Composition comprising organic polymer and functionalized terpenes and methods of wet etching

Abstract

A composition is described comprising an organic polymer; and at least 0.25 wt.% of a compound comprising a terpene moiety comprising at least 8 carbon atoms and a functional group selected from amine, anhydride, imide or carboxylic acid. Also described are articles, methods, and functionalized terpene compounds.

Description

[0001] COMPOSITION COMPRISING ORGANIC POLYMER AND FUNCTIONALIZED TERPENES AND METHODS OF WET ETCHING

[0002] Summary

[0003] In one embodiment, a composition is described comprising an organic polymer; and at least 0.25 wt.% of a compound comprising a terpene moiety comprising at least 8 carbon atoms and a functional group selected from amine, anhydride, imide or carboxylic acid. The organic polymer typically has a Tg of at least 50°C. In some embodiments, the organic polymer is a thermoset such as a polyimide comprising maleimide moieties or polymerized cyclic olefin (e.g., norbornene) polymer. In other embodiments, the organic polymer is a cured thermoset (e.g., epoxy) resin.

[0004] Also described is an article or component thereof comprising at least one conductive metallic substrate or metallic layer comprising a cured composition as described herein. The cured composition may be a coating or an adhesive. In some embodiments, the adhesive bonds a conductive metallic substrate or metallic layer to an insulating resin layer. The conductive metallic substrate(s) may comprise (e.g. smooth) copper including copper traces.

[0005] Also described is a method of wet-etching comprising: providing an article comprising: i) a conductive metallic substrate; ii) an insulating resin layer; and iii) a cured adhesive layer, as described herein, disposed between the conductive metallic substrate and insulating resin layer. The method further comprises contacting the article with at least one liquid, wherein the liquid comprises an organic solvent, an alkaline solution, or an acidic solution. In some embodiments, the liquid comprises a (e.g., permanganate) oxidizer.

[0006] Also described is a functionalized terpene compound comprising the reaction product of:

[0007] a cyclic terpene moiety wherein a carbon atom of the ring comprises a pendent =CH2group; and a compound comprising a thiol group and an amine group. The functionalized terpene may have the formula:

[0008] Cyc-CH2-S-R-NR2R3

[0009] wherein Cyc is a cyclic terpene moiety;

[0010] R is a C1-C24 hydrocarbon group; and

[0011] R2and R3are independently hydrogen or a C1-C4 alkyl group.

[0012] In one embodiment, the functionalized terpene has the formula:

[0013]

[0014] R is a C1-C24 hydrocarbon group.

[0015] Brief Description of the Drawings

[0016] Fig. 1 is a cross-section of a two-layer article;

[0017] Fig. 2 is a cross-section of a three-layer article; and

[0018] Fig. 3 is a cross-section of a portion of an integrated chip 300.

[0019] Detailed Description of the Drawings

[0020] Organic Polymer

[0021] The (e.g., adhesive or coating) composition comprises an organic polymer. In some embodiments, the organic polymer is a thermoset that can permanently harden into a solid state during (e.g., thermal) curing. In other embodiments, the organic polymer is a thermoset resin that has been (e.g., thermally) cured. Common thermoset materials include melamine, polyester resin, urea-formaldehyde, vinyl ester resin, epoxy resin, polyimide, phenolic resins, polymers prepared from cyclic dienes (e.g., polynorbornene). Such organic polymers typically have a glass transition temperature (Tg) of at least 50°C prior to curing. Both thermoset organic polymers and cured thermoset resins typically have a Tg significantly greater than 50°C after curing. Prior to curing, the Tg of an organic polymer can be determined by Dynamic Mechanical Analysis or Differential Scanning Calorimetry. After curing, such materials are highly crosslinked such that the resulting organic polymers typically do not exhibit a thermal transition (Tg or Tm) prior to the decomposition temperature of the organic polymer.

[0022] In some embodiments, the organic polymer is a polyimide that comprises maleimide moieties. Polyimides comprise imide groups, -O=C-N-C=O-, in the polymer backbone. The maleimide moieties have the following formula.

[0023]

[0024] The polyimide may be described as a maleimide terminated polyimide. Such a polyimide may have the following formula:

[0025]

[0026] wherein R1is hydrogen or methyl; and

[0027] Q and R are independently organic linking groups.

[0028] Q and R are typically independently an aliphatic, cycloaliphatic, alkenyl, aromatic, or heteroaromatic group. Such a group may be substituted or unsubstituted.

[0029] In some embodiments, Q is a (e.g., a tetravalent) aromatic group.

[0030] The maleimide terminated polyimides are derived from the reaction of a diamine with an acid dianhydride. The R group is typically the reaction product of one or more diamines.

