co., Ltd.), benzylphenoxycyclotriphosphazene, phenoxyphenoxycyclotriphosphazene, hexaphenoxycyclotriphosphazene (e.g., SPB-100 available from Otsuka Chemical Co., Ltd.), resorcinol bis(di-2,6-dimethylphenyl phosphate) (e.g., PX-200 available from Daihachi Chemical Industry Co., Ltd.), 6H-dibenzo[c,e][1,2]oxaphosphorine-6,6′-(1,4-ethanediyl)bis-6,6′-dioxide (dixoide) (e.g., Altexia products available from Albemarle Corp.), BP-PZ, or PQ-60. BP-PZ is a phosphazene flame retardant available from Otsuka Chemical Co., Ltd. PQ-60 is a flame retardant available from Chin Yee Chemical Industries Co. Ltd., and is also known as BES5-1150 available from Regina Electronic Materials (Shanghai) Co., Ltd. Without wishing to be bound by theory, it is believed that the flame retardant can significantly reduce the flammability of products (e.g., laminates) formed from the curable compositions described herein.

[0047] In some embodiments, the flame retardant comprises at least about 1 wt. % (e.g., at least about 2 wt. %, at least about 4 wt. %, at least about 5 wt. %, at least about 6 wt. %, at least about 8 wt. %, at least about 10 wt. %, at least about 12 wt. %, at least about 14 wt. %, at least about 15 wt. %, at least about 16 wt. %, at least about 18 wt. %, or at least about 20 wt. %) to at most 50 wt. % (e.g., at most 4 In some embodiments, the flame retardant is present in an amount of about 10 wt% to about 30 wt% (e.g., about 15 wt% to about 25 wt%). Without wishing to be bound by theory, it is believed that if the flame retardant is present in less than about 1 wt% of the curable composition, the curable composition may not have sufficient flame retardancy. Additionally, without wishing to be bound by theory, it is believed that if the flame retardant is greater than about 50% by weight of the curable composition, the curable composition may have poor mechanical properties.

[0048] In some embodiments, the curable compositions described herein may optionally further comprise at least one (e.g., two or more) coupling agent. In some embodiments, the coupling agent may include a silane, titanate, or zirconate. Examples of suitable coupling agents include methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, hydrolyzed vinylbenzylaminoethylaminopropyltrimethoxysilane, phenyltrimethoxysilane, p-styryltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecylphosphite)titanate, or tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecylphosphite)zirconate. Without wishing to be bound by theory, it is believed that the coupling agent can improve the dispersibility of the inorganic filler in the curable composition, improve the adhesion between the filler and the polymer in the curable composition and between the glass cloth in the prepreg and the polymer in the curable composition, improve the water and solvent resistance of the curable composition, and reduce the number of voids in the curable composition.

[0049] In some embodiments, the coupling agent is present in an amount of at least about 0.01 wt% (e.g., at least about 0.02 wt%, at least about 0.04 wt%, at least about 0.05 wt%, at least about 0.06 wt%, at least about 0.08 wt%, at least about 0.1 wt%, at least about 0.2 wt%, at least about 0.4 wt%, at least about 0.5 wt%, at least about 0.6 wt%, at least about 0.8 wt%, or at least about 1 wt%) to at most 5 wt% (e.g., at most 4.5 wt%, at most 4 wt%, at most 3.5 wt%, at most 3 wt%, at most 2.5 wt%, at most 2 wt%, at most 1.5 wt%, at most 1 wt%, or at most 0.5 wt%) of the solids of the curable compositions described herein. The crosslinker is preferably present in an amount of about 0.1 wt% to about 5 wt% of the solids of the curable compositions described herein.

[0050] In some embodiments, the curable compositions described herein can optionally further comprise at least one (e.g., two or more) organic solvent. In some embodiments, the organic solvent can be 2-heptanone, methyl ethyl ketone, methyl isobutyl ketone, or the like. Examples of suitable solvents include methyl n-amyl ketone, methyl isoamyl ketone, cyclopentanone, cyclohexanone, benzene, anisole, toluene, 1,3,5-trimethylbenzene, xylene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or a combination thereof.

[0051] In some embodiments, the organic solvent is present in an amount of at least about 20 wt% (e.g., at least about 22 wt%, at least about 24 wt%, at least about 25 wt%, at least about 26 wt%, at least about 28 wt%, at least about 30 wt%, at least about 32 wt%, at least about 34 wt%, at least about 35 wt%, at least about 36 wt%, at least about 38 wt%, or at least about 40 wt%) to at most 50 wt% (e.g., at most 48 wt%, at most 46 wt%, at most 45 wt%, at most 44 wt%, at most 42 wt%, at most 40 wt%, at most 38 wt%, at most 36 wt%, at most 35 wt%, at most 34 wt%, at most 32 wt%, at most 30 wt%, at most 28 wt%, at most 26 wt%, or at most 25 wt%) of the total weight of the curable composition described herein. Without wishing to be bound by theory, it is believed that if the organic solvent is less than about 20% by weight of the curable composition, the viscosity of the curable composition may become too high, making it difficult to process. Additionally, without wishing to be bound by theory, it is believed that if the organic solvent is more than about 50% by weight of the curable composition, the viscosity of the curable composition may become too low, making it difficult to retain the coated composition on the substrate surface, reducing coating uniformity and coating efficiency.

