Low-loss composite layer and composition for forming the same

Abstract

In one embodiment, the composition includes a hydrocarbyl thermoplastic polymer comprising repeating units derived from an alpha-olefin and a C4-30 cycloalkene; a reactive monomer that is free radical crosslinkable to produce a crosslinked network; a free radical source; and a functionalized quartz glass that can be chemically coupled to the crosslinked network.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the interests of U.S. Provisional Patent Application No. 62 / 851,846, filed on 23 May 2019. The related application is incorporated herein by reference in its entirety.

[0002] This application relates to a low-loss composite layer. [Background technology]

[0003] Laminate and prepreg systems used in mobile phone telecommunications, laminate-based chip carriers, high-speed digital servers, etc., must meet several physical and electrical performance criteria, such as low loss, low dielectric constant, good heat resistance, and good dimensional stability. Such systems are increasingly favored for smaller components, requiring higher performance and necessitating improvements at each level. [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Therefore, improvements to the materials used in circuit materials are still needed. In particular, improvements are needed, including, for example, improved peel strength for very low-profile metal foils. Among the desired electrical, thermal, and physical properties, achieving even lower dielectric loss values ​​is a further advantage. [Means for solving the problem]

[0005] This specification discloses low-loss dielectric layers and compositions for forming them.

[0006] In one aspect, the composition comprises a hydrocarbyl thermoplastic polymer; a radically crosslinkable reactive monomer that forms a crosslinked network; a free radical source; and a functionalized silica glass that can chemically couple to the crosslinked network.

[0007] In another aspect, the composite layer can be derived from the composition.

[0008] In one aspect, a method of making a composite layer includes forming a layer from the composition; and polymerizing the reactive monomer in the composition to form a crosslinked network.

[0009] In another aspect, a multilayer article includes the composite layer.

[0010] The features described above, as well as other features, are illustrated by the following figures, detailed description, and claims.

[0011] The following figures are exemplary aspects and are provided to illustrate the present disclosure. The figures are illustrative of examples and are not intended to limit the apparatus manufactured in accordance with the present disclosure to the materials, conditions, or process parameters described herein.

Brief Description of the Drawings

[0012] [Figure 1] A graph showing the filler content of the minimum melt viscosity and coefficient of thermal expansion values. [Figure 2] A scanning electron micrograph of a composition of an example containing silica glass. [Figure 3] A scanning electron micrograph of a composition of an example containing methacrylated silica glass.

Modes for Carrying Out the Invention

[0013] Dielectric compositions for bonding ply layers used in multilayer printed circuit boards need to have a sufficiently low minimum melt viscosity so that they can flow sufficiently into and fill the surface microstructure associated with adjacent signal layers and / or base layers, while maintaining a low coefficient of thermal expansion along the Z axis to ensure high reliability of plated through-holes. Since these two properties are usually diametrically opposed, achieving a dielectric composition with an optimal balance between minimum melt viscosity and coefficient of thermal expansion has been challenging. Compositions have been developed for forming composite layers that not only achieve a good balance between minimum melt viscosity and coefficient of thermal expansion but also exhibit at least one of low loss or high peel strength to copper. The composition comprises a hydrocarbyl thermoplastic polymer; a reactive monomer that is free radical crosslinkable and generates a crosslinking network; a free radical source; and a functionalized fossil quartz glass.

[0014] The presence of functionalized fossilized quartz glass in the composite layer was found to result in greater peel strength against copper compared to a composite layer formed from the same composition except for the presence of quartz glass without functional groups. For example, the composite layer can achieve a high peel strength against copper of 0.54 kilograms (kg / cm) or more per centimeter. The presence of functionalized fossilized quartz glass in the composite layer was also found to result in a reduction in the average coefficient of thermal expansion in the z direction, even without the presence of a reinforcing layer, compared to a composite layer formed from the same composition except for the presence of the aforementioned quartz glass without functional groups. Unlike the bonding ply layer required to enable reinforcement of woven or nonwoven fabrics, the composite layer also has the advantage that it may be non-reinforcing and can be made relatively thin. Furthermore, the composite layer formed from the composition can exhibit a low dielectric loss of 0.0030 or less at 10 gigahertz (GHz).

[0015] The composition comprises a hydrocarbyl thermoplastic polymer. As used herein, the term “hydrocarbyl thermoplastic polymer” refers to a polymer prepared from the addition polymerization of at least one heteroatom-free unsaturated hydrocarbon. The hydrocarbyl thermoplastic polymer may be nonreactive with other components of the composition. The hydrocarbyl thermoplastic polymer may be derived from at least one alpha-olefin or cyclic olefin. Alpha-olefins are at least one C 2~20 The cyclic olefin may contain alkenes, such as ethene, propene, 1-butene, or 1-decene. 4~30 The composition may include cycloalkenes, such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclodecene, norbornene, or other alkyl or aryl-substituted norbornene (e.g., 5-methyl-2-norbornene, 5-hexyl-2-norbornene, 5-phenyl-2-norbornene, 5-ethyl-2-norbornene, 4,5-dimethyl-2-norbornene, or exo-1,4,4a,9,9a,10-hexahydro-9,10(1',2')-benzeno-1,4-methanoanthracene (HBMN)). Other cyclic olefins may include tricyclic monomers (e.g., exo-dihydrodicyclopentadiene) or tetracyclic monomers (e.g., endo,exo-tetracyclododecene). Any residual unsaturation of the hydrocarbyl polymer can be removed by hydrogenation before incorporation into the composition.

[0016] Hydrocarbyl thermoplastic polymers are given by formula (I)

[0017] [ka]

[0018] [In the formula, R1, R2, and R3 are each independently H, C 1~30 Alkyl alkyl group, or C 6~30It may be an aryl group; n may be 0 to 3,500 or 10 to 2,500 or 100 to 1,000; m may be 1 to 5,300 or 100 to 3,000 or 1,000 to 3,000 can have. R1 is H, C 1~30 alkyl group or C 6~30 aryl group, and R2 and R3 may each independently be H, C 1~23 alkyl group or C 6~23 aryl group. The molar ratio of the repeating unit of the cyclic olefin (e.g., of cycloalkene) to the alpha-olefin repeating unit in the hydrocarbyl thermoplastic polymer may be 6:1 to 0.5:1 or 6:1 to 1.5:1.

[0019] The cyclic olefin can contain at least one functional group, such as an alkyl group (e.g., methyl group, ethyl group, propyl group, or butyl group). The cyclic olefin can contain a cyclic alkyl functional group (e.g., bicyclo[2.2.1]hepta-2-ene, 6-methylbicyclo[2.2.1]hepta-2-ene, 5,6-dimethylbicyclo[2.2.1]-hepta-2-ene, 1-methylbicyclo[2.2.1]hepta-2-ene, 6-ethylbicyclo[2.2.1]hepta-2-ene). The cyclic olefin can contain a tetracyclic alkyl functional group (e.g., tetracyclo[4.4.0.1 2,5 .1 7,10 -3-dodecene, 8-methyltetracyclo[4.4.0.1 2,5 .1 7,10 -3-dodecene, 8-ethyltetracyclo[4.4.0.1 2,5 .1 7,10 -3-dodecene, 8,9-dimethyltetracyclo[4.4.0.1 2,5 .1 7,10 -ch3-dodecene, 8-methyl-9-ethyltetracyclo[4.4.0.1 2,5 .1 7,10 -3-dodecene, or 8-stearyltetracyclo[4.4.0.1 2,5 .1 7,10 ​It may contain ]-3-dodecene. The cyclic olefin may contain an aryl group (e.g., a phenyl group, a tolyl group, or a naphthyl group) or a heteroatom-containing group (e.g., a nitrile group or a halogen). The functionalized cyclic olefin repeating unit may be present in the hydrocarbyl thermoplastic polymer in an amount of 5-45 wt%, 35-75 wt%, or 65-85 wt% relative to the total mass of the hydrocarbyl thermoplastic polymer.

[0020] Alpha-olefins may contain at least one functional group, such as an alkyl group, an aryl group (e.g., a phenyl group, a tolyl group, or a naphthyl group), or a heteroatom-containing group (e.g., a nitrile group or a halogen). Functionalized alpha-olefin repeating units may be present in the hydrocarbyl thermoplastic polymer in amounts of 55-95 wt%, 25-65 wt%, or 15-35 wt% relative to the total mass of the hydrocarbyl thermoplastic polymer.