[0031] Suitable diamines include for example 4,4'-methylenebis(2,6-diethylaniline); tricyclodecane diamine (TCD-diamine); bisaniline-P; 2.2-bis [4-( 4-aminophenoxy )phenyl] hexafluoropropane; 1,10-diaminodecane; 1,12-diaminododecane; dimer diamine; hydrogenated dimer diamine; l,2-diamino-2-methylpropane; 1,2-diaminocyclohexane; 1,2-diaminopropane; 1,3 -diaminopropane; 1,4-diaminobutane; 1,5-diaminopentane; l,7-diaminoheptane;l,8-diaminomenthane; 1,8-diaminooctane; 1,9-diamino nonane; 3,3' -diamino-N-methyldipropyl amine; diaminomaleonitrile; 1,3-diaminopentane; 9, 10-diaminophenanthrene; 4,4'-diaminooctafluorobiphenyl; 3, 5 -diaminobenzoic acid; 3, 7 -diamino -2-methoxyfluorene; 4,4'-diaminobenzophenone; 3, 4 -diaminobenzophenone; 3,4-diaminotoluene; 2,6-diaminoanthroquinone; 2,6-diaminotoluene; 2,3-diaminotoluene; 1,8-diaminonaphthalene; 2,4-diaminotoluene; 2,5-diaminotoluene; 1,4-diaminoanthroquinone; 1,5-diaminoanthroquinone; 1,5-diaminonaphthalene; 1,2-diaminoanthroquinone; 2,4-cumenediamine; 1,3 -bisaminomethyl benzene; 1,3-bisaminomethylcyclohexane; 2 -chloro- 1,4-diamino benzene; l,4-diamino-2,5-dichloro benzene; 1, 4-diamino-2, 5-dimethyl benzene; 4, 4'-diamino-2,2'-bistrifluoromethyl biphenyl; bis( amino-3-chlorophenyl)ethane; bis( 4-amino-3,5-dimethylphenyl)methane; bis( 4-amino-3,5-diisopropylphenyl)methane; bis( 4-amino-3,5-methyl-isopropylphenyl) methane; bis( 4-amino-3,5-diethylphenyl)methane; bis( 4-amino-3 -ethyl phenyl)methane; diaminofluorene; 4,4' -(9-fluorenylidene) dianiline; diaminobenzoic acid; 2,3-diaminonaphthalene; 2,3 -diaminophenol; -5-methylphenyl)methane; bis( 4-amino-3-methylphenyl)methane; bis( 4-amino-3-ethylphenyl)methane; 4,4' -diaminopheny Isulfone; 3,3 ' -diaminophenyl sulfone; 2,2-bis( 4,-( 4-aminophenoxy )phenyl)sulfone; 2,2-bis( 4-(3-aminophenoxy)phenyl)sulfone; 4,4'-oxydianiline; 4,4'-diaminodiphenyl sulfide; 3, 4'-oxy dianiline; 2,2-bis( 4-(4-aminophenoxy)phenyl)propane; l,3-bis(4-aminophenoxy )benzene; 4,4'-bis( 4-aminophenoxy)bipheny 1; 4, 4'-diamino-3, 3 '-dihydroxybiphenyl; 4, 4'-diamino-3, 3 '-dimethylbiphenyl; 4,4' -diamino-3,3 '-dimethoxy biphenyl; bisaniline M; bisaniline P; 9,9-bis( 4-aminophenyl)fluorene; o-tolidine sulfone; methylene bis(anthranilic acid); 1,3 -bis( 4-aminophenoxy)-2,2-dimethylpropane; 1,3- bis(4-aminophenoxy propane; l,4-bis( -aminophenoxy )butane; l,5-bis(4-aminophenoxy)butane; 2, 3,5,6-tetramethyl-l,4-phenylenediamine; 3,3', 5,5'-tetramehylbenzidine; 4,4'-diaminobenzanilide; 2,2-bis(4-aminophenyl)hexafluoropropane; polyoxyalkylenediamines; l,3-cyclohexanebis(methy 1 amine); mxylylenediamine; p-xylylenediamine; bis( 4-amino-3-methylcyclohexyl)methane; l,2-bis(2-aminoethoxy)ethane; and 3(4),8(9)-bis(aminomethyl)tricyclo(5.2.1.02,6)decane.

[0032] In some embodiments, the diamine is 4,4'-methylenebis(2,6-diethylaniline); bisaniline-P; tricyclodecane diamine (TCD-diamine); 2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane; a fatty (e.g., dimer) diamine such as PRI AMINE™ 1075 or PRIAMINE™ 1074; or a combination thereof.

[0033] In some embodiments, combinations of diamines are utilized. Thus, the polyimide comprises reactions products of at least two different amines. For example, the repeat unit may comprise the reaction product of one diamine and the endcapping group may comprise a different diamine.

