Dielectric film-forming composition

Abstract

The present disclosure pertains to a dielectric film-forming composition comprising (a) at least one methyl (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

Cross-references to related applications

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

[0002] Dielectric materials with low dielectric constant (Dk) and low dielectric loss tangent (Df) can reduce transmission losses in materials used in high-frequency bands. The purpose of this disclosure is to provide dielectric material compositions suitable for suppressing transmission losses of electrical signals in next-generation high-frequency (10 GHz or higher) applications. Summary of the Invention

[0003] In one aspect, the present disclosure is characterized by a dielectric film forming composition comprising: (a) at least one methyl (acrylate) polyphenylene ether resin; (b) at least one second resin selected from the group consisting of: i) at least one fully imidized polyimide polymer; ii) at least one polyamide 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 disclosed herein is a photosensitive composition.

[0005] In another aspect, this disclosure is characterized by a method for preparing a dielectric film, the method comprising: a) coating the dielectric film forming composition described herein onto a substrate to form a dielectric film; and b) optionally coating the film at about 50°C. o C to approximately 150 o Bake at a temperature of C for approximately 20 to 240 seconds.

[0006] In another aspect, this disclosure is characterized by a method for preparing a dry film, the method comprising: a) coating a carrier substrate with the 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 another aspect, this disclosure features a dielectric film comprising (a) at least one methyl (acrylate) 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 cyclic polydiene resin; and iv) a mixture of at least one cyclic polydiene resin and at least one cyanate ester compound. In some embodiments, the dielectric film of the present invention is photosensitive. Detailed Implementation

[0008] Generally speaking, this disclosure relates to dielectric film forming compositions, related methods, dry films, and dielectric films.

[0009] In some embodiments, the dielectric film forming compositions described herein comprise at least one (e.g., two, three, or four) methyl (acrylate)-containing polyphenylene ether resin. As mentioned herein, a methyl (acrylate)-containing polyphenylene ether resin refers to a polyphenylene ether resin containing at least one (e.g., two) end groups having acrylate or methacrylate groups comprising unsaturated double bonds. As used herein, the term "(meth)acrylate" includes both acrylate and methacrylate.

[0010] Examples of methyl (acrylate)-containing polyphenylene ether resins described herein are polymers of structure (I): (I), Each of n1 and n2 is an integer from 0 to 20; X is -C(O)-, -S(O)-, -S(O)2- or -C(RR')-, where each of R and R' is independently H or a C1-C6 alkyl group; each R 1 Independently, it is an aliphatic hydrocarbon group having 1 to 6 carbon atoms (e.g., C1-C6 alkyl); and each R 2 It can be independently H, a halogen (e.g., F, Cl, Br or I) or an aliphatic hydrocarbon group having 1 to 6 carbon atoms (e.g., C1-C6 alkyl).

[0011] Examples of polymers with structure (I) are polymers with structure (II): (II), Each of m and n is independently an integer from 0 to 20, and Y is -C(O)-, -S(O)-, -S(O)2-, or -C(RR')-, wherein each of R and R' is independently H or a C1-C6 alkyl group. A commercially available example of a polymer with structure (I) or (II) is SA9000 resin, which is available from SABIC.

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

[0013] In some embodiments, the dielectric film forming composition described herein comprises at least one (e.g., two, three, or four) second resin (different from the methyl (acrylate)-containing polyphenylene ether 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 cyclized polydiene resin and cyanate ester compound. In some embodiments, the dielectric film forming composition described herein may comprise any combination of polymers i-iv. As used herein, the term “fully imidized” means that the polyimide polymer of this disclosure is at least about 90% (e.g., at least about 95%, at least about 98%, at least about 99%, or about 100%) imidized. Imidization to form a polyimide can be observed at imide ring structures ranging from 1770 to 1700 cm⁻¹. -1 The characteristic absorption in the infrared spectrum is used for confirmation.