[0021] Nickel or palladium diimine complexes, used in combination with single-site catalysts such as highly active metallocenes, geometrically constrained catalysts (CGCs), methylaluminoxane (MAO), or borate co-catalysts, can enable copolymerization of cyclic olefins with alpha-olefins such as ethene or propene.

[0022] The composition may contain 10 to 90 volume percent (vol%), 25 to 75 vol%, or 30 to 50 vol% of hydrocarbyl thermoplastic polymer relative to the total volume of the composition. Where used herein, when referring to a mass percentage or volume percentage of a component relative to the total volume of the composition, the amount is relative to the solids, i.e., the total amount of solids minus any solvent present, and also to the total amount minus any reinforcing fabrics present (e.g., woven or nonwoven). The weight-average molecular weight of the hydrocarbyl thermoplastic polymer may be 500 to 105,000 grams (g / mol), 3,000 to 100,000 g / mol, 20,000 to 90,000 g / mol, or 70,000 to 90,000 g / mol relative to a polystyrene standard.

[0023] The composition comprises a reactive monomer that can be crosslinked to form a crosslinked network. The reactive monomer may include at least one of diallyl compounds, triallyl compounds, divinyl compounds, trivinyl compounds, conjugated dienes, unconjugated dienes, di(meth)acrylate compounds, or tri(meth)acrylate compounds. The reactive monomer may include at least one of trialyl (iso)cyanurate, 1,9-decadiene, 1,7-octadiene, tris(2-hydroxyethyl) triacrylate isocyanurate (THEIC TA), or trimethylolpropane trimethacrylate (TMP TMA). The reactive monomer may include trialyl (iso)cyanurate. As used herein, trialyl (iso)cyanurate includes at least one trialyl isocyanurate or trialyl cyanurate, as described in formulas (2A) and (2B), respectively.

[0024] [ka]

[0025] The composition may contain 1 to 35 vol%, 5 to 25 vol%, or 5 to 15 vol% of the reactive monomer relative to the total volume of the composition. The volume ratio of the hydrocarbyl thermoplastic polymer to the reactive monomer may be 1:1 to 50:1, 1:1 to 10:1, or 2:1 to 5:1.

[0026] The composition may include, for example, a free radical source (also referred to herein as an initiator) that can be activated by heat. Examples of free radical sources that can be activated by heat include peroxides, azo compounds (e.g., α,α'-azobis(isobutyronitrile)), redox initiators (e.g., combinations of peroxides such as H2O2 and ferrous salts), or azides (e.g., acetyl azides). The free radical source may include at least one of peroxide initiators, azo initiators, carbon-carbon initiators, persulfate initiators, hydrazine initiators, hydrazide initiators, or halogen initiators. The free radical source may include at least one of 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, or 1,4-diisopropylbenzene. The free radical source may include at least one of organic peroxides, such as dicumyl peroxide, t-butyl perbenzoate, α,α'-di-(t-butylperoxy)diisopropylbenzene, or 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexine.

[0027] The free radical source may include peroxides having a decomposition temperature of at least 50 degrees Celsius (°C). Examples of peroxides include ketone peroxides (e.g., methyl ethyl ketone peroxide or cyclohexanone peroxide), peroxyketals (e.g., 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane or 2,2-bis(t-butylperoxy)butane), hydroperoxides (e.g., t-butylhydroperoxide or 2,5-dimethylhexane-2,5-dihydroperoxide), dialkylperoxides (e.g., dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3, or α,α'-bis(t-butylperoxy-m-isopropyl)benzene), diacyl peroxides (e.g., octanoyl peroxide or isobutyryl peroxide), or peroxycarbonates (e.g., peroxydicarbonates such as di(4-tert-butylcyclohexyl)peroxydicarbonate).

[0028] The composition may contain a free radical source in an amount of 0.01 to 10 vol%, or 0.05 to 3 vol%, or 0.1 to 2 vol%, or 0.5 to 1 vol%, relative to the total mass of the composition.

[0029] The composition contains functionalized fossilized quartz glass. The composition may contain 10-70 vol%, or 20-60 vol%, or 40-55 vol%, or 10-40 vol%, of the total volume of the composition, of functionalized fossilized quartz glass. The functionalized fossilized quartz glass may have a spherical shape with an average diameter of 1-50 micrometers or 1-10 micrometers.

[0030] The composition consists of alpha-olefin and C 4~30 The hydrocarbyl thermoplastic polymer may include repeating units derived from cycloalkenes; reactive monomers that are free radical crosslinkable and generate a crosslinked network; a free radical source; and functionalized fossil quartz glass that can be chemically coupled to the crosslinked network. The hydrocarbyl thermoplastic polymer may include repeating units derived from at least one of cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclodecene, norbornene, or alkyl or aryl-substituted norbornene (e.g., 5-methyl-2-norbornene, 5-hexyl-2-norbornene, 5-phenyl-2-norbornene, 5-ethyl-2-norbornene, 4,5-dimethyl-2-norbornene, exo-1,4,4a,9,9a,10-hexahydro-9,10(1',2')-benzeno-l,4-methanoanthracene, exo-dihydrodicyclopentadiene, or endo,exo-tetracyclododecene). The hydrocarbyl thermoplastic polymer may have formula (I). C 4~30The molar ratio of cycloalkene repeating units to alpha-olefin repeating units may be 6:1 to 0.5:1 or 6:1 to 1.5:1.0. The weight-average molecular weight of the hydrocarbyl thermoplastic polymer may be 500 to 105,000 grams per mole relative to the polystyrene standard. Reactive monomers may include triallyl (iso)cyanurate. Free radical sources include dicumyl peroxide, dimethyldiphenylhexane, methyl ethyl ketone peroxide, cyclohexanone peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,2-bis(t-butylperoxy)butane, t-butyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3, t-butyl perbenzoate, and α,α'-di-(t-butylperoxy)diiso The composition may contain at least one of the following: propylbenzene, or 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexine (α,α'-bis(t-butylperoxy-m-isopropyl)benzene), octanoyl peroxide (isobutyryl peroxide), peroxydicarbonate, α,α'-azobis(isobutyronitrile), redox initiator, acetyl azide, 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, or 1,4-diisopropylbenzene. The composition may contain a hydrocarbon resin diluent. The hydrocarbon resin diluent may have a weight-average molecular weight of 200 to 2,000 grams per mole relative to a polystyrene standard. The hydrocarbon resin diluent may be derived from piperylene and optionally from aromatic repeating units. The hydrocarbon resin diluent may be saturated. The composition may contain a flame retardant. The functional groups of functionalized fossilized quartz glass may include at least one of the following: (meth)acrylate group, vinyl group, allyl group, propargyl group, butenyl group, or styryl group.

[0031] The composition may contain 10 to 90 volume percent, 25 to 75 volume percent, or 30 to 50 volume percent of a hydrocarbyl thermoplastic polymer relative to the total volume of the composition. The composition may contain 0.1 to 2 volume percent, or 0.5 to 1 volume percent of a free radical source relative to the total mass of the composition. The composition may contain 1 to 35 volume percent, 5 to 25 volume percent, or 5 to 15 volume percent of a reactive monomer relative to the total volume of the composition. The composition may contain 10 to 70 volume percent, 20 to 60 volume percent, or 40 to 55 volume percent of a functionalized fossilized quartz glass relative to the total volume of the composition. The composition may contain 0 to 50 volume percent, 10 to 40 volume percent, or 5 to 30 volume percent of a hydrocarbon resin diluent relative to the total volume of the composition. The composition may contain 5 to 25 volume percent, or 8 to 20 volume percent of a flame retardant relative to the total volume of the composition.