[0034] Suitable anhydrides include for example bisphenol-A-dianhydride (e.g., 4,4'-(4,4 -isopropylidenediphenoxy)bis(phthalic anhydride); biphenyl tetracarboxylic dianhydride; pyromellitic dianhydride; maleic anhydride; polybutadiene-graft-maleic anhydride; polyethylene-graft-maleic anhydride; polyethylene- alt-maleic anhydride; polymaleic anhydride-alt-1 -octadecene; polypropylene-graft-maleic anhydride; poly(styrene-co-maleic anhydride); maleic anhydride; succinic anhydride; 1,2, 3, 4- cyclobutene tetracarboxylic dianhydride; 1,4,5,8-naphthalenetetracarboxylic dianhydride; 3,4,9,10- perylenentetracarboxylic dianhydride; bicyclo(2.2.2)oct-7-ene-2,3,5,6-tetracarboxylic dianhydride; diethylenetriaminepentaacetic dianhydride; ethylenediaminetetraacetic dianhydride;

[0035] 3, 3', 4, 4'- benzophenone tetracarboxylic dianhydride; 3,3',4,4'-biphenyl tetracarboxylic dianhydride; 4,4'-oxydiphthalic anhydride; 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride; 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; 4,4'-bisphenol A diphthalic anhydride; 5-(2,5-dioxytetrahydro)-3 -methyl -3 -cyclohexene-1,2-dicarboxylic anhydride; ethylene glycol bis(trimellitic anhydride); hydroquinone diphthalic anhydride; allylnadic anhydride; 2-octen-l-yl succinic anhydride; phthalic anhydride; 1,2,3,6-tetrahydrophthalic anhydride; 3,4,5,6-tetrahydrophthalic anhydride; 1,8-naphthalic anhydride; glutaric anhydride; dodecenylsuccinic anhydride; hexadecenylsuccinic anhydride; hexahydrophthalic anhydride; methylhexahydrophthalic anhydride; and tetradecenylsuccinic anhydride.

[0036] In some embodiments, the anhydride is bisphenol-A-dianhydride; biphenyl tetracarboxylic dianhydride; pyromellitic dianhydride; maleic anhydride; or a combination thereof.

[0037] In some embodiments, combinations of anhydrides are utilized. Thus, the polyimide comprises reaction products of two different anhydrides. For example, the repeat unit may comprise the reaction product of one anhydride and the endcapping group may comprise a maleic anhydride.

[0038] Maleimide terminated polyimides are commercially available. Some representative maleimide terminated polyimides are depicted in WO2021 / 113415; incorporated herein by reference.

[0039]

[0040] ' Compound 3

[0041]

[0042] Compound

[0043]

[0044] Compound 9

[0045]

[0046] Compound 12

[0047] In some embodiments, the (e.g., adhesive or coating) composition comprises a high Tg maleimide terminated polyimide such as depicted by Compounds 1 and 5-7, wherein R comprises an aromatic or cycloaliphatic group. Any one or combination of such compounds may be utilized. In some embodiments, the composition can further comprise polyphenylene ether (PPE). The glass transition temperature, Tg, of the maleimide terminated polyimides lacking a fatty diamine is typically greater than 170°C, 175°C, 180°C, 195°C, 190°C, 200°C. The Tg is typically no greater than about 210°C. However, the Tg of the composition can be increased by including other (e.g., aromatic) maleimide capped compounds having a high Tg.

[0048] In some embodiments, the (e.g., adhesive or coating) composition comprises a lower Tg maleimide terminated polyimide, such as depicted by Compounds 3 and 8-12, wherein R comprises an aliphatic moiety comprising 4-60 carbon atoms. In this embodiment, the melt temperature of the maleimide terminated polyimide and composition can be less than 100, 90 or 80°C.

[0049] The (e.g., adhesive or coating) composition typically comprises up to 5, 10, 15, 20, 25, or 30 wt.% of moieties comprising an aliphatic moiety comprising 4-60 carbon atoms. The aliphatic moiety can be saturated, as depicted in the above compounds, or may comprise ethylenic unsaturation. The aliphatic moiety may be linear or branched and may comprise a cycloaliphatic moiety. The aliphatic moiety is typically the reaction product of a fatty acid, fatty acid anhydride, or fatty diamine; including dimers thereof. The aliphatic moiety is typically divalent (e.g., derived from a dianhydride or diamine). In some embodiments, the aliphatic moiety comprises at least 6, 8, 10, 12, 14, 16, 18, 20, 24, or greater than 24 carbon atoms. In some embodiments, the aliphatic moiety comprises less than 60, 50, or 40 carbon atoms. This moiety is typically derived from utilizing a maleimide terminated poly imide, such as depicted by Compounds 3 and 8-12, wherein R comprises an aliphatic moiety comprising 4-60 carbon atoms. However, this moiety can also be derived from use of a maleimide terminated compound with such moiety and / or by use of a diamine with such moiety.

[0050] The physical properties of various maleimide terminated polyimides are reported in literature (e.g., previously cited WO2021 / 113415). The maleimide terminated polyimide typically has a molecular weight of at least 2,000; 4,000, 6,000, 8,000 or 10,000 Daltons. The molecular weight is typically no greater than 25,000 Daltons. In some embodiments, the molecular weight is no greater than 20,000; 15,000; 10,000 or 5,000 Daltons.

[0051] The glass transition temperature, Tg, of the maleimide terminated poly imides comprising fatty diamine moieties is typically less than 170°C, 160, 150, 140, 130, 120°C. The Tg is typically at least 50, 75, or 100°C. Thus, lower concentrations of such moieties is amenable to compositions with higher Tg.