[0014] In some embodiments, at least one fully imidized polyimide described herein is prepared by reacting 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, but are not limited to, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,2-phenylenediamine, 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, 1,4-diaminocyclohexane, 1,3-cyclohexanebis(methylamine), 5-amino-1,3,3-trimethylcyclohexanemethylamine, 2,5-diaminotrifluoromethylbenzene, 3,5-diaminotrifluoromethylbenzene, 1,3-diamino-2,4,5,6-tetrafluorobenzene, 4,4'-diamino 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-isopropylidene diphenylamine, 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-diphenyl)propane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 2,2'-bis-[4-(4-diphenyl)propane, 4,4'-diaminodiphenyl sulfone ...3,3'-bis-(trifluoromethyl)benzidine, 2,2'-bis-[4-(4-diphenyl)propane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulf [-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-tert-butylphenyl) ether, p-bis-2-(2-methyl-4-aminopentyl(aminopentyl))benzene, p-bis(1,1 (dimethyl-5-aminopentyl)benzene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ketone, 3'-dichlorobenzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methyl-ethylene)]diphenylamine, 4,4'-[1,4-phenylenebis(1-methyl-ethylene)]diphenylamine, 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.

[0015] In some embodiments, at least one diamine comprises a compound selected from the group consisting of diamines of structure (IIIa) and diamines of structure (IIIb): (IIIa) and (IIIb) Among them, R 1 R 2 R 3 R 4 R 5 R 11 R 12 R 13 and R 14 Each of them 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 straight-chain or branched alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, 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 include, but are not limited to, cyclopentyl, cyclohexyl, and cycloheptyl.

[0017] Examples of diamines with structures (IIIa) or (IIIb) include, but are not limited to, 1-(4-aminophenyl)-1,3,3-trimethyldihydroindene-5-amine (also known as 4,4'-[1,4-phenylene-bis(1-methylethylene)]diphenylamine, 1-(4-aminophenyl)-1,3,3-trimethyl-2H-dihydroindene-5-amine, 1-(4-aminophenyl)-1,3,3-trimethyl-dihydroindene-5-amine, [1-(4-aminophenyl)-1,3,3-trimethyl-dihydroindene-5-yl]amine and 1-(4-aminophenyl)-2,3-dihydro-1,3 ,3-trimethyl-1H-dihydroindene-5-amine), 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethyldihydroindene, 4-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethyldihydroindene, 5,7-diamino-1,1-dimethyldihydroindene, 4,7-diamino-1,1-dimethyldihydroindene, 5,7-diamino-1,1,4-trimethyldihydroindene, 5,7-diamino-1,1,6-trimethyldihydroindene and 5,7-diamino-1,1-dimethyl-4-ethyldihydroindene.

[0018] In some embodiments, at least one diamine comprises (a) a compound selected from the group consisting of diamines of structure (IIIa) and diamines of structure (IIIb); and (b) at least one diamine of structure (IV). (IV), Where R 15 R 16 R 17 and R 18 Each can be independently H, a substituted or unsubstituted C1-C6 straight-chain or branched alkyl group, or a C5–C7 cycloalkyl group, provided that R 15 R 16 R 17 and R 18 At least two of them are not hydrogen.

[0019] R 15 R 16 R 17 and R 18 Examples of substituted or unsubstituted C1-C6 straight-chain or branched alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, and 2-methylhexyl. 15 R 16 R 17 and R 18 Examples of C5–C7 cycloalkyl groups include, but are not limited to, cyclopentyl, cyclohexyl, and cycloheptyl.

[0020] Examples of diamines with 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 diamines of structures (IIIa) and (IIIb) constitute a molar percentage of at least about 10% (e.g., at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50%) to at most about 90% (e.g., at most about 85%, at most about 80%, at most about 75%, at most about 70%, at most about 65%, or at most about 60%) of the total diamines.

[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 at least about 10% (e.g., at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45% or at least about 50%) to at most about 90% (e.g., at most about 85%, at most about 80%, at most about 75%, at most about 70%, at most about 65% or at most about 60%).

[0023] Generally, in order to form the polyimide polymer described herein, a diamine can be reacted with at least one dianhydride (such as at least one tetracarboxylic dianhydride).

[0024] Examples of tetracarboxylic dianhydrides include, but are not limited to, 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethyldihydroindene-5,6-dicarboxylic dianhydride, 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethyldihydroindene-6,7-dicarboxylic dianhydride, 1-(3',4'-dicarboxyphenyl)-3-methyldihydroindene-5,6-dicarboxylic dianhydride, 1-(3 ',4'-Dicarboxyphenyl)-3-methyldihydroindene-6,7-dicarboxylic dianhydride, benzopyrene dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 2,3,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4, 5,8-Tetracarboxylic 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 acid Dihydride, 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, norbornene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-3,4,8,9-tetracarboxylic dianhydride, tetracyclo[4.4.1.0] 2,5 .0 7 ,10 Undecane-1,2,3,4-Tetracarboxylic Anhydride, 3,3',4,4'-Diphenylketone Tetracarboxylic Anhydride, 2,2',3,3'-Diphenylketone Tetracarboxylic Anhydride, 2,3,3',4'-Diphenylketone Tetracarboxylic Anhydride, 3,3',4,4'-Diphenylsulfone Tetracarboxylic Anhydride, 2,2',3,3'-Diphenylsulfone Tetracarboxylic Anhydride, 2,3,3',4'-Diphenylsulfone Tetracarboxylic Anhydride Anhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 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(dehydrated trimellitate) and 5-(2,5-dioxytetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride.

