Dielectric film forming composition

Abstract

This disclosure relates to a dielectric film-forming composition comprising (a) at least one meth(acrylate)-containing polyphenylene ether resin, and (b) at least one second resin selected from the group consisting of i) at least one fully imidized polyimide polymer, ii) at least one polyamic acid ester, iii) at least one cyclized polydiene resin, and iv) a mixture of a cyclized polydiene resin and a cyanate ester compound.

Description

[Technical Field]

[0001] Related applications This application claims priority to U.S. Provisional Application No. 63 / 531,581, filed on 9 August 2023, the contents of which are incorporated herein by reference in their entirety. [Background technology]

[0002] Dielectric materials having a low dielectric constant (Dk) and a low dielectric loss tangent (Df) can reduce transmission loss in materials used in high-frequency bands. The object of this disclosure is to provide dielectric material compositions suitable for suppressing electrical signal transmission loss in next-generation high-frequency (10 GHz and above) applications. [Overview of the project]

[0003] In one embodiment, the present disclosure features a dielectric film-forming composition comprising: (a) at least one meth(acrylate)-containing polyphenylene ether resin; (b) i) at least one fully imidized polyimide polymer; ii) at least one polyamic acid ester; iii) at least one cyclized polydiene resin; and iv) a mixture of at least one cyclized polydiene resin and at least one cyanate ester compound.

[0004] In some embodiments, the dielectric film-forming composition of the present disclosure is a photosensitive composition.

[0005] In another embodiment, the present disclosure features a method for preparing a dielectric film, the method comprising: a) coating a dielectric film-forming composition described herein onto a substrate to form a film; and b) optionally baking the film at a temperature of about 50°C to about 150°C for about 20 seconds to about 240 seconds.

[0006] In another aspect, the present disclosure features a method for preparing a dry film, the method comprising: a) coating a carrier substrate with a dielectric film-forming composition described herein to form a coated composition; b) drying the coated composition to form a dry film; and c) optionally, applying a protective layer to the dry film.

[0007] In yet another aspect, the present disclosure features a dielectric film comprising at least one second resin selected from the group consisting of: (a) at least one meta(acrylate)-containing polyphenylene ether resin; (b) i) at least one fully imidized polyimide polymer; ii) at least one polyamic acid ester; iii) at least one cyclized polydiene resin; and iv) a mixture of at least one cyclized polydiene resin and at least one cyanate ester compound. In some embodiments, the dielectric film of the present invention is photosensitive.

BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Generally, the present disclosure relates to a dielectric film-forming composition, and related methods, dry films, and dielectric films.

[0009] In some embodiments, the dielectric film-forming composition described herein comprises at least one (e.g., two, three, or four) meta(acrylate)-containing polyphenylene ether resin. As referred to herein, the meta(acrylate)-containing polyphenylene ether resin represents a polyphenylene ether resin comprising at least one (e.g., two) end groups having an acrylate group or a methacrylate group containing an unsaturated double bond. As used herein, the term “(meth)acrylate ” includes both acrylate and methacrylate.

[0010] An example of the meta(acrylate)-containing polyphenylene ether resin described herein is a structure (I) polymer, wherein:

Chemical formula

[0011] An example of the polymer of structure (I) is the polymer of structure (II):

Chemical formula

[0012] In some embodiments, the meta(acrylate)-containing polyphenylene ether resin is present in the dielectric film-forming composition described herein in an amount of about 5 wt% or more (e.g., about 10 wt% or more, about 15 wt% or more, about 20 wt% or more, about 25 wt% or more, about 30 wt% or more, about 35 wt% or more, or about 40 wt% or more) to about 50 wt% or less (e.g., about 45 wt% or less, about 40 wt% or less, about 35 wt% or less, about 30 wt% or less, about 25 wt% or less, about 20 wt% or less, about 15 wt% or less, or about 10 wt% or less).

[0013] In some embodiments, the dielectric film-forming compositions described herein include: i) at least one fully imidized polyimide polymer; ii) at least one polyamic acid ester; iii) at least one cyclized polydiene resin; and iv) at least one (e.g., two, three, or four) secondary resin (different from meth(acrylate)-containing polyphenylene ether resin) selected from the group consisting of mixtures of cyclized polydiene resins and cyanate ester compounds. In some embodiments, the dielectric film-forming compositions described herein may include any combination of polymers i to iv. As used herein, the term “fully imidized” means that the polyimide polymers of this disclosure are imidized by about 90% or more (e.g., about 95% or more, about 98% or more, about 99% or more, or about 100%). Imidization for producing polyimide is due to the imide ring structure resulting from 1770 cm². -1 and 1700cm -1 This can be confirmed by observing characteristic absorption in the infrared spectrum.

[0014] In some embodiments, at least one fully imidized polyimide described herein is prepared by the reaction of at least one diamine as a monomer with at least one dianhydride (e.g., at least one tetracarboxylic dianhydride) as another monomer. Examples of diamines include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,2-benzene-diamine, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,2-diaminocyclohexane, and 1,4-diaminocyclohexane. Xane, 1,3-cyclohexanebis(methylamine), 5-amino-1,3,3-trimethylcyclohexanemethaneamine, 2,5-diaminobenzotrifluoride, 3,5-diaminobenzotrifluoride, 1,3-diamino-2,4,5,6-tetrafluorobenzene, 4,4'-oxydianiline, 3,4'-oxydianiline, 3,3'-oxydianiline, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'- Sopropylidenedianiline, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4-aminophenyl-3-aminobenzoate, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)benzidine, 3,3' -Bis(trifluoromethyl)benzidine, 2,2-bis[4-(4-aminophenoxyphenyl)]hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)-hexafluoropropane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 1,3-bis-(4-aminophenoxy)benzene, 1,3-bis-(3-aminophenoxy)benzene, 1,4-bis-(4-aminophenoxy)benzene, 1,4-bis-(3-aminophenoxy)benzene, 1-(4-aminophenoxy)-3-(3-aminophenoxy)benzene, 2,2’-bis-(4-phenoxyaniline) isopropylidene, bis(p-β-amino-t-butylphenyl) ether, p-bis-2-(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 3,3’-dimethyl-4,4’-diaminobiphenyl, 4,4’-diaminobenzophenone, 3’-dichlorobenzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4’-[1,3-phenylenebis(1-methyl-ethylidene)]bisaniline, 4,4’-[1,4-phenylenebis(1-methyl-ethylidene)]bisaniline, 2,2-bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)benzene], 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, (1,3’-bis(3-aminophenoxy)benzene, and 9H-fluorene-2,6-diamine, but are not limited thereto.,