[0052] The curable compositions described herein can be prepared by methods well known in the art, for example, by mixing the components together.

[0053] In some embodiments, the present disclosure features a film (e.g., a free-standing or supported film) prepared from the curable composition described herein. For example, a supported film can be prepared by coating the curable composition onto a substrate to form a supported film with the substrate. In another example, a free-standing film can be prepared by coating the curable composition onto a substrate to form a layer (e.g., a polymer layer) and removing (e.g., peeling) the layer from the substrate to form a free-standing film. In some embodiments, the film (e.g., a free-standing or supported film) is partially cured. In some embodiments, the film (e.g., a free-standing or supported film) is not cured.

[0054] In some embodiments, the disclosure features a prepreg product prepared from the curable composition described herein. In some embodiments, the prepreg product includes a substrate (e.g., a woven or nonwoven substrate (such as a cloth)) impregnated with the curable composition described herein. The substrate is also known as a support or reinforcing material. The prepreg products described herein can be used in the electronics industry, for example, to produce printed wiring or circuit boards.

[0055] Generally, the prepreg products described herein can be produced by impregnating a substrate (typically glass fiber-based, either as a woven or nonwoven substrate, or in the form of a cross-ply laminate of unidirectionally aligned parallel filaments) with a curable composition described herein, followed by full or partial curing of the curable composition (e.g., at a temperature in the range of about 150°C to about 250°C). The substrate impregnated with the partially cured composition is typically referred to as a "prepreg." The terms "prepreg" and "prepreg product" referred to herein are used interchangeably. To prepare a printed wiring board from the prepreg, one or more layers of prepreg are laminated, for example, with one or more layers of copper.

[0056] In some embodiments, the substrate (e.g., including a woven or nonwoven substrate) used in the prepregs described herein may include inorganic fiber substrates such as glass and asbestos. Glass fiber substrates are preferred from the standpoint of flame retardancy. Examples of glass fiber substrates include, but are not limited to, woven fabrics made from E-glass, NE-glass (Nittobo, Japan), C-glass, D-glass, S-glass, T-glass, quartz glass, L-glass, L2-glass, or NER-glass; glass nonwoven fabrics in which short fibers are bonded to a sheet-like material with an organic binder; and fabrics made from a mixture of glass fiber and other fiber types.

[0057] In some embodiments, a prepreg can be produced by impregnating a substrate (e.g., a woven or nonwoven substrate) with a curable composition described herein, followed by drying. In some embodiments, a prepreg described herein can have a resin content described herein of at least about 50% by weight (e.g., at least about 52%, at least about 54%, at least about 55%, at least about 56%, at least about 58%, at least about 60%, at least about 62%, at least about 64%, or at least about 65% by weight) to at most 80% by weight (e.g., at most 78%, at most 76%, at most 75%, at most 74%, at most 72%, at most 70%, at most 68%, at most 66%, or at most 65% by weight). Without wishing to be bound by theory, it is believed that prepregs with a relatively high resin content have improved electrical properties, and prepregs with a relatively low resin content have improved thermal properties.

[0058] In some embodiments, a metal substrate can be applied to one or both sides of the thus-formed prepreg to form a laminate. In some embodiments, the previously formed prepreg can be optionally laminated with one or more layers of prepreg as needed to create a composite structure, and a metal foil (e.g., copper or aluminum foil) can be applied to one or both sides of the composite structure to obtain a laminate (or metal-clad laminate). The thus-formed laminate can optionally be subjected to further processing, such as pressing and hot pressing, to at least partially (or fully) cure the prepreg layers. The laminate (e.g., copper-clad laminate) can be further layered with additional prepreg layers and cured to create a multilayer printed circuit board.

[0059] In some embodiments, the present disclosure features a laminate including at least one (e.g., two or three or more) layers prepared from the prepreg products described herein. In some embodiments, the laminate may include (1) a copper substrate (e.g., copper foil) and (2) at least one prepreg layer laminated onto the copper substrate. In some embodiments, one or both sides of the prepreg layer may be laminated with the copper substrate. In some embodiments, the present disclosure features a multilayer laminate in which multiple copper-clad laminates described herein are stacked on top of each other, optionally with one or more prepreg layers between two copper-clad laminates. The multilayer laminate thus formed may be pressed and cured to form a multilayer printed circuit board.