[0032] Functionalized fossilized quartz glass can be prepared by reacting a silane containing a functional group. The functional group may include at least one of the following: (meth)acrylate group, vinyl group, allyl group, propargyl group, butenyl group, or styryl group. Examples of (meth)acrylate-functionalized silanes include (3-acryloxypropyl)trimethoxysilane, n-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (3-acryloxypropyl)methyldimethoxysilane, methacryloxypropyltrimethoxysilane, o-(methacryloxyethyl)-n-(triethoxysilylpropyl)urethane, n-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropyltriethoxysilane, (methacryloxymethyl)methyldiethoxysilane, (methacryloxymethyl)methyldimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyldimethylethoxysilane, or methacryloxypropyldimethylmethoxysilane. Examples of vinyl-functionalized silanes include vinyltriacetoxysilane, vinyltriethoxysilane, vinyltriisopropeneoxysilane, vinyltriisopropoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltris(methylethylketoxymino)silane, (divinylmethylsilylethyl)triethoxysilane, docosenyltriethoxysilane, hexadecafluorododeca-11-enyl-1-trimethoxysilane, hexenyltriethoxysilane, and 7-octenyl Trimethoxysilane, 0-undecenyltrimethoxysilane, o-(vinyloxybutyl)-n-(triethoxysilyl-propyl)urethane, vinyltri-t-butoxysilane, vinyltris(methoxypropoxy)silane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyldimethylethoxysilane, trivinylmethoxysilane, bis(triethoxysilylethyl)vinylmethylsilane, triethoxysilyl-modified poly-1,2-butadiene, or diethoxymethylsilyl-modified The formula includes poly-1,2-butadiene. Examples of allyl-functionalized silanes include 3-(n-allylamino)propyltrimethoxysilane, n-allyl-aza-2,2-dimethoxysilacyclopentane, allyltrimethoxysilane, allyloxyundecyltrimethoxysilane, allyltriethoxysilane, or 2-(chloromethyl)allyltrimethoxysilane. Examples of propargyl-functionalized silanes include o-(propargyloxy)-n-(triethoxy-silylpropyl)urethane. Examples of butenyl-functionalized silanes include butenyltriethoxysilane. Examples of styryl-functionalized silanes include 3-(n-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane or styrylethyltrimethoxysilane. Examples of cyclopentadienyl-functionalized silanes include (3-cyclopentadienylpropyl)trimethoxysilane. Examples of cyclohexenyl-functionalized silanes include [2-(3-cyclohexenyl)ethyl]trimethoxysilane or [2-(3-cyclohexenyl)ethyl]trimethoxysilane. Functionalized silanes may include methacrylsilanes such as at least one of γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, or γ-methacryloxypropyltriethoxysilane.

[0033] The composition may include a hydrocarbon resin diluent. The hydrocarbon resin diluent may include an amorphous thermoplastic oligomer or polymer produced by polymerization of unsaturated hydrocarbons. When used herein, the hydrocarbon resin diluent oligomer may have a weight-average molecular weight of 2,500 g / mol or less relative to the polystyrene standard. The hydrocarbon resin diluent may result in at least one of a reduced minimum melt viscosity, increased resin flow, or improved leveling.

[0034] Hydrocarbon resin diluent is C 2~9 It may contain a hydrocarbon resin diluent. The hydrocarbon resin diluent is an aliphatic C 2~9 Hydrocarbons or aromatic C 6~9It may be derived from at least one hydrocarbon. The hydrocarbon resin diluent may be saturated. The hydrocarbon resin diluent is C 5~25 The hydrocarbon resin diluent does not need to contain repeating units derived from cycloalkenes (or may contain 0 mole percent). The hydrocarbon resin diluent may contain repeating units derived from cyclooctene.

[0035] Hydrocarbon resin diluents may include polybutenes (e.g., oligomeric polybutenes). Oligomers of C4 olefins (primarily isobutenes) with a wide range of weight-average molecular weights are commercially available. Short-chain polybutenes are free-flowing; medium-chain polybutenes are sticky with a honey-like consistency, while those with the longest chain lengths are very viscous semi-solids. Examples of polybutenes include INDOPOL®, commercially available from INEOS Oligomers, London, and PANALANE®, commercially available from Vantage Specialty Ingredients, Inc., Warren, NJ.

[0036] Hydrocarbon resin diluents may include C5 hydrocarbon resin diluents that can be prepared from piperylene or its derivatives, such as at least one of cis / trans 1,3-pentadiene, 2-methyl-2-butene, cyclopentene, cyclopentadiene (CPD), or dicyclopentadiene (DCPD). Piperylene monomers and their derivatives can be cationically polymerized using a Lewis acid catalyst to produce oligomeric resins having low to high softening points. C5 hydrocarbon resin diluents may be mainly aliphatic and therefore may be compatible with at least one of natural rubber, styrene-isoprene-styrene (SIS) copolymer, amorphous polyolefin (APO) (e.g., amorphous polyalpha-olefin (APAO)), polyolefin (e.g., low-density polyethylene (LDPE)), many synthetic elastomers, or low-polarity cyclic olefin copolymers (COC). C5 hydrocarbon resin diluents may have a weight-average molecular weight of 200 to 2,500 grams per mole (g / mol) relative to a polystyrene standard. C5 hydrocarbon resin diluents can have a softening point of 85-115°C (solid grade) or 5-10°C (liquid grade). C5 hydrocarbon resin diluents can be hydrogenated to reduce discoloration and improve thermal oxidation and UV stability. Examples of C5 hydrocarbon resin diluents are WINGTACK® 10, WINGTACK® 95, and WINGTACK® 98, which are commercially available from Cray Valley, Exton, and PA.

[0037] Hydrocarbon resin diluents include, for example, C, which contains aromatic repeating units. 8~9 It may contain a hydrocarbon resin diluent. 8~9 Hydrocarbon resin diluents can be prepared from coal tar or crude oil distillates, such as indene, methylindene, styrene, methylstyrene (e.g., alpha-methylstyrene), or vinyltoluene. Aromatic C 8~9 Hydrocarbon monomers can be cationically polymerized using Lewis acid catalysts to produce oligomeric resins within the weight-average molecular weight range. Compared with C5 hydrocarbon resin diluents, aromatic C 8~9Hydrocarbon resin diluents can have higher melt viscosity and softening point (100-150°C). Aromatic C 8~9 Hydrocarbon resin diluents are compatible with a variety of polymers.

[0038] Hydrocarbon resin diluents are C5 resin diluents and C 8~9 Both hydrocarbon resin diluents may be included, for example, as a blend or as a co-oligomer or copolymer thereof. C5 and C 8~9 A hydrocarbon resin diluent composition (e.g., as a blend or copolymer) may contain 0 to 50 wt%, 1 to 50 wt%, or 5 to 25 wt% aromatic repeating units relative to the total mass of the diluent. Aromatic C 8~9 Examples of modified C5 hydrocarbon resin diluents include Wingtack® STS, Wingtack® Extra, and Wingtack® 86, which are commercially available from Cray Valley, Exton, and PA.

[0039] A hydrocarbon resin diluent may include a blend of any of the disclosed hydrocarbon resin diluents or a co-oligomer or copolymer. For example, a hydrocarbon resin diluent may include a co-oligomer or copolymer derived from petroleum-based feedstocks, such as at least one of aliphatic C5, aromatic C9, styrene, ethylene, propylene, or butadiene. A hydrocarbon resin diluent may include at least one of styrene-ethylene butadiene-styrene copolymer or styrene-propylene butadiene-styrene copolymer; it may be optionally hydrogenated. An example of such a hydrocarbon resin diluent is REGALREZ® resin, commercially available from Eastman.

[0040] Hydrocarbon resin diluents may contain crosslinkable elastomers. The crosslinkable elastomer may contain at least one unsaturated or unsaturated side chain group in its backbone, and may be an olefin (e.g., ethene, propene, butene, butadiene, piperine, or isoprene). 2~8The crosslinkable elastomer may be derived from at least one of alkenes or cyclic olefins (e.g., norbornene-type monomers containing unsaturated side chain groups such as 5-vinyl-2-norbornene). Examples of crosslinkable elastomers are derived from ethene, propene, and dicyclopentadiene. When a composition contains a crosslinkable elastomer containing repeating units derived from a cyclic olefin, it can be distinguished from a hydrocarbyl thermoplastic polymer in that the hydrocarbyl thermoplastic polymer may not contain crosslinkable groups, or the crosslinkable elastomer may have a lower weight-average molecular weight. For example, the crosslinkable elastomer may have a weight-average molecular weight of 500 to 50,000 g / mol, or 500 to 10,000 g / mol, or 200 to 2,500 g / mol relative to a polystyrene standard, while the hydrocarbyl thermoplastic polymer may have a weight-average molecular weight of 70,000 to 105,000 g / mol. An example of a crosslinkable ethene-propene-dicyclopentadiene elastomer is TRILENE® 65D, which is commercially available from Lion Elastomers, Geismar, LA.

[0041] Hydrocarbon resin diluents can be distinguished from hydrocarbyl thermoplastic polymers in at least one of the following ways: 1) the diluent may have a lower weight-average molecular weight, for example, the weight-average molecular weight of the diluent may be 60% or less of the weight-average molecular weight of the hydrocarbyl resin diluent; 2) the diluent may have a lower heat distortion temperature; 3) the diluent may have a lower glass transition temperature; or 4) the diluent may be reactive. One or more of these outstanding features allow hydrocarbon resin diluents to have a plasticizing effect on hydrocarbyl thermoplastic polymers and their ceramic-filled versions, thereby increasing resin flow and reducing the minimum melt viscosity for the systems into which they are formulated.