[0015] In some embodiments, at least one diamine comprises a compound selected from the group consisting of the diamine of structure (IIIa) and the diamine of structure (IIIb): [Chemical formula] and [Chemical formula] wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 11 , R 12 , R 13 , and R 14 is independently H, a substituted or unsubstituted C1-C6 straight-chain or branched alkyl group, or a C5-C7 cycloalkyl group.

[0016] R 1 , R 2 , R 3 , R 4 , R 5 , R 11 , R 12 , R 13 , and R 14 Examples of substituted or unsubstituted C1-C6 linear or branched alkyl groups in include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, hexyl, and 2-methylhexyl. 1 , R 2 , R 3 , R 4 , R 5 , R 11 , R 12 , R 13 , and R 14 Examples of C5-C7 cycloalkyl groups in this context include, but are not limited to, cyclopentyl, cyclohexyl, and cycloheptyl.

[0017] Examples of diamines of structure (IIIa) or (IIIb) include 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (also known as 4,4'-[1,4-phenylene-bis(1-methylethylidene)]bisaniline), 1-(4-aminophenyl)-1,3,3-trimethyl-2H-inden-5-amine, 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine, [1-(4-aminophenyl)-1,3,3-trimethylindan-5-yl]amine, and 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl Examples include, but are not limited to, 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindan, 4-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindan, 5,7-diamino-1,1-dimethylindan, 4,7-diamino-1,1-dimethylindan, 5,7-diamino-1,1,4-trimethylindan, 5,7-diamino-1,1,6-trimethylindan, and 5,7-diamino-1,1-dimethyl-4-ethylindan.

[0018] In some embodiments, at least one diamine is (a) a compound selected from the group consisting of diamines of structure (IIIa) and diamines of structure (IIIb), and (b) at least one compound of structure (IV): [ka] A diamine of which, in formula (IV), R 15 , R 16 , R 17 and R 18 Each of these can independently be H, a substituted or unsubstituted C1-C6 linear or branched alkyl group, or a C5-C7 cycloalkyl group, provided that R 15 , R 16 , R 17 and R 18 It contains diamines, at least two of which are not hydrogen.

[0019] R15 , R 16 , R 17 and R 18 Examples of substituted or unsubstituted C1-C6 linear or branched alkyl groups in include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, hexyl, and 2-methylhexyl. 15 , R 16 , R 17 and R 18 Examples of C5-C7 cycloalkyl groups in this context include, but are not limited to, cyclopentyl, cyclohexyl, and cycloheptyl.

[0020] Examples of diamines of structure (IV) include, but are not limited to, 2,3,5,6-tetramethylphenylenediamine, 2,4-diamino-1,3,5-trimethylbenzene, 2,4-diamino-1,3,5-triethylbenzene, 2,4-diamino-3,5-dimethyl-1-ethylbenzene, 2,4-diamino-1,5-dimethyl-3-ethylbenzene, 2,4-diamino-1,3,5-triisopropylbenzene, 2,3,5,6-tetraisopropylphenylenediamine, and 2,4-diamino-1,3,5,6-tetramethylbenzene.

[0021] In some embodiments, the molar percentage of the diamines of structures (IIIa) and (IIIb) in the total amount of diamines is about 10% or more (e.g., about 20% or more, about 25% or more, about 30% or more, about 35% or more, about 40% or more, about 45% or more, or about 50% or more) to about 90% or less (e.g., about 85% or less, about 80% or less, about 75% or less, about 70% or less, about 65% or less, or about 60% or less).

[0022] In some embodiments, the molar percentage of the diamine of structure (IV) in the total amount of diamines (e.g., the diamines of structures (IIIa), (IIIb), and (IV)) is about 10% or more (e.g., about 20% or more, about 25% or more, about 30% or more, about 35% or more, about 40% or more, about 45% or more, or about 50% or more) to about 90% or less (e.g., about 85% or less, about 80% or less, about 75% or less, about 70% or less, about 65% or less, or about 60% or less).

[0023] In general, to produce the polyimide polymers described herein, a diamine can be reacted with at least one dianhydride, such as at least one tetracarboxylic dianhydride.

[0024] Examples of tetracarboxylic anhydrides include 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindan-5,6-dicarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindan-6,7-dicarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-3-methylindan-5,6-dicarboxylic acid dianhydride, and 1-(3',4'-dicarboxyphenyl)-3-methylindan -6,7-dicarboxylic acid anhydride, pyromellitic acid dianhydride, benzene-1,2,3,4-tetracarboxylic acid dianhydride, 2,3,5,6-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-8,9,10-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride Substance, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, norbornane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]octo-7-ene-3,4,8,9-tetracarboxylic dianhydride, tetracyclo[4.4.1.0 2,5 .0 7,10Undecane-1,2,3,4-tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-diphenylsulfonetetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4' Examples include, but are not limited to, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, ethylene glycol bis(anhydrotrimellitate), and 5-(2,5-dioxotetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride.

[0025] Other fully imidized polyimide polymers are described, for example, in International Publication No. 2016 / 172089, U.S. Patent Nos. 10,036,952 and 10,563,014, and U.S. Patent Application Publication No. 2015 / 0219990, which are incorporated herein by reference.