[0052] The Coefficient of Thermal Expansion (CTE) of the cured film of maleimide terminated polyimides can be less than 50 or 25 ppm / °C. The Dielectric Constant (Dk) @20 GHz of the cured film of maleimide terminated polyimides can be less than 2.7, 2.6, 2.5, 2.4, 2.3 or 2.2. The Dissipation Factor (Df) @20 GHz of the cured film can be less than 0.0080, 0.0070, 0.0060, 0.0050, 0.0040, 0.0030, or 0.0020.

[0053] In some embodiments, the composition comprises maleimide terminated compounds. The compounds may have a molecular weight less than 2,000 or 1,000 Daltons. In some embodiments, such components comprise at least two maleimide end groups bonded to an aliphatic moiety comprising 4-60 carbon atoms, as described above. One representative compound, reported to have a molecular weight of 689 Da and a glass transition temperature of 20°C is depicted as follows:

[0054]

[0055] Notably the aliphatic moiety of these compounds can be saturated or partially unsaturated as described above.

[0056] Other representative compounds include:

[0057]

[0058] Other maleimide terminated polyimides are known in the literature, such as described in WO2017 / 002748; incorporated herein by reference.

[0059] When the (e.g., adhesive or coating) composition is subject to wet etching or exposed to acid or alkaline liquids or organic solvents, the maleimide terminated polyimides are preferably free of ether and / or (non-imide) carbonyl moieties.

[0060] In some embodiments, the (e.g., adhesive or coating) composition may comprise up to 5, 10, 15, 20, 25, or 30 wt.% of polyimide with maleimide moieties, such as BMI-2500, based on the total weight of the composition.

[0061] However, when the composition is not subject to methods of wet etching or exposure to such liquids, the composition may further comprise ether and / or poly ether moieties. Such poly ether moieties may be the reaction product of an amine compound, as described in W02024057206. However, the composition may comprise polyether moieties by utilizing a polyether diamine during the synthesis of the maleimide terminated polyimide. Some representative polyether maleimide compounds are as follows:

[0062]

[0063] Another representative maleimide terminated compound (with ether moieties), reported to have a Tg of 229°C is as follows

[0064]

[0065] Thus, in some embodiments, the (e.g., adhesive or coating) composition may comprise up to 5, 10, or 15 wt.% of polyether moieties, based on the total amount of organic polymer or reactive components thereof. When low Dk and Df values are desired the total amount of polyether moieties is typically no greater than 5, 4, or 3 wt.% of the composition. When the amount of polyether is too high, the Dk and Df values can increase.

[0066] In some embodiments, the (e.g., adhesive or coating) composition comprises a cyclic olefin polymer. Cyclic olefin polymers are prepared from polymerization of unsaturated cyclin olefin comprising one or more carbon-carbon double bonds. The double bonds or in other words ethylenic unsaturation may be characterized as an alkene moiety that is not part of a (meth)acrylate or vinyl ether group. In some embodiments, one of the double bonds of a cyclic diene participates in polymerization of the cyclic diene into a polymer, whereas the other double bond is amenable to thermosetting. In other embodiments, the cyclic olefin may have a pendent crosslinkable group.

[0067] Suitable cyclic dienes include for example 1,3 -cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 5-ethyl-l,3-cyclohexadiene, 1,3-cycloheptadiene, cyclohexadiene, 1,5-cyclooctadiene, 1,3 -cyclooctadiene, norbomadiene, cyclohexenylnorbomene, including oligomers thereof such as dimers, trimers, tetramers, pentamers, etc.

[0068] In some embodiments, the organic polymer of the (e.g., adhesive or coating) composition comprises polymerized units of a dicyclopentadiene (DCPD), depicted as follows:

[0069]

[0070] Various DCPD suppliers and purities may be used such as Lyondell 108 (94.6% purity), Veliscol UHP (99+% purity), Cymetech Ultrene (97% and 99% purities), and Hitachi (99+% purity).

[0071] In some embodiments, the composition comprises polymerized units of cyclopentadiene oligomers including trimers, tetramers, pentamers, and the like; depicted as follows:

[0072]

[0073] cyclopentadiene oligomers, n is typically 3, 4 or 5.

[0074] In some embodiments, the composition comprises polymerized units of a norbomene-based monomer, such as norbomadiene

[0075]

[0076] In other embodiments, the norbomene-based monomer comprise a pendent crosslinkable group, depicted as follows:

[0077]

[0078] where the pendent group R1is an alkenyl or alkylidene group. The alkenyl or alkylidene group can have 2 or more carbon atoms such as, for example, 2 to 10 carbon atoms. The number of carbon atoms can be at least 2, at least 3, or at least 4 and up to 10, up to 8, up to 6, or up to 4 carbon atoms. Examples of such norbomene-based monomers are as follows:

[0079]