[0042] The hydrocarbon resin diluent may have a weight-average molecular weight of 200 to 2,500 g / mol, or 1,000 to 2,200 g / mol, or 1,000 to 8,000 g / mol relative to the polystyrene standard. The hydrocarbon resin diluent may have a number-average molecular weight of 150 to 6,000 g / mol, or 200 to 2,200 g / mol, relative to the polystyrene standard. The composition may contain 0 to 50 vol%, or 10 to 40 vol%, or 5 to 30 vol%, of the hydrocarbon resin diluent relative to the total volume of the composition.

[0043] The composition does not have to contain a reinforcing layer. For example, the composition does not have to contain a woven or nonwoven fabric. As used herein, a composition without a reinforcing layer may mean that it contains 0 wt% of a reinforcing layer.

[0044] The composition may include a reinforcing layer. The reinforcing layer may contain multiple fibers that can help control in-plane shrinkage of the composition during curing and can increase the mechanical strength compared to the same composite layer without the reinforcing layer. The reinforcing layer may be a woven or nonwoven layer. The fibers may include at least one of the following: glass fibers (E glass fibers, S glass fibers, and D glass fibers, etc.), silica fibers, and polymer fibers (polyetherimide fibers, polysulfone fibers, poly(etherketone) fibers, polyester fibers, polyethersulfone fibers, polycarbonate fibers, aromatic polyamide fibers, or liquid crystal polymer fibers such as VECTRAN, which is commercially available from Kuraray). The fibers may have a diameter of 10 nanometers to 10 micrometers. The reinforcing layer may have a thickness of 200 micrometers or less, or 50 to 150 micrometers. The composite layer may include 5 to 15 volume percent, or 6 to 10 volume percent, or 7 to 11 volume percent, or 7 to 9 volume percent of the composite layer and the reinforcing layer.

[0045] The composition may contain at least one of the following additives: a ceramic filler other than functionalized fossilized quartz glass, a flame retardant, a dye (e.g., a fluorescent dye or pigment), a plasticizer, a curing retarder, a curing accelerator, an impact modifier, an antioxidant, or a UV protectant.

[0046] The additives may include fillers other than functionalized fossilized quartz glass. These fillers may include fumed silica (e.g., hydrophobic fumed silica), unfunctionalized fossilized quartz glass, titanium dioxide, barium titanate, strontium titanate, corundum, wollastonite, and Ba2Ti9O 20 The filler may include at least one of the following: zirconium tungstate, hollow ceramic spheres, boron nitride, aluminum nitride, silicon carbide, beryllia, alumina, alumina trihydrate, magnesia, mica, talc, nanoclay, or magnesium hydroxide. The filler may include at least one of solid glass spheres, hollow glass spheres, or core-shell rubber spheres. The ceramic filler may have a D90 particle size of 0.1 to 10 micrometers or 0.5 to 5 micrometers. The filler may have a D90 particle size of 2 micrometers or less, or 0.1 to 2 micrometers. The filler may be present in an amount of 0.1 to 10 wt% or 0.1 to 5 wt% relative to the total mass of the composition or composite layer.

[0047] The additives may include thermally conductive fillers. Examples of thermally conductive fillers include aluminum nitride, boron nitride, silicon carbide, diamond, nanodiamond, graphite, beryllium oxide, zinc oxide, zirconium silicate, magnesia, silica, or alumina.

[0048] The additive may include a flame retardant. The composition may contain 5 to 25 vol% or 8 to 20 vol% of the flame retardant relative to the total volume of the composition. The flame retardant may include, for example, a metal hydrate having a volume-average particle size of 1 to 500 nanometers (nm), or 1 to 200 nm, or 5 to 200 nm, or 10 to 200 nm; alternatively, the volume-average particle size may be 500 nm to 15 micrometers, for example, 1 to 5 micrometers. The metal hydrate may include at least one hydrate of a metal, such as Mg, Ca, Al, Fe, Zn, Ba, Cu, or Ni. At least one of Mg, Al, or Ca hydrates, such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, iron hydroxide, zinc hydroxide, copper hydroxide, nickel hydroxide, or calcium aluminate hydrate, gypsum dihydrate, zinc borate, zinc stannate, or barium metaborate can be used. These hydrates, for example, composite materials of hydrates containing Mg and at least one of Ca, Al, Fe, Zn, Ba, Cu, or Ni, can be used. The composite metal hydrate is of the formula MgM x (OH) y[In the formula, M is Ca, Al, Fe, Zn, Ba, Cu, or Ni, x is 0.1 to 10, and y is 2 to 32]. The flame retardant particles can be coated or otherwise treated to improve the dispersion and other properties. The flame retardant may be reactive. The flame retardant may optionally include organic halogenated flame retardants such as hexachloroendomethylenetetrahydrophthalic acid (HET acid), tetrabromophthalic acid, or dibromoneopentyl glycol. The flame retardant may optionally include halogen-free flame retardants (such as melamine cyanurate), phosphorus-containing compounds (such as phosphinates, diphosphinates, phosphazenes, vinyl phosphazenes, phosphonates, phosphaphenanthrene oxides, fine particle size melamine polyphosphates or phosphates), polysilsesquioxanes, or siloxanes. The flame retardant may also include brominated flame retardants. Brominated flame retardants may include at least one of bis-pentabromophenylethane, ethylenebistetrabromophthalimide, tetradecabromodifenoxybenzene, decabromodiphenyl oxide, or brominated polysilsesquioxane. Flame retardants can be used in combination with synergistic agents; for example, halogenated flame retardants can be used in combination with synergistic agents such as antimony trioxide.

[0049] The composition may include a reinforcing layer, such as a fiber layer. The fiber layer may be a woven fabric or a nonwoven fabric such as felt. The fiber layer may include at least one of glass fibers or polymer fibers. Such heat-stable fiber reinforcement can reduce the shrinkage of the layer containing the composition during curing in the substrate surface. Furthermore, the use of a reinforcing layer can help to provide a substrate with relatively high mechanical strength.

[0050] The glass fiber may include at least one of E glass fiber, S glass fiber, or D glass fiber. The polymer fiber may include high-temperature polymer fiber. The polymer fiber may include liquid crystal polymers such as VECTRAN®, which is commercially available from Kuraray. The polymer fiber may include at least one of polyetherimide, polyetherketone, polysulfone, polyethersulfone, polycarbonate, or polyester.

[0051] The composition can be organically solvated (for example, in a solution containing at least one of toluene or xylene), cast horizontally onto a release liner, and dried to form a composite layer. It is noteworthy that the amount of each component described in relation to the composition can be directly related to the composite layer. For example, a composition containing 10-50 vol% of hydrocarbyl thermoplastic polymer relative to the total volume of the composition can correspond to a composite layer containing 10-50 vol% of hydrocarbyl thermoplastic polymer relative to the total volume of the composite layer. The release liner can have a specific surface energy of 40-50 dynes per centimeter. The release liner may include at least one of biaxially oriented polypropylene (BOPP) or polyester (e.g., poly(ethylene terephthalate)). The release liner may include at least one of silicone-treated liners (e.g., polyester or glassine paper).

[0052] The composite layer can be prepared by impregnating the reinforcing layer with the composition and an optional solvent. The impregnation may include at least one of the following steps: coating the reinforcing layer with the composition (e.g., by casting, dipping, spraying, roll knife coating, plate knife coating, measuring rod coating, pouring, roll coating, or reverse roll coating); curing the composition to form the composite layer; and optionally drying after impregnation.

[0053] A method for forming a composite layer may include the steps of forming a layer from a composition and polymerizing reactive monomers in the composition to form a crosslinked network. Polymerization may include the steps of polymerizing reactive monomers and functionalized quartz glass to form a crosslinked network. Furthermore, the step of polymerizing to form a crosslinked network in the composite layer may further include, if present, the step of polymerizing a reactive hydrocarbon resin diluent.

[0054] Polymerization may include at least one of the steps of raising the temperature of the composite layer (e.g., by stacking) or exposing the composite layer to electron beam irradiation. Stacking may involve stacking a hierarchical structure that includes the composite layer alone or a multilayer stack positioned between two outer layers. The multilayer stack may include multiple alternating layers of the composite layer and substrate layers. The multilayer stack can then be pressed, for example, in a vacuum press, within the composite layer located between the substrate layers for a duration under pressure and temperature suitable for forming a crosslinking network. The multilayer stack may be roll-to-roll stacked or autoclaved.