[0026] In some embodiments, at least one polyamic acid ester described herein can be prepared by using diamines and dianhydrides described herein as monomers. In some embodiments, one or more diamines are combined with one or more tetracarboxylic dianhydrides in at least one (e.g., two, three, or more) polymerization solvents to produce a polyamic acid (PAA) polymer. In some embodiments, the PAA polymer thus produced can be esterified to produce a polyamic acid ester, which may remain dissolved in the polymerization solvent.

[0027] In some embodiments, the cyclized polydiene resins described herein (e.g., substituted or unsubstituted) may include homopolymers of conjugated dienes such as isoprene, butadiene, and pentadiene. In other embodiments, the cyclized polydiene resins include copolymers of such conjugated dienes with olefins (e.g., ethylene or propylene), styrene, or acrylates. Cyclization of polydienes occurs under the influence of heat, light, ultraviolet or nuclear radiation, or in the presence of a cation-donating catalyst (e.g., mineral acid, organic acid, or Lewis acid). For example, two adjacent polymer structural units may participate in cis-olefin-catalyzed cyclization, thereby creating a monocyclic structure by eliminating one double bond. If cyclization continues, a bicyclic or tricyclic structure may be created in later stages. Gradually, the degree of unsaturation and elasticity of the polydiene decreases as a result of the continuous cyclization of cis double bonds, and the toughness of the polydiene increases. In some embodiments, cyclization may be more efficient in polyisoprene than in polybutadiene. By controlling the temperature, catalyst concentration, and / or reaction time, a degree of cyclization of approximately 50% to approximately 95% can be achieved. Examples of such cyclization methods are described, for example, in U.S. Patent Nos. 4,678,841 and 4,248,986, and European Patent No. 0063043, which are incorporated herein by reference.

[0028] Cyclized polydiene resins can have any suitable weight-average molecular weight (Mw) depending on the specific product application, the solvent used, and the method of application to the underlying substrate. For example, cyclized polydiene resins can have a weight-average molecular weight of about 5,000 daltons or more (e.g., about 25,000 daltons or more, about 50,000 daltons or more, about 75,000 daltons or more, about 100,000 daltons or more, about 125,000 daltons or more, or about 150,000 daltons or more) and / or about 500,000 daltons or less (e.g., about 400,000 daltons or less, about 300,000 daltons or less, or about 200,000 daltons or less).

[0029] In some embodiments, the dielectric film-forming compositions described herein may include a mixture of cyclized polydiene resins. The mixture may include: a) At least one cyclized polydiene resin having a weight-average molecular weight of approximately 5,000 Daltons to approximately 20,000 Daltons; b) At least one cyclized polydiene resin having a weight-average molecular weight of approximately 25,000 Daltons to approximately 60,000 Daltons; and c) At least one cyclized polydiene resin having a weight-average molecular weight of approximately 70,000 Daltons to approximately 200,000 Daltons. It can include...

[0030] While we do not wish to be constrained by theory, it is believed that dielectric film-forming compositions containing mixtures of cyclized polydiene resins with different molecular weights can yield dielectric films with excellent coating quality and film properties.

[0031] In some embodiments, the double bond content in non-cyclized polyisoprene is a degree of unsaturation of 14.7 mmol per gram of polyisoprene, i.e., the reciprocal of the molecular weight of isoprene units (i.e., 68 g / mol). Generally, the double bond content in cyclized polyisoprene decreases as the degree of cyclization increases. In some embodiments, the amount of double bonds or degree of unsaturation of a cyclized polydiene resin (e.g., in xylene) may range from about 1 mmol or more (e.g., about 2 mmol or more, about 3 mmol or more, about 4 mmol or more, or about 5 mmol or more) to about 12 mmol or less (e.g., about 11 mmol or less, about 10 mmol or less, about 9 mmol or less, or about 8 mmol or less) per gram of cyclized polyisoprene.

[0032] Generally, an increase in bicyclic and tricyclic structures in cyclized polydiene resins increases the glass transition temperature (Tg) of the polydiene resin. In some embodiments, the Tg of the cyclized polydiene resins disclosed herein may be about 0°C or higher (e.g., about 5°C or higher, about 10°C or higher, about 15°C or higher, about 20°C or higher, or about 25°C or higher) and / or about 100°C or lower (e.g., about 90°C or lower, about 80°C or lower, about 70°C or lower, about 60°C or lower, or about 50°C or lower). In some embodiments, two or more cyclized polydiene resins having different properties (e.g., different degrees of unsaturation or Tg) can be used in combination in the dielectric film-forming compositions described herein.

[0033] In some embodiments, the cyclized polydiene resins described herein may contain one or more substituted or unsubstituted alkenyl groups. When used herein, possible substituents (e.g., substituted alkyl, alkenyl, alkylene, cycloalkyl, cycloalkylene, aryl, arylalkyl, or heteroaryl groups) or substituents in substituted compounds include C1-C11. 10 Examples include alkyl (e.g., methyl, ethyl, or propyl), halogen (F, Cl, Br, or I), cyano, and phenyl.

[0034] In some embodiments, the cyclized polydiene resin described herein may be in an amount of about 2% by weight or more (e.g., about 3% by weight or more, about 4% by weight or more, about 5% by weight or more, about 8% by weight or more, or 10% by weight or more) to about 40% by weight or less (e.g., about 35% by weight or less, about 30% by weight or less, about 25% by weight or less, about 20% by weight or less, or about 15% by weight or less) of the dielectric film-forming composition described herein.