[0080] The cyclic olefin monomers and oligomers may optionally comprise substituents provided the monomer, oligomer, or mixture is suitable for addition polymerization or metathesis reactions. The carbon atoms of the cyclic olefin moiety may optionally comprise substituents derived from radical fragments including halogens, pseudohalogens, alkyl, aryl, acyl, carboxyl, alkoxy, alkyl- and arylthiolate, amino, aminoalkyl, and the like, or in which one or more carbon atoms have been replaced by, for example, silicon, oxygen, sulfur, nitrogen, phosphorus, antimony, or boron. For example, the olefin may be substituted with one or more groups such as thiol, thioether, ketone, aldehyde, ester, ether, amine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, phosphate, phosphite, sulfate, sulfite, sulfonyl, carbodiimide, carboalkoxy, carbamate, halogen, or pseudohalogen. Similarly, the olefin may be substituted with one or more groups such as C1-C20 alkyl, aryl, acyl, C1-C20 alkoxide, aryloxide, C3-C20 alkyldiketonate, aryldiketonate, C1-C20 carboxylate, arylsulfonate, C1-C20 alkylsulfonate, C1-C20 alkylthio, arylthio, C1-C20 alkylsulfonyl, C1-C20 alkylsulfinyl, C-C20 alkylphosphate, and arylphosphate.

[0081] In some embodiments, the cyclic olefin polymer comprises polymerized units of a cyclic diene in the absence of mono-olefin(s). In other embodiments, the cyclic olefin polymer comprises polymerized unit of a cyclic mono-olefin in the absence of cyclic diene(s). In yet other embodiments, the cyclic olefin polymer comprises polymerized units of one or more cyclic diene(s) and one or more mono-olefin(s). Examples include cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbomene, cyclononene, cyclodecene, cycloundecene, cyclododecene, tricyclodecene, tetracyclodecene, octacyclodecene, and cycloeicosene, and substituted versions thereof such as 1 -methylcyclopentene, 1 -ethylcyclopentene, 1-isopropylcyclohexene, 1 -chloropentene, 1 -fluorocyclopentene, 4-methylcyclopentene, 4-methoxy-cyclopentene, 4-ethoxy -cyclopentene, cyclopent-3 -ene-thiol, cyclopent-3 -ene, 4-methylsulfanyl-cyclopentene, 3 -methylcyclohexene, 1 -methylcyclooctene, 1,5-dimethylcyclooctene, etc.

[0082] The cyclic olefin polymers may further comprise polymerized units of alkene comonomers including ethylene. In some embodiments, the cyclic olefin polymers comprise polymerized units of 1-alkene monomers having 6 to 18 carbon atoms such as 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, or the like. The amount of the 1-alkene can be 0, at least 5, at least 10, at least 15, at least 20, at least 25, or at least 30 and up to 60, up to 55, up to 50, up to 45, up to 40 weight percent.

[0083] Various methods of polymerizing cyclic olefins are known. For example, Group 8 transition metals, such as ruthenium and osmium, carbene compounds have been described as effective catalysts for ring opening metathesis polymerization (ROMP). See for example US 10,239,965 and WO2021 / 074749; incorporated herein by reference. Cyclic olefin can also be polymerized by addition polymerization, such as described in WO2024100476; incorporated herein by reference. Addition polymerization catalysts are known in the art and are typically based on organometallic catalysts comprising Ti, Zr, Cr, Co, Fe, Cu, Ni, Pt, or Pd. Of these, addition polymerization catalysts comprising Ni or Pd are commonly used.

[0084] In some embodiments, the polynorbornene copolymer is an (e.g., addition polymerized) reaction product of a plurality of different norbomene-based monomers. The polymerizable composition used to form the polynorbornene copolymer includes at least one norbomene-based monomer that has a pendent crosslinkable group. Other norbomene-based monomers are often further included in the polymerizable composition such as those that have a pendent hydrocarbon group such as, for example, an alkyl group. Additionally, norbomene monomers (i.e., without any pendent groups) can be included. The various monomers are polymerized in the presence of a catalyst that typically includes a Group 10 element of the periodic table of elements. In some embodiments, the polynorbornene polymer is a terpolymer of 20-70 (e.g., 45) mol% decylnorbomene, 20-70 (e.g., 45) vinylnorbomene, 0 to 20 (e.g., 10) mol% norbomene.

[0085] In some embodiments, the cyclic olefin polymer (e.g., polynorbornene copolymer) has a weight average molecular weight (Mw) in a range of 10 to 1000 kiloDaltons (kDa). The Mw is often at least 10, at least 20, at least 25, at least 50, or at least 100 kDa and can be up to 1000, up to 500, up to 200, or up to 100 kDa. The Mw can be measured by Size Exclusion Chromatography (SEC).

[0086] In some embodiments, the cyclic olefin polymer (e.g., polynorbornene copolymer) has a glass transition temperature (Tg) in a range of 80 to 280°C. The Tg can be at least 80, 100, 120, or 150°C. In some embodiments, the Tg is no greater than 280, 260, 250, 220, 200, 180, 160, or 150°C.

[0087] In some embodiments, the (e.g., adhesive or coating) composition typically comprises at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 98 wt.% of organic polymer based on the total amount of the organic polymer or reactive components thereof (i.e., excluding filler). In some embodiments, the composition comprises at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 98 wt.% of maleimide terminated polyimide wherein R comprises an aliphatic moiety comprising 4-60 carbon atoms, such as depicted by Compounds 3 and 8-12. In some embodiments, the composition comprises at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 98 wt.% of a cyclic olefin (e.g., norbornene) polymer, as previously described. In some embodiments, the amount of organic polymer is no greater than 99, 95, 90, 85, 80, 75, 70, 65, 60 or 50 wt.% based on the total amount of organic polymer or reactive components thereof (i.e., excluding filler).