[0055] Lamination and curing can be carried out by a one-stage process using, for example, a vacuum press, or by a multi-stage process. In a one-stage process, the stacks to be laminated can be placed in a press, laminate pressure can be applied, and the stacks can be heated to a laminate temperature. The laminate temperature may be 100-390°C, or 100-250°C, or 100-200°C, or 100-175°C, or 150-170°C. The laminate pressure may be 1-3 megapascals (MPa), or 1-2 MPa, or 1-1.5 MPa. The laminate temperature and pressure can be maintained for a desired holding time (immersion time), for example, 5-150 minutes, or 5-100 minutes, or 10-50 minutes, and then cooled to, for example, below 150°C at an optionally controlled cooling rate (with or without pressure).

[0056] Circuit materials containing composite layers can be prepared by forming a multilayer material having a composite layer containing a conductive layer disposed thereon. Useful conductive layers include, for example, at least one of stainless steel, copper, gold, silver, aluminum, zinc, tin, lead, or transition metals. There are no particular limitations regarding the thickness of the conductive layer, nor any limitations regarding the shape, size, or texture of the surface of the conductive layer. The conductive layer may have a thickness of 3 to 200 micrometers or 9 to 180 micrometers. If two or more conductive layers are present, the thicknesses of the two layers may be the same or different. The conductive layer may include a copper layer. A suitable conductive layer includes a thin layer of a conductive metal, such as copper foil currently used in the formation of circuits, e.g., electrodeposited copper foil. The copper foil may have a root mean square (RMS) roughness of 2 micrometers or less, or 0.7 micrometers or less, and the roughness is measured using a stylus-type surface shape measuring device.

[0057] A conductive layer can be added by lamination of conductive layers and composite layers, by direct laser assembly, or by bonding the conductive layer to the substrate via an adhesive layer. Other methods known in the art can be used to add conductive layers, for example, by special materials and forms of circuit materials such as electrodeposition and chemical vapor deposition.

[0058] Lamination can involve laminating a multilayer stack including a composite layer, a conductive layer, and an optional intermediate layer between the composite layer and the conductive layer to form a hierarchical structure. The conductive layer can be in direct contact with the composite layer without an intermediate layer. The hierarchical structure can then be placed in a press, such as a vacuum press, for a period of time under pressure and temperature suitable for bonding the layers and forming a laminate. Lamination and optional curing can be by a one-step process or a multi-step process, for example, using a vacuum press. In a one-step process, the hierarchical structure can be placed in a press heated to a lamination pressure (e.g., 1.0 to 8.3 megapascals) and a lamination temperature (e.g., 260 to 390°C). The lamination temperature and pressure can be maintained for a desired immersion time, e.g., 20 minutes, after which it is cooled to below 150°C (while still under pressure).

[0059] If present, the intermediate layer may include a polyfluorocarbon film that can be positioned between the conductive layer and the composite layer, and an optional layer of microglass-reinforced fluorocarbon polymer may be positioned between the polyfluorocarbon film and the conductive layer. The layer of microglass-reinforced fluorocarbon polymer can increase the adhesion of the conductive layer to the substrate. Microglass may be present in an amount of 4 to 30 mass percent (wt%) relative to the total mass of the layer. Microglass may have a maximum length scale of 900 micrometers or less, or 500 micrometers or less. Microglass may be of the type commercially available from Johns-Manville Corporation in Denver, Colorado. The polyfluorocarbon film includes fluoropolymers (such as polytetrafluoroethylene, fluorinated ethylene-propylene copolymers, and copolymers having a tetrafluoroethylene backbone with fully fluorinated alkoxy side chains).

[0060] The conductive layer can be added by laser direct assembly. Here, the composite layer may include a laser direct assembly additive; laser direct assembly may include the steps of irradiating the surface of the substrate with a laser, forming conductive paths for the laser direct assembly additive, and adding a conductive metal to the conductive paths. The laser direct assembly additive may include metal oxide particles (such as titanium oxide and copper-chromium oxide). The laser direct assembly additive may also include spinel-based inorganic metal oxide particles such as spinel copper. The metal oxide particles can be coated with a composition containing, for example, tin and antimony (e.g., 50-99 wt% tin and 1-50 wt% antimony relative to the total mass of the coating). The laser direct assembly additive may be included in 2-20 parts per 100 parts of the composition. Irradiation can be performed using a YAG laser having a wavelength of 1,064 nanometers, an output of 10 watts, a frequency of 80 kilohertz (kHz), and a speed of 3 meters per second. The conductive metal can be added, for example, by a plating method in an electroless plating bath containing copper.

[0061] A conductive layer can be added by adhesive bonding. The conductive layer may be a circuit (a metallized layer of another circuit), such as a flexible circuit. The adhesive layer can be placed between one or more conductive layers and a composite layer.

[0062] The composite layer can be used to bond one or more substrate layers, for example, two substrate layers. Each substrate layer may independently contain at least one of the following: fluoropolymers (e.g., polytetrafluoroethylene (PTFE), foamed polytetrafluoroethylene (ePTFE), perfluoroalkoxyalkanes (PFA)), polyimides (e.g., Kapton®), liquid crystal polymers (LCP such as VECTRAN®), polyesters, polyamides, polyolefins, polyphenylene oxides, or conductive metals. The conductive metal may contain at least one of silver, nickel, gold, cobalt, copper, or aluminum. The conductive metal may have a surface roughness (Rz) of less than 10 micrometers or between 1 and 10 micrometers.

[0063] A composite layer formed from the compositions disclosed herein can exhibit thermosetting characteristics through the formation of a crosslinked network. During the polymerization of the crosslinked network, the viscosity and temperature at which the film begins to soften and subsequently reaches its minimum melt viscosity, and before the crosslinking agent begins to increase its molecular weight, can be determined to be the minimum melt viscosity of the composition at the corresponding temperature. The composition was determined using the vibration rheology of parallel plates at a heating rate of 5°C per minute to 80 kg Poise (k P ) or above, or 80-700k P It can have a minimum melt viscosity.

[0064] The composite layer may have a peel strength to copper of 0.54 kg / cm or more, or 0.65 to 1.1 kg / cm, as measured according to IPC Test Method 650, 2.4.8.

[0065] The composite layer may have an average coefficient of thermal expansion in the z direction of less than 95 parts per million per degree Celsius (ppm / °C), or less than 90 ppm / °C at 150-250°C, which can be determined by ASTM D3386-00 using a 1 mil (0.0254 mm) thick sample at -125°C to 20°C.

[0066] The composite layer may have a dielectric constant of 2.5 to 3.5 at 10 GHz. The composite layer may have a dielectric loss of 0.0030 or less, or 0.0021 or less, or 0.001 to 0.0025 at 10 GHz. Dielectric loss and dielectric constant can be measured at a temperature of 23 to 25°C according to the "Stripline Test for Dielectric Constant and Loss Tangent in the X-Band" test method (IPC-TM-650 2.5.5.5).

[0067] The composite layer, with a thickness of 84 to 760 micrometers, can be UL94 V0 grade, as determined according to the Underwriter's Laboratory UL 94 safety standard for "testing the flammability of plastic materials for components in apparatus and equipment".

[0068] The article may include a composite layer. The article may be a printed circuit board. The article may include a metal foil (such as copper) coated with a composite layer composition. The article may be used in mobile phone telecommunications. The article may be a laminate-based chip carrier. The article may be used in high-speed digital applications.