[0060] In some embodiments, a prepreg layer (i.e., a layer prepared from a prepreg product described herein) or laminate has a dielectric constant (Dk) at 10 GHz of at most about 3.5 (e.g., at most about 3.4, at most about 3.3, at most about 3.1, or at most about 3) to at least about 2.5. In some embodiments, the curable composition may include a high Dk filler (e.g., barium titanate). In such embodiments, the prepreg layers within the laminate may have a relatively high Dk, such as at least about 3.5 (e.g., at least about 4) to at most about 15 (e.g., at most about 12, at most about 10, or at most about 8).

[0061] In some embodiments, a prepreg layer (i.e., a layer prepared from a prepreg product described herein) or laminate has a dissipation factor (Df) of at most about 0.0025 (e.g., at most about 0.0024, at most about 0.0023, at most about 0.0022, at most about 0.0021, at most about 0.002, at most about 0.0019, at most about 0.0018, at most about 0.0017, at most about 0.0016, or at most about 0.0015) to at least about 0.0005 (e.g., at least about 0.0006, at least about 0.0008, or at least about 0.001). Preferably, the prepreg layer or laminate has a Df of at most about 0.0017 (e.g., at most about 0.0015).

[0062] In some embodiments, the present disclosure features a printed circuit or wiring board obtained from the laminate described herein. For example, a printed circuit or wiring board can be obtained by performing circuit processing on the copper foil of a copper foil-clad laminate. Circuit processing can be performed, for example, by forming a resist pattern on the surface of the copper foil, removing unnecessary portions of the foil by etching, removing the resist pattern, forming necessary through-holes by drilling, forming a resist pattern again, connecting the through-holes by plating, and finally removing the resist pattern. A multilayer printed circuit or wiring board can be obtained by laminating the above-mentioned copper foil-clad laminate under the same conditions as above on the surface of the printed wiring board obtained in this manner, and then performing circuit processing in the same manner as above. In this case, through-holes do not necessarily have to be formed, and via holes may be formed in place, or both may be formed. For example, in a printed circuit board (PCB), two pads at corresponding positions on different layers of the circuit board can be electrically connected by a via hole passing through the board, where the via hole can be made conductive by electroplating. These laminates are then stacked as many times as necessary to form a printed circuit or wiring board.

[0063] The printed circuit or wiring board produced as described above can be laminated with a copper substrate on one or both sides to form an inner layer circuit board. This lamination is usually carried out under heat and pressure. The resulting metal foil clad laminate can then be subjected to circuit processing in the same manner as described above to obtain a multilayer printed circuit board. [Example]

[0064] The present disclosure is further illustrated by reference to the following examples, which are for illustrative purposes only and should not be construed as limiting the scope of the present disclosure.

[0065] material In the following examples, Septon 2104 is a SEPS elastomer containing approximately 65% ​​by weight styrene monomer units or 65% by weight polystyrene, available from Kuraray Co., Ltd.; Tuftec H1043 is a SEBS elastomer containing approximately 67% by weight styrene monomer units or 67% by weight polystyrene, available from Asahi Kasei Corporation; Tuftec M1913 is a SEBS elastomer containing approximately 30% by weight styrene monomer units or 30% by weight polystyrene and modified with maleic anhydride, available from Asahi Kasei Corporation; Tuftec MP10 is a SEBS elastomer containing approximately 30% by weight styrene monomer units or 30% by weight polystyrene and containing amine end groups, available from Asahi Kasei Corporation; and Septon V9461 is a styrene / 4-methylstyrene / isoprene / butadiene polymer containing approximately 30% by weight styrene monomer units (including both styrene and 4-methylstyrene monomer units), available from Kuraray Co., Ltd. OPE-2st 2200 is a polyphenylene ether having a number average molecular weight of approximately 2200, available from Mitsubishi Gas Chemical Company, Inc. OPE-2st 1200 is a polyphenylene ether having a number average molecular weight of approximately 1200, available from Mitsubishi Gas Chemical Company, Inc. SC2500-SVJ is a silica available from Admatec Co., Ltd., and GT130MC is a silica available from Denka Co., Ltd. Saytex-8010 is 1,1'(ethane-1,2-diyl)bis[pentabromo-benzene] available from Albemarle Corp. Curox CC-DC (CCDFB) is 2,3-dimethyl-2,3-diphenylbutane available from United Initiators, Inc. Al2O3 is available from Sanyo Electric Co., Ltd. under the trade name AX3-32. SMA EF80 is a styrene-maleic anhydride copolymer available from Total Cray Valley and contains 88.9 wt% styrene monomer units or 88.9 wt% polystyrene and 11.1 wt% maleic anhydride. VulCup R is α,α-bis(t-butylperoxy)diisopropylbenzene available from Arkema Inc.BES5-7100 is bis(4-vinylphenyl)ethane (BVPE) available from Regina Electronic materials Co. Ltd. OFS-6030 is methacryloxypropyltrimethoxysilane available from Dow, Inc. A1535H is an SEBS elastomer containing approximately 57% by weight styrene monomer units or 57% by weight polystyrene available from Kraton Corporation 1,2-H-SBS-L is a partially hydrogenated SBS elastomer available from Nisso EQ2410-SMC and EQ1010-SMC are silica particles available from Third Age Technology (TAT).