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

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

[0027] In some embodiments, the cyclized polydiene resins described herein (e.g., substituted or unsubstituted) may comprise homopolymers of conjugated dienes such as isoprene, butadiene, pentadiene, etc. In other embodiments, the cyclized polydiene resins comprise copolymers of such conjugated dienes with olefins (e.g., ethylene or propylene), styrene, or acrylates. Cyclization of polydienes can occur under the influence of heat, light, ultraviolet radiation, or nuclear radiation, or in the presence of a cationic donor catalyst (e.g., an inorganic acid, organic acid, or Lewis acid). For example, two adjacent polymer structural units may participate in cis-olefin-catalyzed cyclization, which can create a monocyclic structure by eliminating a double bond. As the cyclization reaction continues, bi- or tri-cyclic structures may be generated in subsequent stages. Gradually, as a result of the continuous cyclization of the cis-double bond, the unsaturation and elasticity of the polydiene decrease, and the toughness of the polydiene increases. In some embodiments, cyclization in polyisoprene may be more efficient than in polybutadiene. By controlling the temperature, catalyst concentration, and / or reaction time, a cyclization degree of approximately 50% to approximately 95% can be achieved. Examples of such cyclization methods have been described, for example, in U.S. Patent Nos. 4,678,841 and 4,248,986 and European Patent No. 0063043, the contents of which are incorporated herein by reference.

[0028] Depending on the specific product application, the solvent used, and the method of application to the underlying substrate, cyclic polydiene resins may have any suitable weight-average molecular weight (Mw). For example, cyclic polydiene resins may have a weight-average molecular weight of at least about 5,000 Daltons (e.g., at least about 25,000 Daltons, at least about 50,000 Daltons, at least about 75,000 Daltons, at least about 100,000 Daltons, at least about 125,000 Daltons, or at least about 150,000 Daltons) and / or at most about 500,000 Daltons (e.g., at most about 400,000 Daltons, at most about 300,000 Daltons, or at most about 200,000 Daltons).

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

[0030] Without being bound by theory, it is believed that dielectric film forming compositions containing mixtures of cyclized polydiene resins with different molecular weights can produce dielectric films with superior coating quality and film properties.

[0031] In some embodiments, the double bond content in uncyclized polyisoprene is 14.7 mmol of unsaturation per gram of polyisoprene, i.e., the reciprocal of the molecular weight of the isoprene unit (i.e., 68 g / mol). Generally, the double bond content in cyclized polyisoprene decreases with increasing degree of cyclization. In some embodiments, after cyclization, the amount of double bonds or unsaturation in the cyclized polydiene resin (e.g., xylene) can range from at least about 1 mmol (e.g., at least about 2 mmol, at least about 3 mmol, at least about 4 mmol, or at least about 5 mmol) to at most about 12 mmol (e.g., at most about 11 mmol, at most about 10 mmol, at most about 9 mmol, or at most about 8 mmol) per gram of polyisoprene.

[0032] Generally, the increase of 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 at least about 0. o C (e.g., at least about 5°C, at least about 10°C, at least about 15°C, at least about 20°C, or at least about 25°C) and / or up to about 100°C (e.g., up to about 90°C, up to about 80°C, up to about 70°C, up to about 60°C, or up to about 50°C). In some embodiments, two or more cyclized polydiene resins with different properties (e.g., different degrees of unsaturation or Tg) may be used together in the dielectric film forming composition described herein.

[0033] In some embodiments, the cyclized polydiene resins described herein may include one or more substituted or unsubstituted alkenyl groups. As used herein, possible substituents on the substituted groups (e.g., substituted alkyl, alkenyl, alkylene, cycloalkyl, cycloalkylene, aryl, aralkyl, or heteroaryl groups) or on the substituted compounds include C1-C1 substituents. 10 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 present in an amount of at least about 2% by weight (e.g., at least about 3%, at least about 4%, at least about 5%, at least about 8%, or at least about 10% by weight) to at most about 40% by weight (e.g., at most about 35%, at most about 30%, at most 25%, at most 20%, or at most 15% by weight) of the dielectric film forming composition described herein.