[0069] In summary, in one embodiment, the low-loss composition is more preferably one in which the hydrocarbyl thermoplastic polymer has formula (I) as described herein, and the weight-average molecular weight of the hydrocarbyl thermoplastic polymer is 500 to 105,000 grams per mole relative to a polystyrene standard, and contains alpha-olefin and C 4~30A repeating unit derived from at least one of cycloalkenes, preferably cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclodecene, norbornene, or alkyl or aryl-substituted norbornene (5-methyl-2-norbornene, 5-hexyl-2-norbornene, 5-phenyl-2-norbornene, 5-ethyl-2-norbornene, 4,5-dimethyl-2-norbornene, exo-1,4,4a,9,9a,10-hexahydro-9,10(1',2')-benzeno-l,4-methanoanthracene, exo-dihydrodicyclopentadiene, or endo,exo-tetracyclododecene, etc.), in an amount of 10 to 90 volume percent, or 25 to 75 volume percent, or 30 to 50 volume percent. The material comprises a hydrocarbyl thermoplastic polymer; 1 to 35 volume percent, or 5 to 25 volume percent, or 5 to 15 volume percent, of a reactive monomer that is free radical crosslinkable and generates a crosslinked network, preferably trialyl (iso)cyanurate; an effective amount of free radical sources such as peroxides; and preferably, 10 to 70 volume percent, or 20 to 60 volume percent, of functionalized fossil quartz glass that can be chemically coupled to the crosslinked network, wherein the functionalized fossil quartz glass has a spherical shape with an average diameter of 1 to 50 micrometers or 1 to 10 micrometers. Optionally, a hydrocarbon resin diluent having a weight-average molecular weight of 200 to 2,000 grams per mole relative to the polystyrene standard may be present in an amount of 0 to 50 volume percent, or 10 to 40 volume percent, or 5 to 30 volume percent, preferably the hydrocarbon resin diluent is derived from piperylene and optionally aromatic repeating units; the hydrocarbon resin diluent is optionally saturated. Optionally, a flame retardant may be present in an amount of 5 to 25 volume percent, or 8 to 20 volume percent, relative to the total volume of the composition.

[0070] The composite layer derived from the aforementioned composition weighs 80 kg Poise Above, or 80-700 kilometers PoiseThe material may have a minimum melt viscosity; peel strength to copper of 0.54 kilograms or more per centimeter; an average coefficient of thermal expansion in the z direction of parts per 95 million or less per degree Celsius at 150 to 250 degrees Celsius, or parts per 90 million or less per degree Celsius; a dielectric constant of 2.5 to 3.5 at 10 gigahertz; and a dielectric loss of 0.0030 or less, or 0.0021 or less, or 0.001 to 0.0025 at 10 gigahertz. A multilayer article is disclosed that includes a composite layer bonded to the low-profile side of a conductive layer such as a low-profile copper layer.

[0071] The following examples are provided to illustrate the present disclosure. The examples are for illustrative purposes only and are not intended to limit the apparatus made in accordance with the present disclosure to the materials, conditions, or process parameters described herein. [Examples]

[0072] In the examples, the minimum melt viscosity (MMV) was determined using the vibration rheology of parallel plates with a temperature increase of 5°C per minute. The minimum melt viscosity and corresponding temperature can be defined as the viscosity and temperature at which the film begins to soften and reaches the minimum melt viscosity, and before the crosslinking agent begins to increase its molecular weight. The unit of minimum melt viscosity is kilo Poise (k P This is shown by ).

[0073] The dielectric constant (Dk) and dissipation loss (Df) (also known as the loss tangent) were measured at a temperature of 23–25°C according to the "Stripline Test for Dielectric Constant and Loss Tangent in the X-Band" test method (IPC-TM-650 2.5.5.5).

[0074] The glass transition temperature (Tg) and the coefficient of thermal expansion in the z direction (CTE) were determined according to "Glass transition temperature and thermal expansion of materials used in high-density interconnects (HDI) and microvias - TMA method" (IPC-TM-650 2.4.24.5).

[0075] The roughness of copper is determined using a contact atomic force microscope, and the sum of the five maximum peak heights is calculated by subtracting the sum of the five deepest valleys, and then dividing by five, and reported as Rz (micrometers) (JIS-B-0601) (Japanese Industrial Standard); or the roughness of copper is determined using a non-contact white light scanning interferometer, and the topography and texture of the treated surface (ISO 25178) are characterized using sewing techniques and reported as Sa, Sq, Sz height parameters (micrometers).

[0076] The copper peel strength was determined according to the "Peel Strength of Metal-Clad Laminates" test method (IPC-TM-650 2.4.8). For peel strength testing, each stack of composite layers, placed on either side of the composite layer and added to the 1 / 2 ounce copper foil shown in Table 1, was laminated using a typical epoxy curing cycle of 90 minutes at 185°C under a pressure of 1.7 megapascals (MPa). In the examples, the copper-clad laminates were tested for post-solder (AS) peel strength. 1 / 2 ounce copper foil represents the thickness of the copper layer achieved when 1 / 2 ounce copper (18.8 mm) is flattened and uniformly spread over an area of ​​1 square foot (929 square centimeters). The equivalent thickness is 0.01735 mm.

[0077] The components used in the examples are shown in Table 1.

[0078] [Table 1]

[0079] (Examples 1-8) The effect of methacrylic fossil quartz glass A composite layer was prepared by first mixing the components shown in Table 2. The reactive composition was then cast horizontally onto a silicone release liner. The resulting dielectric film layer had a thickness of 75 micrometers (3 mils). The minimum melt viscosity was determined and the results are shown in Table 2 and Figure 1. Outlined symbols represent quartz glass, and filled symbols represent m-quartz glass. Twenty composite layers were then laminated using a typical epoxy curing cycle of 90 minutes at 185°C with a pressure of 1.7 megapascals (MPa). The coefficient of thermal expansion was determined and the results are shown in Table 2 and Figure 1. Dielectric properties were determined at a thickness of 1,500 micrometers (60 mils) and are shown in Table 2.

[0080] [Table 2]

[0081] Table 2 and Figure 1 show that replacing quartz glass with methacrylic quartz glass resulted in a remarkable reduction in both minimum melt viscosity and z-direction thermal expansion coefficient while maintaining good copper peel strength.

[0082] While not bound by theory, it is thought that treating quartz glass with functionalized silanes acts as a coupling agent for inorganic silica to organic isocyanurate-based thermosetting resins. Figures 2 and 3 provide evidence for this coupling. Figure 2 is a scanning electron microscope image of a composition containing untreated quartz glass after polishing. Figure 2 clearly shows the presence of spherical voids on the surface where quartz glass particles were removed (not bonded) during the polishing process. In contrast, Figure 3 is a scanning electron microscope image of a composition containing methacrylic fossilized quartz glass after polishing. Figure 3 clearly shows that methacrylic fossilized quartz glass particles were not removed during the polishing process and remain bonded (present in) the composition.

[0083] (Examples 9-11) Effect of methacrylic fossil quartz glass on peel strength Composite layers of Examples 9-11, containing 33.0-37.5 vol% methacrylate fossil quartz glass, were prepared according to Examples 1-8 and are shown in Table 3. Various properties were determined, and the results are shown in Tables 3 and 4.

[0084] [Table 3]

[0085] Table 3 shows that the layers of Examples 9-11 were advantageous in that increasing the volume packing of methacrylic fossil quartz glass reduced the z-axis CTE, resulting in high copper peel strengths exceeding 3 pli (0.54 kg / cm) for all tested copper foils.

[0086] The dielectric properties of laminates of various thicknesses, including composite layer plies, were determined for Examples 9-11. The results are shown in Table 4.

[0087] [Table 4]

[0088] Table 4 shows that the laminates containing the composite layers of Examples 9-11 exhibited good dielectric constant values ​​and low loss values ​​at 10 GHz.

[0089] (Examples 12-16) Effect of hydrocarbon resin diluent on composite layers Examples 12-16, shown in Table 5, were prepared according to Examples 1-8, except that different diluents were added. The properties of each were determined and are also shown in Table 5.

[0090] [Table 5]

[0091] Table 5 shows that the addition of a hydrocarbon resin diluent resulted in a significant decrease in minimum melt viscosity while maintaining good CTE values ​​and dielectric properties. This suggests that the addition of a hydrocarbon resin diluent is a means of improving resin filling-flow without adversely affecting the thermal reliability performance of plated through-holes.

[0092] Examples 17-20, shown in Table 6, were prepared according to Examples 1-8, except that different diluents were added. The properties of each were determined and are shown in Table 6.

[0093] [Table 6]

[0094] Table 6 shows that the addition of a hydrocarbon resin diluent resulted in a significant reduction in minimum melt viscosity and improvement in hole-filling performance, which is used as an indicator of the resin's filling-flow capability, while maintaining good CTE values ​​and dielectric properties.

[0095] A non-limiting aspect of this disclosure is described below.

[0096] Embodiment 1: Alpha-olefin and C 4~30 A composition comprising: a hydrocarbyl thermoplastic polymer containing repeating units derived from cycloalkenes; a reactive monomer that is free radical crosslinkable and generates a crosslinked network; a free radical source; and a functionalized fossilized quartz glass that can be chemically coupled to the crosslinked network.