[0066] General Procedure 1 Prepreg and Laminate Preparation The curable composition was poured into a metal pan, and glass cloth (2116NE, Nittobo) was impregnated with the curable composition. The impregnated glass cloth was coated through the gap between metal bars with a gap width of 11 to 12 mils. The sample was dried at room temperature for 10 minutes with airflow and then heated to 130°C for 4 minutes to form a dried prepreg. The dried prepreg was cut into 12 x 12 inch pieces, and Cu was laminated to both sides of two layers of prepreg to form a laminate. The laminate was cured as follows: After placing the laminate in a press, 350 psi pressure was applied to the two layers of prepreg, and then cured using either cycle A or B below.

[0067] Cycle A: The laminate was heated from room temperature to 420°F at a heating rate of 6°F / min, held at 420°F for 2 hours, and cooled to room temperature at a cooling rate of 10°F / min.

[0068] Cycle B: The laminate was heated from room temperature to 310°F at a heating rate of 6°F / min, held at 310°F for 30 minutes, heated from 310°F to 420°F at a heating rate of 6°F / min, held at 420°F for 80 minutes, and cooled to room temperature at a cooling rate of 10°F / min.

[0069] General Procedure 2 Measurement of characteristics Resin content (RC) The weight of the glass cloth was measured before it was coated with the curable composition. After coating and drying, the total weight of the prepreg thus formed was measured. RC was calculated based on the following formula: RC = (total weight of prepreg - weight of glass cloth) / (total weight of prepreg)

[0070] Solution stability The components in the curable composition (excluding the filler, flame retardant, and catalyst) were mixed uniformly in a glass vial and kept for 24 hours. After 24 hours, the appearance of the mixture was observed. If there was clear phase separation in the mixture, the mixture was considered unstable. If the solution did not have phase separation, The solution was considered stable.

[0071] Cu peel strength evaluation The Cu peel strength was measured using IPC-TM-650 TEST METHODS MANUAL 2.4.8. Peel Strength based on a Cu weight of approximately 28g (1oz) per unit area. A United SSTM-1 Model was used for Cu peel strength measurements.

[0072] Inner Layer Bond Strength (ILBS) Evaluation ILBS was measured according to IPC-TM650 2.4.40. The SSTM-1 Model was used for the ILBS measurements. Specifically, a two-layer laminate including 2116NE glass cloth (Nittobo) was used.

[0073] Dk and Df evaluation The Df and Dk values ​​were analyzed using the split post dielectric resonator (SPDR) method. The Df and Dk values ​​at 10 GHz were measured using an Agilent Technologies Network Analyzer N5230A. A two-layer laminate containing 2116NE glass cloth was used for the measurements. "AB" refers to measurements after the sample was kept at 120°C for 2 hours. "RT" refers to measurements after the sample was kept at room temperature with a humidity of 45-55% for 16 hours.

[0074] flammable Flammability was evaluated according to UL94.

[0075] Example 1: Preparation of curable composition 1 (CC-1) and its laminate 295.7 g of toluene was added to the vessel, followed by 41.8 g of Tuftec M1913 (used as the third polymer described herein), and the mixture was mixed with an air mixer for 3 hours until a homogeneous solution was formed. 41.8 g of Septon 2104 (used as the second polymer described herein) was added to the vessel, and the mixture was mixed with an air mixer for 3 hours until a homogeneous solution was formed. 669.5 g of a toluene solution containing 50 wt. % Copolymer A (used as the first polymer described herein), described in Example 1 of U.S. Pat. No. 11,130,861, was added to the vessel, and the mixture was mixed with an air mixer for 1 hour until a homogeneous solution was formed. 260.3 g of SC2500-SVJ (used as a silica filler) was added to the vessel, and the mixture was mixed for 2 hours. 173.5 g of SAYTEX-8010 (used as a flame retardant) was added to a container and mixed for 1 hour using a high-shear mixer (Ross HSM-100LH-1) at a rotation speed of 5000 rpm while cooling on ice. 17.4 g of CCDFB (used as a catalyst) was added to the container and the mixture was mixed for 1 hour using an air mixer to obtain composition CC-1. CC-1 was used to form a laminate according to General Procedure 1 and Cycle B.