[0035] In embodiments where the dielectric film forming composition described herein comprises a cyclic polydiene resin, the composition may further comprise at least one cyanate ester compound as part of a second resin. In some embodiments, the cyanate ester compound may have the structure (V): A-(OC≡N) m (V), Where m is an integer of at least 2 (i.e., m ≥ 2) and A is a divalent organic group containing a substituted or unsubstituted aromatic group (e.g., a cyanate group -OC≡N directly bonded to the substituted or unsubstituted aromatic organic group). In some embodiments, the aromatic group may include aryl and heteroaryl groups. The term "aryl" as used herein refers to a hydrocarbon moiety having one or more aromatic rings. Examples of aryl moieties include phenyl (Ph), phenylene, naphthyl, naphthylene, pyrene, anthracene, and phenanthrene. The term "heteroaryl" as used herein 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 furanyl, furinyl, fluorenyl, pyrroleyl, thiopheneyl, oxazolyl, imidazolyl, thiazolyl, pyridinyl, pyrimidinyl, quinazolinyl, quinolinyl, isoquinolinyl, and indoleyl.

[0036] Specific examples of suitable cyanate compounds include 2-bis(4-cyanoxyphenyl)propane, hexafluorobisphenol A dicyanate, bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl) sulfide, and bis(4-cyanatephenyl) ether; polyfunctional cyanates derived from phenolic varnishes, cresol varnishes, or phenolic resins containing a dicyclopentadiene structure, etc. Other examples of cyanate compounds have been described, for example, in U.S. Patent Nos. 3,595,900; 4,894,414, and 4,785,034, the contents of which are incorporated herein by reference. In some embodiments, two or more cyanate compounds may be used in the dielectric film forming compositions described herein.

[0037] In some embodiments, the cyanate ester curing catalyst may be selected from the group consisting of metal carboxylates and metal acetylacetonates. The metal in the metal carboxylates and metal acetylacetonates may 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 zirconium 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; imidazole compounds such as 2-methylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 2-phenyl-4,5-dihydroxymethylimidazolium, and 2-phenyl-4-methyl-5-hydroxymethylimidazolium; amine compounds such as dicyandiamide, benzyl dimethylamine, and 4-methyl-N,N-dimethylbenzylamine; phosphorus compounds such as phosphine compounds and phosphonium compounds; epoxy-imidazolium adduct compounds; and peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, bis-tert-butyl peroxide, diisopropyl peroxide, and bis-2-ethylhexyl peroxide. 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 KogyoCo., Ltd.). One or more of these catalysts can be used in the compositions described herein. Other examples of such catalysts have been described, for example, in U.S. Patent Application No. 2018 / 0105488 and U.S. Patent No. 9,822,226, the contents of which are incorporated herein by reference.

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

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

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

[0041] Examples of compounds containing at least two cyclic olefin groups include, but are not limited to, dicyclopentadiene, norbornene, etc. Examples of compounds containing two olefin groups include divinylbenzene, ethylene norbornene, etc. In some embodiments, compounds containing at least two (meth)acrylate groups include unsubstituted or substituted straight-chain, branched, or cyclic C1-C... 10 Di(meth)acrylates with alkyl groups, and di(meth)acrylates with unsubstituted or substituted aromatic groups. Examples of such compounds include, but are not limited to, 1,3-butanediol 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, cyclohexanediethanol di(meth)acrylate, tricyclodecanediethanol di(meth)acrylate, 1,4-phenylene di(meth)acrylate, 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane, tricyclodecanediethanol di(meth)acrylate, and trimethylolpropane ethoxylated tri(meth)acrylate. Other examples of crosslinking agents have been described, for example, in U.S. Patent Nos. 10,036,952; 10,563,014 and U.S. Application Publication No. 2015219990, the contents of which are incorporated herein by reference. In some embodiments, two or more crosslinking agents may be used together in the dielectric film forming compositions described herein.