[0035] In embodiments of the dielectric film-forming composition described herein, which includes a cyclized polydiene resin, the composition may further include at least one cyanate ester compound as part of the second resin. In some embodiments, the cyanate ester compound has structure (V): [ka] In the formula, m is an integer greater than or equal to 2 (i.e., m≧2), and A is a divalent organic group containing a substituted or unsubstituted aromatic group (for example, the cyanate ester group -OC≡N is directly bonded to a substituted or unsubstituted aromatic organic group). It may have these. In some embodiments, the aromatic group may include aryl and heteroaryl groups. As used herein, the term "aryl" refers to a hydrocarbon moiety having one or more aromatic rings. Examples of aryl moieties include phenyl (Ph), phenylene, naphthyl, naphthylene, pyrenyl, anthryl, and phenanthryl. As used herein, the term "heteroaryl" refers to a moiety having one or more aromatic rings containing at least one heteroatom (e.g., N, O, or S). Examples of heteroaryl moieties include furyl, furylene, fluorenyl, pyrrolyl, thienyl, oxazolyl, imidazolyl, thiazolyl, pyridinyl, pyrimidinyl, quinazolinyl, quinolyl, isoquinolyl, and indolyl.

[0036] Specific examples of suitable cyanate ester compounds include 2-bis(4-cyanatophenyl)propane, hexafluorobisphenol A dicyanate, bis(4-cyanato-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether; polyfunctional cyanate esters derived from phenol novolacs, cresol novolacs, or dicyclopentadiene structure-containing phenolic resins, or similar. Other examples of cyanate ester compounds are described, for example, in U.S. Patent No. 3,595,900; No. 4,894,414, and No. 4,785,034, the contents of which are incorporated herein by reference. In some embodiments, two or more cyanate ester compounds can be used in the dielectric film-forming compositions described herein.

[0037] In some embodiments, the cyanate curing catalyst can be selected from the group consisting of metal carboxylates and metal acetylacetonates. The metal in the metal carboxylates and metal acetylacetonates can be selected from the group consisting of zinc, copper, manganese, cobalt, iron, nickel, aluminum, titanium, zirconium, and mixtures thereof. Examples of cyanate curing catalysts include metal salts such as zirconyl dimethacrylate, zinc octanoate, zinc naphthenate, cobalt naphthenate, copper naphthenate, and iron acetylacetone; phenolic compounds such as octylphenol and nonylphenol; alcohols such as 1-butanol and 2-ethylhexanol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and 2-phenyl-4,5-dihydroxy Examples of catalysts include imidazole compounds such as methylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, and 4-methyl-N,N-dimethylbenzylamine; phosphorus compounds such as phosphine compounds and phosphonium compounds; epoxy-imidazole adducts; and peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate, and di-2-ethylhexyl peroxycarbonate. These catalysts are commercially available. Examples of commercially available catalysts include Amicure PN-23 (trade name, manufactured by Ajinomoto Fine-Techno Co., Inc.), Novacure HX-3721 (trade name, manufactured by Asahi Kasei Corporation), and Fujicure FX-1000 (trade name, manufactured by Fuji Kasei Kogyo Co., Ltd.). One or more combinations of these catalysts can be used in the compositions described herein. Other examples of such catalysts are described, for example, in U.S. Patent Application Publication No. 2018 / 0105488 and U.S. Patent No. 9,822,226, which are incorporated herein by reference.

[0038] In some embodiments, the cyanate ester compound described herein may be in an amount of about 1% by weight or more (e.g., about 2% by weight or more, about 3% by weight or more, about 4% by weight or more, or about 5% by weight or more) to about 25% by weight or less (e.g., about 20% by weight or less, about 15% by weight or less, about 10% by weight or less, or about 8% by weight or less) of the dielectric film-forming composition described herein.

[0039] In some embodiments, the second resin may be in an amount of about 50% by weight or more (e.g., about 55% by weight or more, about 60% by weight or more, about 65% by weight or more, about 70% by weight or more, about 75% by weight or more, about 80% by weight or more, or about 85% by weight or more) to about 90% by weight or less (e.g., about 90% by weight or less, about 85% by weight or less, about 80% by weight or less, about 75% by weight or less, about 70% by weight or less, about 65% by weight or less, or about 60% by weight or less) of the dielectric film-forming composition described herein.

[0040] In some embodiments, the dielectric film-forming compositions described herein may optionally contain at least one (e.g., two, three, or four) crosslinking agents. In some embodiments, the crosslinking agents described herein may contain two or more (e.g., three or four) functional groups that can react with substituted or unsubstituted alkenyl groups on a cyclized polydiene resin to form a crosslinked dielectric film. Examples of crosslinking agents include compounds comprising two or more (meth)acrylate groups, two or more olefin groups, two or more cycloolefin groups, or two or more alkynyl groups.

[0041] Examples of compounds containing two or more cycloolefin groups include, but are not limited to, dicyclopentadiene, norbornadiene, and the like. Examples of compounds containing two olefin groups include divinylbenzene, ethylenenorbornene, and the like. In some embodiments, compounds containing two or more (meth)acrylate groups include unsubstituted or substituted linear, branched, or cyclic C1-C1 10Examples include di(meth)acrylates of alkyl groups and di(meth)acrylates of unsubstituted or substituted aromatic groups. Examples of such compounds include, but are not limited to, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, tricyclodecanedimethanol diacrylate, 1,4-phenylenedi(meth)acrylate, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane, tricyclodecanedimethanol di(meth)acrylate, and trimethylolpropane ethoxylate tri(meth)acrylate. Other examples of crosslinking agents are described, for example, in U.S. Patent No. 10,036,952; No. 10,563,014 and U.S. Patent Application Publication No. 2015219990, which are incorporated herein by reference. In some embodiments, two or more crosslinking agents may be used in combination in the dielectric film-forming compositions described herein.

[0042] In some embodiments, at least one crosslinking agent may be present in an amount of about 1% by weight or more (e.g., about 2% by weight or more, about 3% by weight or more, about 4% by weight or more, or 5% by weight or more) to about 25% by weight or less (e.g., about 20% by weight or less, about 15% by weight or less, about 10% by weight or less, or about 8% by weight or less) of the total weight of the dielectric film-forming composition described herein. While we do not wish to be bound by theory, it is thought that crosslinking agents can result in crosslinking in the dielectric film (e.g., upon exposure to radiation or heat), which facilitates the formation of a solubility contrast before and after exposure. In addition, while we do not wish to be bound by theory, it is thought that dielectric film-forming compositions containing a relatively large amount of crosslinking agent can result in a dielectric film having a relatively high Tg.