[0076] Example 2: Preparation of curable composition 2 (CC-2) and its laminate Curable composition CC-2 was identical to curable composition CC-1. CC-2 was used to form laminates according to General Procedure 1 and Cycle A.

[0077] Example 3: Preparation of curable composition 3 (CC-3) and its laminate Curable composition CC-3 was prepared in a manner similar to curable composition CC-1, except that 41.8 g of Tuftec M1913 was replaced with 41.8 g of Tuftec MP10. CC-3 was used to form a laminate according to General Procedure 1 and Cycle B.

[0078] Example 4: Preparation of curable composition 4 (CC-4) and its laminate Curable composition CC-4 was prepared in a manner similar to that of curable composition CC-1, except that 263.3 g of toluene, 21.1 g of Septon V9461, 42.2 g of Tuftec H1043, 718 g of a toluene solution containing 50 wt. % Copolymer A described in Example 1 of U.S. Pat. No. 11,130,861, 262.7 g of SC2500-SVJ, 175.1 g of saytex-8010, and 17.5 g of CCGFB were used to prepare CC-4. A laminate was formed using CC-4 according to General Procedure 1 and Cycle A.

[0079] Example 5: Preparation of curable composition 5 (CC-5) and its laminate Curable composition CC-5 was prepared in a manner similar to that of curable composition CC-1, except that 398.2 g of toluene, 62.2 g of Tuftec M1911, 62.2 g of Septon 2104, 542.2 g of a toluene solution containing 50 wt. % Copolymer A described in Example 1 of U.S. Pat. No. 11,130,861, 253 g of Al2O3 as filler, 165.9 g of saytex-8010, and 14.1 g of CCDFB were used to prepare CC-5. Laminates were formed using CC-5 according to General Procedure 1 and Cycle A.

[0080] Example 6: Preparation of curable composition 6 (CC-6) and its laminate Curable composition CC-6 was prepared by mixing 401.9 g of toluene, 41.8 g of BES5-7100 as a crosslinker, 59.7 g of Tuftec M1911, 59.7 g of Septon 2104, 521.8 g of a toluene solution containing 50 wt. % Copolymer A described in Example 1 of U.S. Pat. No. 11,130,861, Al2O3 CC-6 was prepared in a manner similar to that of curable composition CC-1, except that 242.6 g of acrylic acid, 159.1 g of saytex-8010, and 13.5 g of CCDFB were used. CC-6 was used to form a laminate according to General Procedure 1 and Cycle A.

[0081] Example 7: Preparation of curable composition 7 (CC-7) and its laminate Curable composition CC-7 was prepared by mixing 343.2 g of toluene, 18.9 g of BES5-7100 as a crosslinker, 33.2 g of 1,2-H-SBS-L as additives, 44.2 g of Tuftec M1913, 44.2 g of Septon 2104, 604.9 g of a toluene solution containing 53 wt. % Copolymer A described in Example 1 of U.S. Pat. No. 11,130,861, and EQ2410-SMC as a silica filler. CC-7 was prepared in a manner similar to that of curable composition CC-1, except that 288.3 g of EQ1010-SMC, 123.6 g of EQ1010-SMC, 209.4 g of saytex-8010, and 9.0 g of CCDFB were used. CC-7 was used to form a laminate according to General Procedure 1 and Cycle A.

[0082] Comparative Example 1: Preparation of Comparative Curable Composition 1 (CCC-1) and Laminates Thereof Comparative curable composition CCC-1 was prepared in a manner similar to curable composition CC-1, except that 98.3 g of toluene, 837.4 g of a toluene solution containing 50 wt. % Copolymer A described in Example 1 of U.S. Pat. No. 11,130,861, 325.5 g of SC2500-SVJ, 217 g of saytex-8010, and 21.7 g of CCDFB were used in preparing CCC-1. CCC-1 was used to form a laminate according to General Procedure 1 and Cycle A.

[0083] Comparative Example 2: Preparation of Comparative Curable Composition 2 (CCC-2) and Laminates Thereof Comparative curable composition CCC-2 was prepared by mixing 287.6 g of toluene, 40.7 g of Tuftec M1913, 732.8 g of a toluene solution containing 50 wt. % Copolymer A described in Example 1 of U.S. Pat. No. 11,130,861, 253.2 g of SC2500-SVJ, 168.8 g of saytex-8010, and CCD CCC-2 was prepared in a similar manner to curable composition CC-1, except that 16.9 g of FB was used. CCC-2 was used to form a laminate according to General Procedure 1 and Cycle A.

[0084] Comparative Example 3: Preparation of Comparative Curable Composition 3 (CCC-3) and Laminates Thereof Comparative curable composition CCC-3 was prepared in a manner similar to curable composition CC-1, except that 287.6 g of toluene, 40.7 g of Septon 2104, 732.8 g of a toluene solution containing 50 wt. % Copolymer A described in Example 1 of U.S. Pat. No. 11,130,861, 253.2 g of SC2500-SVJ, 168.8 g of saytex-8010, and 16.9 g of CCDFB were used to prepare CCC-3. Laminates were formed using CCC-3 according to General Procedure 1 and Cycle A.