[0042] In some embodiments, at least one crosslinking agent may be present in an amount from at least about 1% by weight (e.g., at least about 2%, at least about 3%, at least about 4%, or at least about 5% by weight) to at most about 25% by weight (e.g., at most about 20%, at most about 15%, at most about 10%, or at most about 8% by weight) of the total weight of the dielectric film forming composition described herein. It is not intended to be limited by theory, but it is believed that the crosslinking agent can cause crosslinking in the dielectric film (e.g., upon exposure to radiation or heat), which contributes to the formation of a solubility contrast before and after exposure. Furthermore, it is not intended to be limited by theory, but it is believed that dielectric film forming compositions containing a relatively large amount of crosslinking agent can produce dielectric films with 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) catalyst (e.g., an initiator). When exposed to a source of heat (thermal initiator) and / or radiation (photoinitiator), the catalyst is capable of inducing a crosslinking or polymerization reaction. Specific examples of thermal initiators include, but are not limited to, benzoyl peroxide, dicumyl peroxide, 2,2-azobis(2-methylbutyronitrile), etc. Other examples of thermal initiators have been described, for example, in U.S. Patent No. 10,563,014, the contents of which are incorporated herein by reference. Specific examples of photoinitiators include, but are not limited to, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone (Irgacure OXE-01 from BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetophenone-1-(O-acetyl oxime) (Irgacure OXE-2 from BASF), ethoxy(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Lucerin TPO-L from BASF), NCI-831 (ADEKA Corp.), NCI-930 (ADEKA Corp.), N-1919 (ADEKA Corp.), etc. Other examples of photoinitiators have been described, for example, in U.S. Patent Nos. 10,036,952 and 10,563,014 and U.S. Patent Application Nos. 2015 / 0219990 and 2019 / 0018321, the contents of which are incorporated herein by reference.

[0044] In some embodiments, the amount of catalyst is at least about 0.2% by weight (e.g., at least about 0.5% by weight, at least about 0.8% by weight, at least about 1.0% by weight, or at least about 1.5% by weight) and / or at most about 3.0% by weight (e.g., at most about 2.8% by weight, at most about 2.6% by weight, at most about 2.4% by weight, or at most about 2.0% by weight) 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 include 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, butenyl carbonate, and glyceryl carbonate; lactones such as γ-butyrolactone, ε-caprolactone, γ-caprolactone, and δ-valerolactone; cyclic ketones such as cyclopentanone and cyclohexanone; straight-chain 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 tetrahydronaphthalene; and pyrrolidones such as N-methyl-2-pyrrolidone.

[0047] In some embodiments, the amount of solvent is at least about 40% by weight (e.g., at least about 45% by weight, at least about 50% by weight, at least about 55% by weight, at least about 60% by weight, or at least about 65% by weight) and / or at most about 98% by weight (e.g., at most about 95% by weight, at most about 90% by weight, at most about 85% by weight, at most about 80% by weight, or at most about 75% by weight) 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 comprise at least one (e.g., two, three, or four) adhesion promoter (e.g., a silane containing an alkoxy group). 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, the contents of which are incorporated herein by reference.

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

[0050] In some embodiments, this disclosure describes a photosensitizing composition comprising: a. At least one polyphenylene ether resin containing methyl (acrylate), b. At least one fully imidized polyimide polymer; c. At least one second resin described herein; d. At least one crosslinking agent; e. At least one catalyst; f. at least one adhesive aid of choice; and g. At least one solvent of your choice.

[0051] In some embodiments, this disclosure is characterized by a dielectric film (e.g., a cross-linked dielectric film) comprising (a) at least one methyl (acrylate) 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 may be prepared by a method comprising: a) coating the 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., from about 50°C to about 150°C) for a period of time (e.g., from about 20 seconds to about 240 seconds); and c) optionally exposing the film to radiation, heat, or a combination of both (e.g., full-sheet exposure without a mask, such as a patterned mask). In some embodiments, the dielectric film prepared by the above methods (which may be used with extensive exposure without a mask) may be crosslinked, but does not include patterned or embossed images.

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

[0054] The thickness of the dielectric film disclosed herein is not particularly limited. In some embodiments, the dielectric film has a thickness of at least about 1 micrometer (e.g., at least about 2 micrometers, at least about 3 micrometers, at least about 4 micrometers, at least about 5 micrometers, at least about 7 micrometers, at least about 10 micrometers, at least about 15 micrometers, at least about 20 micrometers, at least about 25 micrometers, at least 50 micrometers, or at least 100 micrometers) and / or at most about 5000 micrometers (5 mm) (e.g., at most about 4000 micrometers, at most about 3000 micrometers, at most about 2000 micrometers, at most about 1000 micrometers, at most about 500 micrometers, at most about 400 micrometers, at most about 300 micrometers, or at most 200 micrometers).