[0097] Embodiment 2: The composition of Embodiment 1, wherein the hydrocarbyl thermoplastic polymer comprises repeating units derived from at least one of cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclodecene, norbornene, or alkyl or aryl-substituted norbornene (e.g., 5-methyl-2-norbornene, 5-hexyl-2-norbornene, 5-phenyl-2-norbornene, 5-ethyl-2-norbornene, 4,5-dimethyl-2-norbornene, exo-1,4,4a,9,9a,10-hexahydro-9,10(1',2')-benzeno-l,4-methanoanthracene, exo-dihydrodicyclopentadiene, or endo,exo-tetracyclododecene).

[0098] Embodiment 3: A composition according to Embodiment 1 or 2, wherein the hydrocarbyl thermoplastic polymer has formula (I).

[0099] Appearance 4: C 4~30 A composition according to any one of embodiments 1 to 3, wherein the molar ratio of cycloalkene repeating units to alpha-olefin repeating units is 6:1 to 0.5:1 or 6:1 to 1.5:1.0.

[0100] Embodiment 5: A composition according to any one of Embodiments 1 to 4, wherein the weight-average molecular weight of the hydrocarbyl thermoplastic polymer is 500 to 105,000 grams per mole relative to a polystyrene standard.

[0101] Embodiment 6: Any one of Embodiments 1 to 5, comprising 10 to 90 volume percent, 25 to 75 volume percent, or 30 to 50 volume percent of a hydrocarbyl thermoplastic polymer based on the total volume of the composition. The hydrocarbyl thermoplastic polymer may be nonreactive with the other components of the composition.

[0102] Embodiment 7: A composition according to any one of Embodiments 1 to 6, wherein the reactive monomer comprises triallyl (iso)cyanurate.

[0103] Embodiment 8: A composition according to any one of Embodiments 1 to 7, comprising 1 to 35 volume percent, 5 to 25 volume percent, or 5 to 15 volume percent of a reactive monomer based on the total volume of the composition.

[0104] Embodiment 9: The free radical source is peroxide, dimethyldiphenylhexane, methyl ethyl ketone peroxide, cyclohexanone peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,2-bis(t-butylperoxy)butane, t-butyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3, t-butyl perbenzoate, α,α'-di-(t-butylperoxy)diisopropylbenzene, or 2,5-dimethyl-2,5-di(t-butylperoxy) A composition according to any one of embodiments 1 to 8, comprising at least one of -3-hexine, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, octanoyl peroxide, isobutyryl peroxide, peroxydicarbonate, α,α'-azobis(isobutyronitrile), a redox initiator, acetyl azide, 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane or 1,4-diisopropylbenzene, and / or comprising a free radical source in an amount of 0.1 to 2 volume percent or 0.5 to 1 volume percent relative to the total mass of the composition.

[0105] Embodiment 10: A composition according to any one of Embodiments 1 to 9, wherein the functionalized fossilized quartz glass has a spherical shape with an average diameter of 1 to 50 micrometers or 1 to 10 micrometers.

[0106] Embodiment 11: A composition according to any one of Embodiments 1 to 10, comprising 10 to 70 volume percent, 20 to 60 volume percent, or 40 to 55 volume percent of functionalized fossilized quartz glass based on the total volume of the composition.

[0107] Embodiment 12: A composition according to any one of Embodiments 1 to 11, further comprising a hydrocarbon resin diluent having a weight-average molecular weight of 200 to 2,000 grams per mole relative to a polystyrene standard.

[0108] Embodiment 13: A composition according to any one of Embodiments 1 to 12, further comprising a hydrocarbon resin diluent, wherein the hydrocarbon resin diluent is derived from piperylene and optionally from aromatic repeating units, and the hydrocarbon resin diluent is optionally saturated.

[0109] Embodiment 14: Any one of the compositions from Embodiments 1 to 13, comprising 0 to 50 volume percent, 10 to 40 volume percent, or 5 to 30 volume percent of a hydrocarbon resin diluent based on the total volume of the composition.

[0110] Embodiment 15: Any one of the compositions from Embodiments 1 to 14, further comprising 5 to 25 volume percent or 8 to 20 volume percent of a flame retardant based on the total volume of the composition.

[0111] Embodiment 16: A composite layer derived from the composition described in any one of Embodiments 1 to 15.

[0112] Embodiment 17: The composite layer according to Embodiment 16 having one or more of the following properties. The composition is 80k P Above or 80-700k P The composite layer can have a minimum melt viscosity of 0.54 kg / cm or more. The composite layer can have an average coefficient of thermal expansion in the z direction of 95 ppm / °C or less, or 90 ppm / °C or less, at 150 to 250°C. The composite layer can have a dielectric constant of 2.5 to 3.5 at 10 GHz. The composite layer can have a dielectric loss of 0.0030 or less, or 0.0021 or less, or 0.001 to 0.0025 at 10 GHz.

[0113] Embodiment 18: A method for producing a composite layer according to embodiments 16 and 17, comprising the steps of: forming a layer from a composition according to any one of embodiments 1 to 15; and polymerizing reactive monomers in the composition to form a crosslinked network.

[0114] Embodiment 19: The method according to Embodiment 18, wherein the polymerization step includes at least one step of raising the temperature of the layer, exposing the layer to ultraviolet irradiation, or exposing the layer to electron beam irradiation.

[0115] Embodiment 20: The method according to Embodiment 18 or 19, wherein the layer-forming step includes a step of casting a composition onto a release liner.

[0116] Embodiment 21: The method according to Embodiment 18 or 19, wherein the layer-forming step includes a step of casting the composition onto a metal foil such as copper or aluminum.

[0117] Embodiment 22: Any one of Embodiments 18 to 21, wherein the step of forming a layer includes a step of impregnating a reinforcing layer with a composition. The impregnation may include at least one of casting the composition onto the reinforcing layer, dipping the composition into the reinforcing layer, or roll-coating the reinforcing layer with the composition.

[0118] Embodiment 23: A multilayer article comprising any one of the composite layers from Embodiments 16 to 22.

[0119] Embodiment 24: A composition according to any one of Embodiments 1 to 23, wherein the functional group of the functionalized fossilized quartz glass comprises at least one of a (meth)acrylate group, a vinyl group, an allyl group, a propargyl group, a butenyl group, or a styryl group.

[0120] Embodiment 25: Functionalized fossilized quartz glass is (3-acryloxypropyl)trimethoxysilane, n-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (3-acryloxypropyl)methyldimethoxysilane, methacryloxypropyltrimethoxysilane, o-(methacryloxyethyl)-n-(triethoxysilylpropyl)urethane, n-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, methacryloxymethyltriethoxysilane, methacryloxy Methyltrimethoxysilane, methacryloxypropyltriethoxysilane, (methacryloxymethyl)methyldiethoxysilane, (methacryloxymethyl)methyldimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyldimethylethoxysilane, methacryloxypropyldimethylmethoxysilane, vinyltriacetoxysilane, vinyltriethoxysilane, vinyltriisopropeneoxysilane, vinyltriisopropoxysilane, vinyltrimethoxy Sisilane, vinyltris(2-methoxyethoxy)silane, vinyltris(methylethylketoxymino)silane, (divinylmethylsilylethyl)triethoxysilane, docosenyltriethoxysilane, hexadecafluorododeca-11-enyl-1-trimethoxysilane, hexenyltriethoxysilane, 7-octenyltrimethoxysilane, 0-undecenyltrimethoxysilane, o-(vinyloxybutyl)-n-(triethoxysilyl-propyl)urethane, vinyltri-t-butoxysilane, vinyltris(methoxypropoxy)silane, vinyl Methyldiethoxysilane, vinylmethyldimethoxysilane, vinyldimethylethoxysilane, trivinylmethoxysilane, bis(triethoxysilylethyl)vinylmethyl-silane, triethoxysilyl-modified poly-1,2-butadiene, diethoxymethylsilyl-modified poly-1,2-butadiene, 3-(n-allylamino)propyltrimethoxysilane, n-allyl-aza-2,2-dimethoxysilacyclopentane, allyltrimethoxysilane, allyloxyundecyltrimethoxysilane, allyltriethoxysilane, 2-(chloromethyl)allytrimeth A composition any one of embodiments 1 to 24, derived from a functional silane comprising xysilane, o-(propargyloxy)-n-(triethoxysilylpropyl)urethane, butenyltriethoxysilane, 3-(n-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane, styrylethyltrimethoxysilane, (3-cyclopentadienylpropyl)trimethoxysilane, [2-(3-cyclohexenyl)ethyl]trimethoxysilane, or [2-(3-cyclohexenyl)ethyl]trimethoxysilane. The functional silane may include at least one methacrylsilane, such as γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, or γ-methacryloxypropyltriethoxysilane.