[0043] In some embodiments, the dielectric film-forming compositions described herein may optionally include at least one (e.g., two, three, or four) catalysts (e.g., initiators). The catalysts can induce crosslinking or polymerization reactions when exposed to heat (thermal initiator) and / or a radiation source (photoinitiator). Specific examples of thermal initiators include, but are not limited to, benzoyl peroxide, dicumyl peroxide, 2,2-azobis(2-methylbutyronitrile), and similar. Other examples of thermal initiators are described, for example, in U.S. Patent No. 10,563,014, which is incorporated herein by reference. Specific examples of photoinitiators include, but are not limited to, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone (BASF Irgacure OXE-01), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) (BASF Irgacure OXE-2), ethoxy(2,4,6-trimethylbenzoyl)phenylphosphine oxide (BASF Lucerin TPO-L), NCI-831 (ADEKA Corp.), NCI-930 (ADEKA Corp.), N-1919 (ADEKA Corp.), and similar products. Other examples of photoinitiators are described, for example, in U.S. Patent Nos. 10,036,952 and 10,563,014, and U.S. Patent Application Publications Nos. 2015 / 0219990 and 2019 / 0018321, which are incorporated herein by reference.

[0044] In some embodiments, the amount of catalyst is about 0.2% by weight or more (e.g., about 0.5% by weight or more, about 0.8% by weight or more, about 1.0% by weight or more, or about 1.5% by weight or more) and / or about 3.0% by weight or less (e.g., about 2.8% by weight or less, about 2.6% by weight or less, about 2.4% by weight or less, or about 2.0% by weight or less) of the total weight of the dielectric film-forming composition described herein.

[0045] In some embodiments, the dielectric film-forming compositions described herein may optionally contain at least one (e.g., two, three, or four) solvents (e.g., organic solvents).

[0046] Examples of suitable organic solvents include, but are not limited to, alkylene carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and glycerin carbonate; lactones such as γ-butyrolactone, ε-caprolactone, γ-caprolactone, and δ-valerolactone; cycloketones such as cyclopentanone and cyclohexanone; linear ketones such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); esters such as n-butyl acetate; ester alcohols such as ethyl lactate; ether alcohols such as tetrahydrofurfuryl alcohol; glycol esters such as propylene glycol methyl ether acetate; glycol ethers such as propylene glycol methyl ether (PGME); cyclic ethers such as tetrahydrofuran (THF); aromatic hydrocarbons such as toluene, xylene, mesitylene, and tetralin; and pyrrolidones such as N-methyl-2-pyrrolidone.

[0047] In some embodiments, the amount of solvent is about 40% by weight or more (e.g., about 45% by weight or more, about 50% by weight or more, about 55% by weight or more, about 60% by weight or more, or about 65% by weight or more) and / or about 98% by weight or less (e.g., about 95% by weight or less, about 90% by weight or less, about 85% by weight or less, about 80% by weight or less, or about 75% by weight or less) of the total weight of the dielectric film-forming composition described herein.

[0048] In some embodiments, the dielectric film-forming compositions described herein may optionally further include at least one (e.g., two, three, or four) adhesion promoters (e.g., silanes containing alkoxy groups). Suitable adhesion promoters are described in “Silane Coupling Agent” Edwin P. Plueddemann, 1982 Plenum Press, New York; and U.S. Patent No. 9,519,216, which are incorporated herein by reference.

[0049] In some embodiments, the amount of an optional adhesion promoter used is about 0.5% by weight or more (e.g., about 0.8% by weight or more, about 1% by weight or more, or about 1.5% by weight or more) and / or about 4% by weight or less (e.g., about 3.5% by weight or less, about 3% by weight or less, about 2.5% by weight or less, or about 2% by weight or less) of the total weight of the dielectric film-forming composition described herein.

[0050] In some embodiments, this disclosure includes: a. Polyphenylene ether resin containing at least one type of meth(acrylate); b. At least one fully imidized polyimide polymer; c. At least one second resin as described herein; d. At least one crosslinking agent; e. At least one catalyst; f. Optionally, at least one adhesion promoter; and g. Optionally, at least one solvent A photosensitive composition containing [the specified element] is described.

[0051] In some embodiments, the disclosure features a dielectric film (e.g., a crosslinked dielectric film) comprising (a) at least one meth(acrylate)-containing polyphenylene ether resin, and (b) at least one second resin selected from the group consisting of i) at least one fully imidized polyimide polymer; ii) at least one polyamic acid ester; iii) at least one cyclized polydiene resin; and iv) a mixture of at least one cyclized polydiene resin and at least one cyanate ester compound.

[0052] In some embodiments, the dielectric film can be prepared by a method comprising: a) coating a dielectric film-forming composition described herein onto a substrate (e.g., a semiconductor substrate such as a wafer) to form a film (e.g., a dielectric film); b) optionally baking the film at a high temperature (e.g., about 50°C to about 150°C) for a certain period of time (e.g., about 20 seconds to about 240 seconds); and c) optionally exposing the film to radiation, heat, or a combination of both radiation and heat (flood exposure without the use of a mask, such as a patterned mask). In some embodiments, the dielectric film prepared by the above method (broad-area exposure without a mask may be used) can be crosslinked, but does not include a pattern or relief image.

[0053] Coating methods for preparing dielectric films include, but are not limited to, spin coating, spray coating, roll coating, rod coating, rotational coating, slit coating, compression coating, curtain coating, die coating, wire bar coating, knife coating, and dry film lamination. The semiconductor substrate may have a circular shape, such as a wafer, or it may be a panel. In some embodiments, the semiconductor substrate may be a silicon substrate, a copper substrate, an aluminum substrate, a silicon oxide substrate, a silicon nitride substrate, a glass substrate, an organic substrate, a copper-clad laminate, or a dielectric material substrate.