[0085] Comparative Example 4: Preparation of Comparative Curable Composition 4 (CCC-4) and Laminates Thereof Comparative curable composition CCC-4 was prepared in a manner similar to curable composition CC-1, except that 113.9 g of toluene, 673.6 g of a toluene solution containing 50 wt. % Copolymer A described in Example 1 of U.S. Pat. No. 11,130,861, 6 g of OFS-6030 as a coupling agent, 440.1 g of SC2500-SVJ, 165 g of saytex-8010, and 1.4 g of Vul-Cup® were used to prepare CCC-4. Laminates were formed using General Procedure 1 and Cycle A.

[0086] Comparative Example 5: Preparation of Comparative Curable Composition 5 (CCC-5) and Laminates Thereof Comparative curable composition CCC-5 was prepared by mixing 165.1 g of toluene, 269.6 g of OPE-2st 2200, 500.1 g of a toluene solution containing 50 wt. % Copolymer A described in Example 1 of U.S. Pat. No. 11,130,861, 293.4 g of GT130MC, 195.6 g of saytex-8010, and CCDFB. CCC-5 was prepared in a similar manner to curable composition CC-1, except that 10.1 g was used. CCC-5 was used to form laminates according to General Procedure 1 and Cycle A.

[0087] Comparative Example 6: Preparation of Comparative Curable Composition 6 (CCC-6) and Laminates Thereof Comparative curable composition CCC-6 was prepared in a manner similar to curable composition CC-1, except that 287.6 g of toluene, 40.7 g of SMA EF80, 732.8 g of a toluene solution containing 50 wt. % Copolymer A described in Example 1 of U.S. Pat. No. 11,130,861, 253.2 g of SC2500-SVJ, 168.8 g of saytex-8010, and 16.9 g of CCDFB were used to prepare CCC-6. A laminate was formed using CCC-6 according to General Procedure 1 and Cycle A.

[0088] Comparative Example 7: Preparation of Comparative Curable Composition 7 (CCC-7) and Laminates Thereof Comparative curable composition CCC-7 was prepared in a manner similar to curable composition CC-1, except that 407.3 g of toluene, 43.6 g of Tuftec M1913, 43.6 g of Septon 2104, 536.1 g of OPE-2ST 1200, 270.9 g of SC2500-SVJ, 180.6 g of saytex-8010, and 18.1 g of CCDFB were used in preparing CCC-7. CCC-7 was used to form a laminate according to General Procedure 1 and Cycle A.

[0089] Comparative Example 8: Preparation of Comparative Curable Composition 8 (CCC-8) and Laminates Thereof Comparative curable composition CCC-8 was prepared by mixing 295.7 g of toluene, 41.8 g of Tuftec M1913, 41.8 g of A1535H, 669.5 g of a toluene solution containing 50 wt. % Copolymer A described in Example 1 of U.S. Pat. No. 11,130,861, 260.3 g of SC2500-SVJ, and 260.3 g of saytex-8010. Curable composition CC-A was used except that 173.5 g of CF3 and 17.4 g of CCDFB were used. 1. CCC-8 was used to form a laminate according to General Procedure 1 and Cycle A.

[0090] Evaluation example 1 The properties of curable compositions 1 to 7 (CC-1 to CC-7) and the laminates formed from these compositions are summarized below in Table 1. The copper layer of the laminate had a thickness of about 35 μm.

[0091] [Table 1]

[0092] The properties of comparative curable compositions 1 to 8 (CCC-1 to CCC-8) and the laminates formed from these compositions are summarized in Table 2 below.

[0093] [Table 2]

[0094] As shown in Table 2, inventive compositions CC-1 through CC-7 surprisingly exhibited superior properties compared to comparative compositions CCC-1 through CCC-8. Specifically, without wishing to be bound by theory, it is believed that because CCC-1 did not contain the second and third polymers described herein, laminates prepared from this composition exhibited poor ILBS and Cu peel strength. Without wishing to be bound by theory, it is believed that because CCC-2 did not contain the second polymer described herein, this composition exhibited severe phase separation and therefore poor solution stability. Without wishing to be bound by theory, it is believed that because CCC3 did not contain the third polymer described herein, laminates prepared from this composition exhibited poor ILBS. CCC-4 was similar to CCC-1 but contained a different amount of silica and a different catalyst. However, the results indicate that even laminates prepared from CCC-4 exhibited insufficient ILBS and Cu peel strength. Without wishing to be bound by theory, it is believed that because CCC-5 did not contain the second and third polymers described herein, the laminates prepared from CCC-5 exhibited insufficient ILBS. Without wishing to be bound by theory, it is believed that because CCC-6 did not contain the third polymer described herein (SMA EF80 contains more than 60 wt. % styrene and has a relatively low molecular weight, which contributes to brittleness), the laminates prepared from this composition exhibited insufficient ILBS and Cu peel strength. Without wishing to be bound by theory, it is believed that because CCC-7 did not contain the first polymer, the laminates prepared from this composition exhibited a relatively high Df. Without wishing to be bound by theory, it is believed that because CCC-8 contained A1535H as a second polymer, laminates prepared from this composition exhibited severe phase separation and therefore poor solution stability.