[0121] Compositions, methods, and articles may, as alternatives, consist of, or essentially consist of, any preferred materials, processes, or components disclosed herein. Compositions, methods, and articles may be further or alternatively formulated to exclude, or substantially exclude, any materials (or types), processes, or components that are otherwise necessary for achieving the function or purpose of the composition, method, and article.

[0122] The terms "a" and "an" indicate the presence of at least one of the items being referred to, not a limitation of quantity. The term "or" means "and / or" unless otherwise clearly indicated by the context. References throughout the specification to "one aspect," "another aspect," "several aspects," etc., mean that certain elements described in relation to an aspect (e.g., features, structure, process, or characteristics) are included in at least one aspect described herein and may or may not be present in other aspects. Furthermore, it should be understood that the elements described may be combined in any suitable manner in various aspects.

[0123] When an element such as a layer, film, region, or substrate is said to be "on top of" another element, it may be directly on top of the other element, or there may be an intervening element. In contrast, when an element is said to be "directly on top of" another element, there is no intervening element. It is understood that the composite layer may be directly on one or more substrate layers.

[0124] Unless otherwise expressly stated herein, all test standards are the most recent standards in effect as of the filing date of this application, or, if priority is claimed, as of the filing date of the first priority application in which the test standard appears.

[0125] All endpoints within a range covering the same component or property include both endpoints, are independently combinable, and include all intermediate points and ranges. For example, the range "25 wt% or less, or 5 to 20 wt%" includes the endpoints and all intermediate values ​​of ranges such as "5 to 25 wt%" (e.g., 10 to 23 wt%).

[0126] All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if any terminology in this application is incompatible with or contradicts any terminology in any of the incorporated references, the terminology from this application shall prevail over the contradictory terminology from the incorporated references.

[0127] While specific embodiments are described, alternative methods, modifications, variations, improvements, and substantial equivalents that exist now or are not currently visible may arise for the applicants or others skilled in the art. Therefore, the claims at the time of filing and, if amended, attached claims are intended to encompass all such alternative methods, modifications, variations, improvements, and substantial equivalents.

Claims

1. Alpha-olefins and C 4～30 Hydrocarbyl thermoplastic polymers containing repeating units derived from cycloalkenes; A reactive monomer that exhibits free radical crosslinking properties and generates a crosslinking network; Free radical sources; Functionalized fossilized quartz glass (fused silica) that can be chemically coupled to a cross-linked network; and Hydrocarbon resin diluents having a weight-average molecular weight of 200 to 2,000 grams per mole relative to polystyrene standard. A composition comprising, Hydrocarbyl thermoplastic polymers do not have residual unsaturation. Hydrocarbon resin diluents, - C 2～9 Hydrocarbon resin diluent; - C containing aromatic repeating units 8～9 Hydrocarbon resin diluents; and - C2-9 resin diluents and C containing aromatic repeating units 8～9 A resin diluent containing both a hydrocarbon resin diluent and a blend or as a co-oligomer or copolymer. A composition comprising a hydrocarbon resin diluent selected from the above, wherein the hydrocarbon resin diluent may optionally be saturated.

2. The composition according to claim 1, wherein the hydrocarbyl thermoplastic polymer comprises repeating units derived from at least one of cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclodecene, norbornene, or alkyl or aryl-substituted norbornene (e.g., 5-methyl-2-norbornene, 5-hexyl-2-norbornene, 5-phenyl-2-norbornene, 5-ethyl-2-norbornene, 4,5-dimethyl-2-norbornene, exo-1,4,4a,9,9a,10-hexahydro-9,10(1',2')-benzeno-1,4-methanoanthracene, exo-dihydrodicyclopentadiene, or endo,exo-tetracyclododecene).

3. Hydrocarbyl thermoplastic polymers are given by formula (I) 【Chemistry 1】 [wherein, R 1 , R 2 , and R 3 are each independently H, C 1～30 alkyl group, C 6～30 aryl group; n may be from 10 to 3,500; m may be from 1 to 5,300] A composition according to claim 1 or 2, having the following characteristics.

4. C 4～30 The composition according to any one of claims 1 to 3, wherein the molar ratio of cycloalkene repeating units to alpha-olefin repeating units is 6:1 to 0.5:1 or 6:1 to 1.5:1.

0.

5. The composition according to any one of claims 1 to 4, wherein the weight-average molecular weight of the hydrocarbyl thermoplastic polymer is 500 to 105,000 grams per mole relative to a polystyrene standard.

6. The composition according to any one of claims 1 to 5, comprising 10 to 90 volume percent, or 25 to 75 volume percent, or 30 to 50 volume percent of a hydrocarbyl thermoplastic polymer based on the total volume of the composition.

7. The composition according to any one of claims 1 to 6, wherein the reactive monomer comprises (iso)cyanurate trialyl.

8. The composition according to any one of claims 1 to 7, comprising 1 to 35 volume percent, or 5 to 25 volume percent, or 5 to 15 volume percent of a reactive monomer based on the total volume of the composition.

9. Free radical sources include dicumyl peroxide, dimethyldiphenylhexane, methyl ethyl ketone peroxide, cyclohexanone peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,2-bis(t-butylperoxy)butane, t-butyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3, t-butyl perbenzoate, α,α'-di-(t-butylperoxy)diisopropylbenzene, or 2,5-dimethyl-2,5-di(t-butylperoxy)-3- A composition according to any one of claims 1 to 8, comprising hexine, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, octanoyl peroxide, isobutyryl peroxide, peroxydicarbonate, α,α'-azobis(isobutyronitrile), redox initiator, acetyl azide, 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, or 1,4-diisopropylbenzene, and / or comprising a free radical source in an amount of 0.1 to 2 volume percent or 0.5 to 1 volume percent of the total mass of the composition.

10. The composition according to any one of claims 1 to 9, wherein the functionalized fossilized quartz glass has a spherical shape having an average diameter of 1 to 50 micrometers or 1 to 10 micrometers.

11. The composition according to any one of claims 1 to 10, comprising 10 to 70 volume percent, or 20 to 60 volume percent, of functionalized fossilized quartz glass based on the total volume of the composition.

12. The composition according to any one of claims 1 to 11, wherein the hydrocarbon resin diluent is derived from piperylene and optionally from aromatic repeating units, and the hydrocarbon resin diluent may optionally be saturated.

13. The composition according to any one of claims 1 to 12, comprising 10 to 40 volume percent, or 5 to 30 volume percent, of a hydrocarbon resin diluent based on the total volume of the composition.

14. The composition according to any one of claims 1 to 13, further comprising 5 to 25 volume percent or 8 to 20 volume percent of a flame retardant based on the total volume of the composition.

15. The composition according to any one of claims 1 to 14, wherein the functional group of the functionalized fossilized quartz glass comprises at least one of a (meth)acrylate group, a vinyl group, an allyl group, a propargyl group, a butenyl group, or a styryl group.

16. The composition according to any one of claims 1 to 15, having a minimum melt viscosity of 80 kilopoise or more, or 80 to 700 kilopoise.

17. A composite layer derived from the composition according to any one of claims 1 to 16.

18. The composite layer according to claim 17, having a peel strength against copper of 0.54 kilograms or more per centimeter.

19. The composite layer according to claim 17, having an average coefficient of thermal expansion in the z-direction of parts per 95 million or less per 10 degrees Celsius at 150 to 250 degrees Celsius, or parts per 90 million or less per 10 degrees Celsius.

20. The composite layer according to claim 17, having a dielectric constant of 2.5 to 3.5 at 10 gigahertz.

21. The composite layer according to claim 17, having a dielectric loss of 0.0030 or less, or 0.0021 or less, or 0.001 to 0.0025 at 10 gigahertz.

22. A method for producing a composite layer according to any one of claims 17 to 21, comprising the steps of forming a layer from a composition according to any one of claims 1 to 16, and polymerizing reactive monomers in the composition to form a crosslinked network.

23. The method according to claim 22, wherein the polymerization step includes raising the temperature of at least one layer or exposing the layers to electron beam irradiation.

24. The method according to claim 22 or 23, wherein the step of forming a layer includes the step of casting the composition onto a release liner.

25. The method according to claim 22 or 23, wherein the step of forming a layer includes the step of casting the composition onto a metal foil.

26. The method according to any one of claims 22 to 25, wherein the step of forming a layer includes the step of impregnating the reinforcing layer with the composition.

27. A multilayer article comprising a composite layer according to any one of claims 17 to 21.

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