[0055] In some embodiments, the dielectric film forming composition of this disclosure is photo-patternable. In such embodiments, a method of preparing a patterned dielectric film includes converting a dielectric film prepared from the dielectric film forming composition into a patterned dielectric film using a photolithography process. In this case, the conversion may include exposing the dielectric film to high-energy radiation (such as electron beams, ultraviolet light, and X-rays) using a patterned mask.

[0056] After exposure, the dielectric film can selectively remain at at least about 50°C. o C (for example, at least about 55) o C. At least approximately 60 o C or at least about 65 o C) Up to approximately 100 o C (for example, at most about 95) o C or at most about 90 o C. At most about 85 o C. At most about 80 o C. At most about 75 o C or at most about 70 o A heat treatment at a temperature of (C) lasting from at least about 60 seconds (e.g., at least about 80 seconds or at least about 100 seconds) to at most about 240 seconds (e.g., at most about 180 seconds, at most about 120 seconds or at most about 90 seconds). The heat treatment is typically performed using a hot plate or an oven.

[0057] After exposure and / or heat treatment, a developer can be used to develop the dielectric film, removing unexposed portions to form openings or embossed images on the substrate. Development can be performed by, for example, immersion or spraying methods. After development, micropores and fine lines can be formed 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, but are not limited to, cyclohexanone, xylene, toluene, tetrahydronaphthalene, γ-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, etc. Tetrahydronaphthalene, isophorone, ethylene glycol monobutyl ether, diethylene 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-didehydrosorbitan, isosorbitol dimethyl ether, 1,4:3,6-didehydrosorbitan, 2,5-diethyl ether (2,5-diethylisosorbitol), and mixtures thereof. Preferred developers are cyclohexanone, xylene, toluene, and tetrahydronaphthalene. These developers can be used alone or in combination of two or more to optimize image quality for specific compositions and photolithography processes.

[0059] In some embodiments, the dielectric film described herein cannot be optically patterned. In such cases, patterning can be accomplished by mechanical laser drilling or by a two-layer process. Laser drilling generally involves a fixed laser beam that uses its high power density to melt or evaporate material from a target substrate or workpiece. In principle, laser drilling is subject to the energy balance between the irradiation energy of the laser beam and the conductive heat entering the substrate, the energy lost to the environment, and the energy required for phase transitions in the workpiece. Examples of mechanical laser drilling are described in U.S. Patent No. 6,353,999, the contents of which are incorporated herein by reference.

[0060] In some embodiments, the dielectric film described herein may have a relatively low loss factor (Df). For example, when measured after curing at 5-50 GHz, the dielectric film described herein may have a Df of up to about 0.01 (e.g., up to about 0.008, up to about 0.006, up to about 0.005, up to about 0.004, up to about 0.002, or up to about 0.001) and at least about 0.0001. The dielectric constant (Dk) and loss factor (Df) are measured using a discrete cylindrical resonator at a variable frequency from 1 GHz to 75 GHz, according to the method well known to those skilled in the art, IPC TM-650 2.5.5.13.

[0061] In some embodiments, this disclosure features a method for preparing a dry film. In some embodiments, the method includes a) coating a carrier substrate with the dielectric film forming composition described herein to form a coated composition; b) drying the coated 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 an optional protective layer.

[0062] In some embodiments, the carrier substrate is a single-layer or multi-layer plastic film, which may include one or more polymers (e.g., polyethylene terephthalate). In some embodiments, the carrier substrate has excellent optical transparency and is substantially transparent to photochemical radiation used to form an embossed pattern in the polymer layer. The thickness of the carrier substrate is preferably in the range of at least about 10 micrometers (e.g., at least about 15 micrometers, at least about 20 micrometers, at least about 30 micrometers, at least about 40 micrometers, at least about 50 micrometers, or at least about 60 micrometers) to at most about 150 micrometers (e.g., at most about 140 micrometers, at most about 120 micrometers, at most about 100 micrometers, at most about 90 micrometers, at most about 80 micrometers, or at most about 70 micrometers).

[0063] In some embodiments, the protective layer is a single-layer or multi-layer film, which may include one or more polymers (e.g., polyethylene or polypropylene). Examples of carrier substrates and protective layers have been described, for example, in U.S. Application Publication No. 2016 / 0313642, the contents of which are incorporated herein by reference.