[0054] The thickness of the dielectric film of this disclosure is not particularly limited. In some embodiments, the dielectric film has a thickness of about 1 micron or more (e.g., about 2 microns or more, about 3 microns or more, about 4 microns or more, about 5 microns or more, about 7 microns or more, about 10 microns or more, about 15 microns or more, about 20 microns or more, about 25 microns or more, 50 microns or more, or 100 microns or more) and / or about 5000 microns (5 mm) or less (e.g., about 4000 microns or less, about 3000 microns or less, about 2000 microns or less, about 1000 microns or less, about 500 microns or less, about 400 microns or less, about 300 microns or less, or 200 microns or more).

[0055] In some embodiments, the dielectric film-forming compositions of the present disclosure are photopatternable. In such embodiments, a method for preparing a patterned dielectric film includes converting a dielectric film prepared from a dielectric film-forming composition into a patterned dielectric film by a lithography process. In such cases, the conversion may include exposing the dielectric film to high-energy radiation (such as electron beams, ultraviolet rays, and X-rays) using a patterned mask.

[0056] After exposure, the dielectric film can optionally be heat-treated at a temperature of approximately 50°C or higher (e.g., approximately 55°C or higher, approximately 60°C or higher, or approximately 65°C or higher) to approximately 100°C or lower (e.g., approximately 95°C or lower, or approximately 90°C or lower, approximately 85°C or lower, approximately 80°C or lower, approximately 75°C or lower, or approximately 70°C or lower) for approximately 60 seconds or higher (e.g., approximately 80 seconds or higher, or approximately 100 seconds or higher) to approximately 240 seconds or lower (e.g., approximately 180 seconds or lower, approximately 120 seconds or lower, or approximately 90 seconds or lower). Heat treatment is usually achieved by using a hot plate or oven.

[0057] After exposure and / or heat treatment, the dielectric film can be developed using a developer to remove unexposed areas, thereby forming openings or relief images on the substrate. Development can be carried out, for example, by immersion or spraying. After development, micropores and fine lines can be generated in the dielectric film on the laminated substrate.

[0058] In some embodiments, the dielectric film can be developed using an organic developer. Examples of such developers include cyclohexanone, xylene, toluene, tetralin, gamma-butyrolactone (GBL), dimethyl sulfoxide (DMSO), N,N-diethylacetamide, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), 2-heptanone, cyclopentanone (CP), cyclohexanone, n-butyl acetate (nBA), propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), ethyl lactate (EL), propyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether, and diethyl Examples of suitable developers include, but are not limited to, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethyl malonate, ethylene glycol, 1,4:3,6-dianhydrosorbitol, isosorbide dimethyl ether, 1,4:3,6-dianhydrosorbitol 2,5-diethyl ether (2,5-diethyl isosorbide), and mixtures thereof. Preferred developers are cyclohexanone, xylene, toluene, and tetralin. These developers can be used alone or in combination of two or more to optimize the image quality of the composition and the lithography method.

[0059] In some embodiments, the dielectric films described herein are not photopatternable. In such cases, patterning can be achieved by mechanical laser drilling or a two-layer method. Laser drilling generally involves a fixed laser beam that uses a high power density to melt or vaporize material from a target substrate or workpiece. In principle, laser drilling is governed by the energy balance between the irradiation energy from the laser beam and the heat conducted to the substrate, energy loss to the environment, and the energy required for the phase change of the workpiece. An example of mechanical laser drilling is described, for example, in U.S. Patent No. 6,353,999, which is incorporated herein by reference.

[0060] In some embodiments, the dielectric films described herein can have relatively low dielectric loss tangents (Df). For example, the dielectric films described herein can have a Df of about 0.01 or less (e.g., about 0.008 or less, about 0.006 or less, about 0.005 or less, about 0.004 or less, about 0.002 or less, or about 0.001 or less) and about 0.0001 or more when measured at 5 GHz to 50 GHz after curing. The dielectric constant (Dk) and dielectric loss tangent (Df) are measured at a variable frequency of 1 GHz to 75 GHz using a split-cylinder resonator according to the IPC TM-650 2.5.5.13 method, which is well known to those skilled in the art.

[0061] In some embodiments, the present disclosure features a method for preparing a dry film. In some embodiments, the method includes a) coating a carrier substrate with a dielectric film-forming composition described herein to form a coating composition; b) drying the coating composition to form a dielectric film; and c) optionally applying a protective layer to the dielectric film. In some embodiments, the dry film may include a carrier substrate, a dielectric film, and optionally a protective layer.

[0062] In some embodiments, the carrier substrate is a single-layer or multi-layer plastic film that may contain one or more polymers (e.g., polyethylene terephthalate). In some embodiments, the carrier substrate has excellent optical transparency and is substantially transparent to chemical irradiation used to form a relief pattern in the polymer layer. The thickness of the carrier substrate is preferably in the range of about 10 microns or more (e.g., about 15 microns or more, about 20 microns or more, about 30 microns or more, about 40 microns or more, about 50 microns or more, or about 60 microns or more) to about 150 microns or less (e.g., about 140 microns or less, about 120 microns or less, about 100 microns or less, about 90 microns or less, about 80 microns or less, or about 70 microns or less).

[0063] In some embodiments, the protective layer is a single-layer or multilayer film that may contain one or more polymers (e.g., polyethylene or polypropylene). Examples of carrier substrates and protective layers are described, for example, in U.S. Patent Application Publication 2016 / 0313642, the contents of which are incorporated herein by reference in their entirety.

[0064] In some embodiments, the dielectric film of a dry film can be peeled from the carrier layer as a self-supporting dry film. A self-supporting dry film is a film that can maintain its physical integrity without using any supporting layer, such as a carrier layer. In some embodiments, the self-supporting dielectric dry film is not crosslinked or cured and may contain components of the dielectric film-forming compositions described herein, except for the solvent.