[0088] Functionalized Terpene Compound

[0089] The composition further comprises a compound comprising a terpene moiety and a functional group selected from amine, anhydride, imide or carboxylic acid; also referred to herein as a functionalized terpene compound.

[0090] Terpenes are a class of hydrocarbons occurring widely in plants and animals and empirically regarded as built up from isoprene having the chemical formula:

[0091] CH2=C(CH3)CH=CH2.

[0092] Terpenes have two or more isoprene units as their common structural feature. Terpenes are classified according to the number of isoprene units they contain. Monoterpenes contain two isoprene units. Sesquiterpenes are made up of three isoprene units. Monoterpenes and sesquiterpenes can be linear or cyclic structures.

[0093] In some embodiments, the terpene moiety may be characterized as a terpenoid, i.e., a derivative of terpene. Tn some embodiments, terpenoids are terpenes that have bad unsaturated groups removed by hydrogenation. The hydrogenated terpene moiety is characterized by a pendent methyl group at the former location of the unsaturated (i.e., alkene) group. Thus, a terpene moiety may have an alkylene backbone wherein the fifth and / or tenth and / or fifteen carbon atoms comprising a pendent methyl group rather titan an unsaturated (i.e., alkene) group. In other embodiments, terpenoids are terpenes that have had oxygen-containing moieties added. For example, perillyl alcohol and its precursor limonene are

[0094]

[0095] selected from amine, anhydride, imide or carboxylic acid.

[0096]

[0097] monoterpenoids may have less than 10 carbon atoms. In some embodiments, the (e.g., monoterpene

[0098]

[0099] Various compounds comprising a terpene moiety and a functional group are commercially available. Others can be synthesized according to methods known in the art. See for example WO2013148842. Notably the synthesis of the functionalized terpene compound (i.e. terpene or terpenoid further comprising a functional group is selected from amine, anhydride, imide or carboxylic acid) or an intermediate thereof can increase the number of carbon atoms. In other words, a compound derived from a sesquiterpene terpene or terpenoid may srrve greater than i 5 carbon atoms.

[0100] In some embodiments, the functionalized terpene compound comprises the reaction product of: a cyclic terpene moiety wherein a carbon atom of the ring comprises a pendent — CH2group; and a compound comprising a thiol group and an amine group.

[0101] Suitable cyclic terpene compounds include for example (3-carophyllene, P- pinene, limonene, camphene, valencene, pimarane, nootketene, germacrene, atisene, p-cedrene, prezizaene, a-pinguisene, elemene, a-bulnesene, a-guaiene, a-selinene, p-selinene, p-humulene, and iso-pimaradiene.

[0102] Suitable compounds comprising a thiol group and an amine group include cysteamine, 3-amino-1 -propanethiol, 2-dimethylaminoethanethiol, 2-diethylaminoethanethiol, 2-butylaminoethanethiol, and leucinethiol,

[0103] The functionalized terpene may have the formula:

[0104] Cyc-CH2-S-R-NH2

[0105] wherein Cyc is a cyclic terpene moiety; and

[0106] R is a C1-C24 hydrocarbon group (e.g., alkyl, alkenyl); and

[0107] R2and R3are independently hydrogen or a C1-C4 alkyl group (e.g. methyl, ethyl, propyl, butyl).

[0108] In one embodiment, the functionalized terpene may be represented by the formula:

[0109]

[0110] R is a C1-C24 hydrocarbon group.

[0111] Other commercially available compounds that comprise terpene moieties and a functional group are depicted as follows:

[0112]

[0113]

[0114] The presence of terpene (including terpenoid) moieties can be identified using Nuclear Magnetic Resonance.

[0115] As illustrated by the forthcoming examples, adhesive and coating compositions with a compound comprising a terpene moiety and a functional group can provide good initial adhesion to conductive metallic substrates, such as copper. It is appreciated that these compounds can also react with the maleimide moieties and other optional components of the composition. Thus, the cured composition may comprise unreacted functionalized terpene compound as well as reaction products thereof. The composition also has good adhesion to insulating resin layers such an epoxy resin and silicon carbide. Further, in some embodiments the composition is resistant to wet etching and thus also provides good adhesion between the conductive metallic substrate and insulating layer during and after wet etching.

[0116] The (e.g., adhesive or coating) composition comprises a compound comprising a terpene moiety and a functional group in an amount of at least 0.25, 0.5, 1, 2, 3, 4, or 5 wt.% based on the total amount of organic polymer or reactive components thereof (e.g., polyimide with maleimide moieties). In some embodiments, the composition comprises no greater than 15 or 10 wt.% of compound(s) comprising a terpene moiety and a functional group. In some embodiments, the composition comprises less than 10, 9, 8, 7, 6, 5, 4, or 3 wt.% of compounds(s) comprising a terpene moiety and a functional group. A single compound or combinations of two or more compounds can be utilized. The combination of two or more compounds may comprise the same or different functional groups. Typically the minimum amount of compound that can provide the desired cross hatch adhesion is utilized. The preferred amount of compounds(s) comprising a terpene moiety and a functional group can vary depending on the compound(s) utilized.