[0095] Other embodiments are within the scope of the following claims.

Claims

1. A curable composition, comprising: At least one first polymer comprising a first monomer unit and a second monomer unit different from the first monomer unit, wherein the first monomer unit is represented by formula (I): 【Chemistry 1】 (In the formula, R １ , R ２ , R ３ , R ４ , and R ５ each independently represents H, halo, C １ ~C ６ Alkyl or C ２ ~C ６ alkenyl (where R １ ~R ５ and wherein the second monomer unit has a structure represented by formula (II): 【Chemistry 2】 (wherein Z is arylene and R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ each independently represents H or C １ ~C ６ at least one first polymer having a structure represented by the formula: at least one second polymer comprising at least 60% by weight of styrene monomer units; at least one third polymer comprising 20% ​​to 40% by weight of styrene monomer units; Including, the at least one first polymer is present in an amount of 5% to 60% by weight of the solids of the composition; the at least one second polymer is present in an amount of 0.1% to 25% by weight of the solids of the composition; A curable composition wherein said at least one third polymer is present in an amount of from 0.1% to 25% by weight of the solids of said composition.

2. The composition of claim 1, wherein the at least one third polymer comprises from 20% to 30% by weight of styrene monomer units.

3. the at least one first polymer is present in an amount of 10% to 50% by weight of the solids of the composition; the at least one second polymer is present in an amount of 1% to 10% by weight of the solids of the composition; The composition of claim 1, wherein the at least one third polymer is present in an amount of from 1% to 10% by weight of the solids of the composition.

4. R １ , R ２ , R ３ , R ４ , and R ５ The composition of claim 1 , wherein each of is independently H, methyl, ethyl, or vinyl.

5. The composition of claim 1 wherein Z is phenylene.

6. R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ The composition of claim 1 , wherein each of

7. 2. The composition of claim 1, wherein the at least one first polymer further comprises a third monomer unit different from the first and second monomer units, the third monomer unit comprising the structure of Formula (I), a norbornene group, a (meth)acrylate group, or an indane group.

8. 2. The composition of claim 1, wherein the styrene monomer units in the at least one second or third polymer comprise unsubstituted styrene monomer units, methylstyrene monomer units, t-butylstyrene monomer units, or bromostyrene monomer units.

9. 10. The composition of claim 1, wherein said at least one second polymer comprises at least 62% by weight of said styrene monomer units.

10. 10. The composition of claim 1, wherein the at least one second polymer further comprises ethylene monomer units, propylene monomer units, butylene monomer units, isobutylene monomer units, butadiene monomer units, isoprene monomer units, or cyclohexene monomer units.

11. 10. The composition of claim 1, wherein the at least one second polymer comprises a styrene-isoprene-styrene block copolymer, a styrene-isoprene-propylene-styrene block copolymer, a styrene-isoprene-butylene-styrene block copolymer, a styrene-butylene-styrene block copolymer, a styrene-propylene-styrene block copolymer, a styrene-butylene block copolymer, a styrene-butadiene block copolymer, a styrene-ethylene-propylene-styrene block copolymer, or a styrene-ethylene-butylene-styrene block copolymer.

12. 10. The composition of claim 1, wherein the at least one third polymer further comprises ethylene monomer units, propylene monomer units, butylene monomer units, isobutylene monomer units, butadiene monomer units, isoprene monomer units, or cyclohexene monomer units.

13. The composition of claim 1 , wherein the at least one third polymer comprises a polymer modified with maleic anhydride or a polymer containing amine end groups.

14. 10. The composition of claim 1, wherein the at least one third polymer comprises a maleic anhydride modified styrene ethylene butylene styrene block copolymer, a styrene ethylene butylene styrene block copolymer containing amine end groups, a styrene 4-methylstyrene isoprene butylene block copolymer, a 4-methylstyrene butylene block copolymer, or a styrene butadiene styrene block copolymer.

15. The composition of claim 1 further comprising at least one filler.

16. 16. The composition of claim 15, wherein the at least one filler comprises silica, boron nitride, barium titanate, barium strontium titanate, titanium oxide, glass, a fluorine-containing polymer, or a silicone.