[0064] In some embodiments, the dielectric film of the dry film may be delaminated from the carrier layer to form a self-supporting dry film. A self-supporting dry film is a film that maintains its physical integrity without the use of any support layer (such as a carrier layer). In some embodiments, the self-supporting dielectric dry film is uncrosslinked or uncured and may include components other than the solvent of the dielectric film forming composition described herein.

[0065] In some embodiments, the dielectric film prepared by the dielectric film forming composition 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 by the dielectric film forming composition of this disclosure, measured at 10 GHz, may be in the range of at least about 0.001 (e.g., at least about 0.005, at least about 0.01, or at least about 0.05) to at most about 0.1 (e.g., at most about 0.08, at most about 0.06, at most about 0.05, at most about 0.04, or at most about 0.020).

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

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

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

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

[0070] The dielectric film forming composition 1 prepared above was applied onto a 35-micron-thick PET substrate using an applicator to form a dielectric film. The film was then heated to 95°C using a hot plate. o Baking at C for 10 minutes removes most of the solvent. The film is then baked in nitrogen at 150°C for 1 hour to obtain a stable dielectric film with a thickness of 120 micrometers. The dielectric film is peeled off from the PET film and placed on a 25-micrometer KAPTON film, followed by baking in nitrogen at 200°C. o Bake at C for an additional hour.

[0071] After cooling to room temperature, the dielectric film was removed from the KAPTON film and cut into 3 mm wide films. The thermomechanical properties of the films were analyzed using a TMA450 (available from TA Instruments, USA) via thermomechanical analysis (“TMA”). o C to 120 o The CTE (coefficient of linear thermal expansion) measured in the temperature range of C is 100 ppm / K.

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

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

[0074] Dielectric film forming composition 2 is applied onto a 35-micron-thick PET film using an applicator to form a dielectric film. The film is then heated at 105°C using a hot plate. o Baking at C for 7 minutes removes most of the solvent. The film is then baked in nitrogen at 160°C for 185 minutes to obtain a stable dielectric film with a thickness of 90 micrometers. The dielectric film is peeled off from the PET film and placed on a 25-micrometer KAPTON film, followed by baking in nitrogen at 210°C. o Bake at C for an additional hour.

[0075] After cooling to room temperature, the dielectric film was removed from the KAPTON film and cut into 3 mm wide films. The thermomechanical properties of the films were analyzed by TMA. o C to 120 o The CTE (coefficient of linear thermal expansion) measured in the temperature range of C is 60 ppm / K.

[0076] Synthesis Example 1 (P-1) Preparation of 6FDA / DAPI polyimide Polymer (Poly-1) At room temperature, solid 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) (3.34 kg, 7.52 mol) was added to a solution of 4,4'-[1,4-phenylene-bis(1-methylethylene)]bisphenylamine (DAPI) (2.18 kg, 8.19 mol) prepared in NMP (22.06 kg). The dianhydride was flushed into the solution with additional NMP (8.16 kg). The reaction temperature was increased to 60 °C. o C, and allow the mixture to react for 3.5 hours. Then, acetic anhydride (1.257 kg) and pyridine (495 g) are added, and the reaction temperature is increased to 100 °C. o C, and allow the mixture to react for 12 hours.

[0077] Allow the reaction mixture to cool to room temperature and transfer it to a larger container equipped with a mechanical stirrer. Dilute the reaction solution with ethyl acetate as a purification solvent and wash with water for one hour. Stop stirring and allow the mixture to stand. Once phase separation has occurred, remove the aqueous phase. Dilute the organic phase with a combination of cyclopentanone and toluene as a purification solvent and wash three more times with water. The amounts of purification solvent (i.e., cyclopentanone and toluene) and water used in all washes are shown in Table 1.

[0078] Table 1 The washed organic phase was concentrated by vacuum distillation. Cyclopentanone (7.1 kg) was added as an isolation solvent, and vacuum distillation continued to form a polymer solution (P-1). The polymer Poly-1 had a molecular weight of 53,500 Daltons, and the solids content in the solution (P-1) was 31.85%. In this example, the molar ratio of dianhydride to diamine was 0.92.