[0117] In some embodiments, the functionalized terpene compound may be uniformly distributed within the adhesive or coating layer. In other embodiments, the functionalized terpene compound is concentrated at an interface with the conductive metallic substrate or an interface with the insulating resin layer, or a combination thereof.

[0118] Optional Amine and Thiol Compounds

[0119] The adhesive and coating compositions may optionally comprise amine and / or thiol compound(s). The presence of such compounds may also contribute to improving adhesion.

[0120] Amine compounds comprise at least one amine group and more typically two or more amine groups. The amine compound may comprise amine groups that include a primary amine, a secondary amine, a tertiary amine, or a combination thereof. The amine compounds are preferably aliphatic since aromatic amines can increase the Dk. In some embodiments, the amine compound comprises at least 3, 4, 5, or 6 amine groups. In some embodiments, the amine compound comprises no greater than 6, 5, 4, 3, or 2 amine groups.

[0121] Thiol compounds comprise at least one thiol group and more typically two or more thiol groups. The thiol compound is also preferably aliphatic. In some embodiments, the thiol compound comprises at least 3, 4, 5, or 6 thiol groups. In some embodiments, the thiol compound comprises no greater than 6, 5, 4, 3, or 2 thiol groups.

[0122] The amine and / or thiol compound / s) is preferably aliphatic, lacking an aromatic moiety. The amine and / or thiol compound(s) typically comprises an aliphatic (e.g., hydrocarbon) moiety comprising 4-60 carbon atoms. The aliphatic (e.g., hydrocarbon) moiety of the amine and / or thiol compounds(s) can be alkyl, alkylene, alkene, alkyne, or combinations thereof. In some embodiments, the hydrocarbon moiety comprises at least 6 or 8 carbon atoms. In some embodiments, the hydrocarbon moiety comprises no greater than 50, 40, 30, or 24 carbon atoms. In some embodiments, the hydrocarbon moiety comprises no greater than 22, 20, 18, 16, 14, or 12 carbon atoms. The aliphatic (e.g., hydrocarbon) moiety of the amine and / or thiol compounds(s)may be straight-chained, branched, and may comprise cycloaliphatic groups. In some embodiments, the compound comprises a single aliphatic moiety (e.g., hydrocarbon chain). In other embodiments, the compound comprises at least two, three, or four aliphatic moieties (e.g., hydrocarbon chains).

[0123] The amine and / or thiol compound(s) comprise at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 75, 80, 85, or 90 wt.% methylene (CH2) and / or methine (CH). In some embodiments, the amine and / or thiol compound(s) comprise no greater than 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 30, 25 wt.% methylene (CH2) and / or methine (CH). Various compounds can be defined by a range formed by a minimum and maximum wt.% methylene (CH2) and / or methine (CH), as just described. Examples of amines comprising more than one aliphatic moieties (e.g., hydrocarbon chains) include fatty diamines such as PRIAMINE™ 1071, PRIAMINE™ 1075 or PRIAMINE™ 1074. The structure of the fatty dimer diamine is as follows:

[0124]

[0125] PRIAMINE™ 1074 comprises 99% dimer diamine. PRIAMINE™ 1075 comprises greater than 99% dimer diamine. Notably, such fatty dimer diamines are highly compatible with polyimide resin comprising maleimide moieties prepared from these same diamines.

[0126] In some embodiments, the (e.g., adhesive or coating) composition (e.g., suitable for wet etching) comprises the fatty diamine compound, as just described. In other embodiments, the composition utilizes other amine and / or thiol compounds and thus lacks the fatty diamine just described. In yet other embodiments, the composition may comprise a combination of compounds wherein a first compound comprises the fatty diamine, as just described and the second compound is a different amine and / or thiol compound as described herein.

[0127] In some embodiments, the amine compound comprises a cycloaliphatic moiety. Representative amine compounds include, for example, 4,4'-methylenebiscyclohexylamine, isophorone diamine, and the PRIAMINE fatty diamines just described.

[0128] In some embodiments, the amine an / or thiol compound comprises a hydrocarbon moiety wherein carbon atoms of the hydrocarbon moiety are substituted with sulfur or -NH. Representative compounds include, for example, N-3-trimethoxysilylpropyldiethylene triamine and 2,3-bis-2-mercaptoethylthio-l-propanethiol.