17. 16. The composition of claim 15, wherein the at least one filler is present in an amount of from 1% to 80% by weight of the solids of the composition.

18. The composition of claim 1 further comprising at least one radical initiator.

19. 20. The composition of claim 18, wherein the at least one radical initiator comprises a peroxide, an aromatic hydrocarbon, or an azo compound.

20. 20. The composition of claim 19, wherein the at least one radical initiator comprises di-(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, 3,4-dimethyl-3,4-diphenylhexane, or 2,3-dimethyl-2,3-diphenylbutane.

21. 19. The composition of claim 18, wherein the at least one radical initiator is present in an amount of 0.01% to 10% by weight of the solids of the composition.

22. The composition of claim 1 further comprising at least one crosslinker.

23. The at least one crosslinker may be selected from the group consisting of triallyl isocyanurate, triallyl cyanurate, bis(vinylphenyl)ether, bromostyrene, polybutadiene, poly(butadiene-co-styrene) copolymer, divinylbenzene, di(meth)acrylate, maleimide, dimethylimidazole, dicyclopentadiene, tricyclopentadiene, allylbenzoxazine, allylphosphazene, 2,4-diphenyl-4-methyl-1-pentene, trans-stilbene, 5-vinyl-2-nonene, 5-methyl ...

23. The composition of claim 22, comprising 1,2-bis(4-vinylphenyl)ethane, 1,2-bis(3-vinylphenyl-4-vinylphenyl)ethane, 1,2-bis(3-vinylphenyl)ethane, silane, siloxane, or silsesquioxane.

24. 23. The composition of claim 22, wherein the at least one crosslinking agent is present in an amount of 0.01% to 10% by weight of the solids of the composition.

25. The composition of claim 1 further comprising a flame retardant.

26. 26. The composition of claim 25, wherein the flame retardant comprises 1,1'-(ethane-1,2-diyl)bis(pentabromobenzene), N,N-ethylene-bis(tetrabromophthalimide), aluminum diethylphosphinate, allylphosphazene, benzylphenoxycyclotriphosphazene, phenoxyphenoxycyclotriphosphazene, hexaphenoxycyclotriphosphazene, resorcinol bis(di-2,6-dimethylphenylphosphate), 6H-dibenzo[c,e][1,2]oxaphosphorine-6,6'-(1,4-ethanediyl)bis-6,6'-dixoide, BP-PZ, or PQ-60.

27. 26. The composition of claim 25, wherein the flame retardant is present in an amount of from 1% to 50% by weight of the solids of the composition.

28. The composition of claim 1 further comprising at least one coupling agent.

29. 30. The composition of claim 28, wherein the at least one coupling agent comprises a silane, titanate, or zirconate.

30. 30. The composition of claim 29, wherein the at least one coupling agent comprises methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, hydrolyzed vinylbenzylaminoethylaminopropyltrimethoxysilane, phenyltrimethoxysilane, p-styryltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecylphosphite)titanate, or tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecylphosphite)zirconate.

31. 29. The composition of claim 28, wherein the at least one coupling agent is present in an amount of 0.01% to 5% by weight of the solids of the composition.

32. The composition of claim 1 further comprising an organic solvent.

33. 33. The composition of claim 32, wherein the organic solvent comprises 2-heptanone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl isoamyl ketone, cyclopentanone, cyclohexanone, benzene, anisole, toluene, 1,3,5-trimethylbenzene, xylene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or a combination thereof.

34. 33. The composition of claim 32, wherein the organic solvent is present in an amount of 20% to 50% by weight of the composition.

35. A coating prepared from the composition of any one of claims 1 to 34.

36. A textile or nonwoven substrate impregnated with the composition of any one of claims 1 to 34. Prepreg product.

37. 37. The prepreg product of claim 36, wherein the woven or nonwoven substrate comprises glass cloth.

38. 37. The prepreg product of claim 36, wherein the prepreg product is partially cured.

39. 37. A laminate comprising at least one layer prepared from the prepreg product of claim 36.

40. 40. The laminate of claim 39, further comprising at least one layer of metal foil on a surface of said at least one layer prepared from said prepreg product.

41. 41. The laminate of claim 40, wherein the metal foil is a copper foil.

42. 41. The laminate of claim 40, wherein the layer prepared from the prepreg product has a dielectric constant of at most 3.5 at 10 GHz.

43. 41. The laminate of claim 40, wherein the layer prepared from the prepreg product has a dissipation factor of at most 0.0025 at 10 GHz.

44. 40. The laminate of claim 39, wherein the laminate is cured.

45. 40. A circuit board for use in an electronic product comprising the laminate of claim 39.

46. Impregnating a woven or nonwoven substrate with the composition of any one of claims 1 to 34; and curing the composition to form a prepreg product; A method comprising:

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