[0065] In some embodiments, dielectric films prepared from the dielectric film-forming compositions described herein may have a relatively low dielectric loss tangent. For example, the dielectric loss tangent of a dielectric film (e.g., a crosslinked or uncrosslinked dielectric film) prepared from the dielectric film-forming compositions of this disclosure, measured at 10 GHz, may range from about 0.001 or higher (e.g., about 0.005 or higher, about 0.01 or higher, or about 0.05 or higher) to about 0.1 or lower (e.g., about 0.08 or lower, about 0.06 or lower, about 0.05 or lower, about 0.04 or lower, or about 0.020 or lower).

[0066] In some embodiments, the disclosure features a three-dimensional object comprising at least one layer of a conductive metal and a dielectric film (e.g., a crosslinked and patterned dielectric film) formed using the dielectric film-forming composition of the disclosure. In some embodiments, the three-dimensional object may include dielectric films in at least two layers (e.g., at least three layers).

[0067] The following embodiments are provided to more clearly illustrate the principles and practices of this disclosure. It should be understood that this disclosure is not limited to the embodiments described herein. [Examples]

[0068] Example 1: Preparation and application of dielectric film-forming composition 1 Dielectric film-forming composition 1 is prepared by mixing cycloadhesive polyisoprene (SC rubber, supplied by Fujifilm Electronic Materials USA, 57.90 g, 28.5% solution in xylene), SA9000 (available from Sabic, 6.6 g), 2,2-bis(4-cyanatophenyl)propane (8.25 g), dicumyl peroxide (0.50 g), and xylene (1.75 g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0069] In this example, SC rubber is used as a cyclized polydiene; 2,2-bis(4-cyanatophenyl)propane is used as a cyanate ester compound; SA9000 is used as a low-Df methacrylate-containing polyphenylene ether resin; dicumyl peroxide is used as a thermal initiator; and xylene is used as a solvent.

[0070] The dielectric film-forming composition 1 prepared above is applied to a 35-micron thick PET film using an applicator to form a dielectric film. This film is baked at 95°C for 10 minutes using a hot plate to remove most of the solvent. This film is then baked at 150°C for 1 hour under nitrogen to obtain a stable dielectric film with a thickness of 120 microns. After lifting the dielectric film from the PET film, it is placed on a 25-micron thick KAPTON film and then baked for another 1 hour at 200°C under nitrogen.

[0071] After cooling to room temperature, the dielectric film is removed from the KAPTON film, slit to form a 3 mm wide film, and its thermomechanical properties are analyzed by thermomechanical analysis ("TMA") using a TMA 450 (TA Instruments, available from the USA). The CTE (coefficient of linear thermal expansion) is 100 ppm / K measured in the temperature range of 25°C to 120°C.

[0072] Example 2: Preparation and application of dielectric film-forming composition 2 Dielectric film-forming composition 2 is prepared by mixing cyclized polyisoprene (SC rubber, supplied by Fujifilm Electronic Materials USA, 28.5% solution in 57.90 g xylene), SA9000 (available from Sabic, 6.6 g), tricyclodecanedimethanol diacrylate (6.60 g), 2,2-bis(4-cyanatophenyl)propane (8.25 g), silica (12.0 g, silica nanoparticles SUPSIL® PREMIUM, monodisperse, charge-stabilized, supplied by Superior Silica), dicumyl peroxide (0.50 g), and xylene (1.75 g) to obtain a homogeneous solution. This solution is filtered using a 5.0 micron PTFE filter.

[0073] In this embodiment, SC rubber is used as a cyclized polydiene, silica is used as an inorganic particle filler, SA9000 is used as a low-Df methacrylate-containing polyphenylene ether resin, tricyclodecanedimethanol diacrylate is used as a crosslinking agent, 2,2-bis(4-cyanatophenyl)propane is used as a cyanate ester compound, dicumyl peroxide is used as a thermal initiator, and xylene is used as a solvent.

[0074] Dielectric film-forming composition 2 is applied to a 35-micron thick PET film using an applicator to form a dielectric film. This film is baked at 105°C for 7 minutes using a hot plate to remove most of the solvent. The film is then baked under nitrogen at 160°C for 185 minutes to obtain a stable dielectric film with a thickness of 90 microns. After lifting the dielectric film from the PET film, it is placed on a 25-micron KAPTON film and then baked further under nitrogen at 210°C for 1 hour.

[0075] After cooling to room temperature, the dielectric film is removed from the KAPTON film, slit to form a 3 mm wide film, and its thermomechanical properties are analyzed by TMA. The CTE (coefficient of linear thermal expansion) is 60 ppm / K measured in the temperature range of 25°C to 120°C.

[0076] Synthesis example 1 (P-1) 6. Preparation of FDA / DAPI polyimides [ka] Polymer (Poly-1) Solid 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) (3.34 kg, 7.52 mol) was added at room temperature to a solution of 4,4'-[1,4-phenylene-bis(1-methylethylidene)]bisaniline (DAPI) (2.18 kg, 8.19 mol) in NMP (22.06 kg). The dianhydride was washed into the solution using an additional NMP (8.16 kg). The reaction temperature was raised to 60°C and the mixture was reacted for 3.5 hours. Next, acetic anhydride (1.257 kg) and pyridine (495 g) were added, the reaction temperature was raised to 100°C, and the mixture was reacted for 12 hours.

[0077] The reaction mixture was cooled to room temperature and transferred to a larger vessel equipped with a mechanical stirrer. The reaction solution was diluted with ethyl acetate as the purification solvent and washed with water for 1 hour. Stirring was stopped and the mixture was allowed to stand. After phase separation occurred, the aqueous phase was removed. The organic phase was diluted with a combination of cyclopentanone and toluene as the purification solvent and washed three more times with water. The amounts of purification solvents (i.e., cyclopentanone and toluene) and water used in all washes are shown in Table 1.