[0079] Example 3: Preparation and application of photosensitive dielectric film forming composition The photosensitive dielectric film forming composition 3 was prepared using more than 89.7 g of a polymer solution (P-1), 8.00 g of cyclopentanone, 2.04 g of a 0.5 wt% solution of cyclopentanone in PolyFox 6320 (available from OMNOVA Solutions), 1.92 g of methacryloyloxypropyltrimethoxysilane, 1.92 g of 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetone (obtained from BASF's OXE-02), 0.077 g of p-benzoquinone, 15.840 g of tetraethylene glycol diacrylate, and 5.280 g of SA 9000. After mechanical stirring for 24 hours, the solution was filtered through a 0.2-micron PTFE filter to form the photosensitive dielectric film forming composition 3.

[0080] In this embodiment, the polyimide solution (P-1) is used as a fully cyclized polyimide, SA9000 is used as a low-Df polyphenylene ether resin containing methacrylate, tetraethylene glycol diacrylate is used as a crosslinking agent, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetone is used as a photoinitiator, methacryloyloxypropyltrimethoxysilane is used as a tackifier, and cyclopentanone is used as a solvent.

[0081] The photosensitive dielectric film forming composition 3 was applied onto a 35-micron-thick PET film using an applicator to form a dielectric film. The film was then heated to 95°C using a hot plate. o Baking at C for 7 minutes removes most of the solvent. The film is then baked in nitrogen at 160°C for 185 minutes to obtain a stable dielectric film with a thickness of 70 micrometers. The dielectric film is peeled off from the PET film and placed on a 25-micrometer KAPTON film, followed by baking in nitrogen at 200°C. o Bake at C for an additional hour.

[0082] After cooling to room temperature, the dielectric film was removed from the KAPTON film and cut into 3 mm wide films. The thermomechanical properties of the films were analyzed by TMA. o C to 120 o The CTE (coefficient of linear thermal expansion) measured in the temperature range of C is 65 ppm / K.

[0083] Table 2 summarizes the dielectric constant (Dk) and loss factor (Df) of the composition of Example 3.

[0084] Table 2. Other aspects, embodiments, and features are within the scope of the following claims.

Claims

1. A dielectric film forming composition comprising: (a) at least one polyphenylene ether resin containing methyl (acrylate), 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 cyclic polydiene resin and at least one cyanate ester compound.

2. The composition of claim 1, wherein the at least one methyl (acrylate)-containing polyphenylene ether resin comprises a polyphenylene ether resin having at least one methyl (acrylate) group as an end group.

3. The composition of claim 2, wherein the at least one methyl (acrylate)-containing polyphenylene ether resin comprises a polymer of structure (I): (I)， in n1 and n2 are each independent integers from 0 to 20; X is -C(O)-, -S(O)-, -S(O)2- or -C(RR')-, where R and R' are each independently H or C1-C6 alkyl; Each R 1 Independently, it is an aliphatic hydrocarbon group having 1 to 6 carbon atoms; and Each R 2 It can be independently H, a halogen group, or an aliphatic hydrocarbon group having 1 to 6 carbon atoms.

4. The composition of claim 2, wherein the at least one methyl (acrylate)-containing polyphenylene ether resin comprises a polymer of structure (II): (II), Where m and n are each an independent integer from 0 to 20, and Y is -C(O)-, -S(O)-, -S(O)2- or -C(RR')-, where R and R' are each an independent H or C1-C6 alkyl group.

5. The composition according to any one of claims 1 to 4, wherein the at least one methyl (acrylate)-containing polyphenylene ether resin accounts for about 5 wt% to about 50 wt% of the composition.

6. The composition according to any one of claims 1 to 5, wherein the at least one second resin accounts for about 50 wt% to about 90 wt% of the composition.

7. The composition according to any one of claims 1 to 6 further comprises at least one crosslinking agent, at least one catalyst, at least one adhesive aid, and at least one solvent.

8. A method for preparing a dielectric film, comprising: a) Applying the dielectric film forming composition as described in any one of claims 1 to 7 onto a substrate to form a film; and b) Selectively place the membrane at approximately 50 o C to approximately 150 o Bake at a temperature of C for approximately 20 to 240 seconds.

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

10. A method for preparing a dry film, comprising: a) Coating a carrier substrate with the dielectric film forming composition as described in any one of claims 1 to 7 to form the coated composition; b) Dry the coated composition to form a dielectric film; and c) Apply a protective layer to the dielectric film at any location.

11. The dielectric film of claims 1 to 10, wherein the dielectric film has a loss factor (Df) of up to about 0.01 at 5 GHz after curing by exposing the film to radiation, heat or a combination thereof without a mask.

12. A photosensitive dielectric film forming composition, comprising: (a) at least one polyphenylene ether resin containing methyl (acrylate), 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 cyclic 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.

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