[0078] [Table 1]

[0079] The washed organic phase was concentrated by vacuum distillation. Cyclopentanone (7.1 kg) was added as an isolation solvent, and vacuum distillation was continued to obtain polymer solution (P-1). The molecular weight of polymer Poly-1 was 53,500 daltons, and the solid content in solution (P-1) was 31.85%. The molar ratio of dianhydride to diamine in this example was 0.92.

[0080] Example 3: Preparation and application of photosensitive dielectric film-forming composition Photosensitive dielectric film-forming composition 3 is prepared using 89.7 g of the polymer solution (P-1) prepared above, 8.00 g of cyclopentanone, 2.04 g of a 0.5 wt% solution of PolyFox 6320 (available from OMNOVA Solutions) in cyclopentanone, 1.92 g of methacryloxypropyltrimethoxysilane, 1.92 g of 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone (OXE-02 from BASF), 0.077 g of parabenzoquinone, 15.840 g of tetraethylene glycol diacrylate, and 5.280 g of SA 9000. After mechanical stirring for 24 hours, the solution is filtered using a 0.2 micron PTFE filter to obtain photosensitive dielectric film-forming composition 3.

[0081] In this example, polyimide solution (P-1) is used as a fully cyclized polyimide, SA9000 is used as a low-Df methacrylate-containing polyphenylene ether resin, tetraethylene glycol diacrylate is used as a crosslinking agent, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone is used as a photoinitiator, methacryloxypropyltrimethoxysilane is used as an adhesion promoter, and cyclopentanone is used as a solvent.

[0082] The photosensitive dielectric film-forming composition 3 is applied to a 35-micron thick PET film using an applicator to form a dielectric film. This film is baked at 95°C for 7 minutes using a hot plate to remove most of the solvent. The film is then baked under nitrogen at 160°C for 185 minutes to obtain a stable dielectric film with a thickness of 70 microns. After lifting the dielectric film from the PET film, it is placed on a 25-micron thick KAPTON film and then baked for a further 1 hour under nitrogen at 200°C.

[0083] After cooling to room temperature, the dielectric film is removed from the KAPTON film, slit to form a 3 mm wide film, and its thermomechanical properties are analyzed by TMA. The CTE (coefficient of linear thermal expansion) is 65 ppm / K, measured in the temperature range of 25°C to 120°C.

[0084] Table 2 summarizes the dielectric constant (Dk) and dielectric loss tangent (Df) of the composition of Example 3.

[0085] [Table 2]

[0086] Other aspects, embodiments, and features are within the scope of the following claims.

Claims

1. (a) A polyphenylene ether resin containing at least one meth(acrylate), and (b) At least one second resin selected from the group consisting of i) to iv), i) At least one fully imidized polyimide polymer; ii) At least one polyamic acid ester; iii) At least one type of cyclopolydiene resin; iv) A mixture of at least one cyclized polydiene resin and at least one cyanate ester compound, A dielectric film-forming composition containing the following:

2. The composition according to claim 1, wherein the at least one meth(acrylate)-containing polyphenylene ether resin comprises a polyphenylene ether resin having at least one meth(acrylate) group as a terminal group.

3. The composition according to claim 2, wherein the at least one meth(acrylate)-containing polyphenylene ether resin comprises a structural (I) polymer: 【Chemistry 1】 In formula (I), Each of n1 and n2 is an integer between 0 and 20, independently of each other; X is -C(O)-, -S(O)-, -S(O) ２ -, or -C(RR')-, where each of R and R' is independently H or C １ ~C ６ It is alkyl, Each R １ These are independently aliphatic hydrocarbon groups having 1 to 6 carbon atoms; and Each R ２ These are independently H, halo, or an aliphatic hydrocarbon group having 1 to 6 carbon atoms.

4. The composition according to claim 2, wherein the at least one meth(acrylate)-containing polyphenylene ether resin comprises a structural (II) polymer: 【Chemistry 2】 In formula (II), Each of m and n is an integer between 0 and 20, and Y is -C(O)-, -S(O)-, -S(O) ２ It is -, or -C(RR')-, where each of R and R' is independently H or C1-C6 alkyl.

5. The composition according to any one of claims 1 to 4, wherein the at least one meth(acrylate)-containing polyphenylene ether resin is present in an amount of about 5% to about 50% by weight of the composition.

6. The composition according to any one of claims 1 to 5, wherein the at least one second resin is present in an amount of about 50% to about 90% by weight of the composition.

7. The composition according to any one of claims 1 to 6, further comprising at least one crosslinking agent, at least one catalyst, at least one adhesion promoter, and at least one solvent.

8. a) Forming a film by applying the dielectric film-forming composition according to any one of claims 1 to 7 onto a substrate, and b) Optionally, bake the film at a temperature of approximately 50°C to approximately 150°C for approximately 20 seconds to approximately 240 seconds. A method for preparing a dielectric film, including [the specified element].

9. The method according to claim 8, further comprising exposing the film to radiation, heat, or a combination thereof without a mask.

10. A method for preparing a dry film, wherein the method is: a) A carrier substrate is coated with a dielectric film forming composition according to any one of claims 1 to 7 to form a coating composition; b) Drying the coating composition to form a dielectric film; c) Optionally, a protective layer may be applied to the dielectric film. Methods that include...

11. The dielectric film according to any one of claims 1 to 10, wherein after curing the film by exposure to radiation, heat, or a combination thereof without a mask, the dielectric film has a dielectric loss tangent (Df) of about 0.01 or less at 5 GHz.

12. (a) At least one meth(acrylate)-containing polyphenylene ether resin, (b) At least one second resin selected from the group consisting of i) to iv), i) At least one fully imidized polyimide polymer; ii) At least one polyamic acid ester; iii) At least one type of cyclopolydiene resin; iv) A mixture of at least one cyclized polydiene resin and at least one cyanate ester compound, (c) at least one crosslinking agent, (d) at least one catalyst, and (e) at least one solvent, A photosensitive dielectric film-forming composition containing the following.

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