[0129] In some embodiments, the amine and / or thiol compound comprises at least one amine or thiol group and at least one terminal alkoxy silane group. Such a compound typically comprises a hydrocarbon moiety with at least 4, 5, 6, 7, or 8 carbon atoms. The at least one amine or thiol group can react with the polyimide (e.g., maleimide moieties). The alkoxy silane group can form a covalent bond with siliceous (e.g., filler) components of the composition or insulating layer. Representative compounds of this type include, for example, trimethoxysilyloctyldiamine, aminobutyltriethoxysilane, aminoundecyltriethoxysilane, N-3-trimethoxy-silylpropyldiethylene triamine, 3-mercaptopropyltrimethoxy silane and 3 -mercaptooctyltrimethoxy silane

[0130] Although poly ether amine compounds, such as described in W02024057206 can improve adhesion to metallic substrates, such as copper, it has been found that such compounds are not resistant to wet etching. Thus, when the composition, electronic article or component thereof is subject to wet etching or exposure to organic solvent, acids, or bases; the functionalized terpene compound and optional amine and / or thiol compound lacks oxygen substituents, such as ether, other carbonyl that is not an imide (e.g., ester), and hydroxyl moieties. The (e.g., adhesive or coating) composition may optionally comprise other amine and / or thiol (e.g., adhesion promoting) compounds(s) in an amount of at least 0.25, 0.5, 1, 2, 3, 4, or 5 wt.% based on the total amount of organic polymer. In some embodiments, the composition comprises no greater than 5, 4, 3, 2, 1 or 0.5 wt.% of amine and / or thiol compound(s). A single compound or combinations of two or more compounds can be utilized. Such combinations can include two or more amine compounds, two or more thiol compounds, or at least one amine compound and at least one thiol compound. Typically the minimum amount of compound that can provide the desired cross hatch adhesion is utilized. The preferred amount of amine and / or thiol compounds(s) can vary depending on the compound(s) utilized.

[0131] Additional Components

[0132] The (e.g., adhesive or coating) composition may further comprise other components including for example a thermal initiator, an oligomer (e.g., polyimide oligomer), inorganic filler, epoxy resin, reactive diluent, oxidizing agent, and combinations thereof.

[0133] The (e.g., adhesive or coating) composition is typically a one-part composition comprising all the requisite and optional components combined with each other. However, it is also contemplated that some of the components may be added immediately prior to use. For example, the composition may have a longer shelf life when the amine compound and / or thermal initiator are added immediately prior to use. It is also contemplated that the composition is a two-part composition wherein the combination of first and second part comprises all the requisite and optional components. For example, the first part may be applied to the conductive metallic substrate and the second part applied to the insulating resin layer. In these embodiments, the first and second part are combined during manufacture of the article.

[0134] The (e.g., adhesive or coating) composition typically comprises a thermal free radical initiator such as an organoperoxide. Representative compounds include dialkyl peroxides and dicumyl peroxide available under the trade designation LUPEROX from Arkema.

[0135] Suitable thermal radical initiators include various azo compounds such as those commercially available under the trade designation VAZO from Chemours Co. (Wilmington, DE, USA) including VAZO 67, which is 2,2 ’-azobis(2 -methylbutane nitrile), VAZO 64, which is 2,2’-azobis(isobutyronitrile), VAZO 52, which is (2,2’-azobis(2,4-dimethylpentanenitrile), and VAZO 88, which is 1,1’-azobis(cyclohexanecarbonitrile); various peroxides such as benzoyl peroxide, cyclohexane peroxide, lauroyl peroxide, di-tert-amyl peroxide, tert-butyl peroxy benzoate, di-cumyl peroxide, and peroxides commercially available from Atofina Chemical, Inc. (Philadelphia, PA, USA) under the trade designation LUPERSOL (e.g., LUPERSOL 101, which is 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, and LUPERSOL 130, which is 2,5-dimethyl-2,5-di-(tert-butylperoxy)-3-hexyne); various hydroperoxides such as tert-amyl hydroperoxide, tert-butyl hydroperoxide, and cumene hydroperoxide; and mixtures thereof.

[0136] In typical embodiments, the (e.g., adhesive or coating) composition may lack triazine compound curatives. In this embodiment, a bismaleimide-triazine (BT) resin is not formed. The (e.g., adhesive or coating) composition may optionally comprise an epoxy resin. Various aromatic and aliphatic epoxy resins are known in the art. In some embodiments, composition comprises and epoxy resin in combination with a polyimide. The amount of epoxy resin may be less than the amount of polyimide. Thus, the epoxy resin can be present in an amount less than 50, 40, 30 wt.% of the sum of the polyimide and epoxy. In some embodiments, the composition comprises less than 25, 15, 10, 5, 4, 3, 2, 1, 0.5, or zero epoxy resin. Small amounts of epoxy resin may be beneficial to adjust the properties or co-cure with the B-stage epoxy pre-preg. In such embodiments, the amount of epoxy resin is typically at least 1, 2, 3, 4, 5, 10, 15, or 20 wt.% of the sum of the polyimide and epoxy.

[0137] The (e.g., adhesive or coating) composition optionally comprises a reactive diluent.

[0138] Representative reactive diluents include for example acrylates, methacrylates, styrenics, isopropenylbenzene derivatives, acrylamides, methacrylamides, maleates, cinnamates, vinyl pyridine; aldehydes; episulfides, cyclosiloxanes, oxetanes, lactones, acrylonitrile, cyanoacrylates, vinyl ketones, acrolein, vinyl sulfones, vinyl sulfoxides, vinyl silanes, glycidol, isocyanates and combinations thereof. The amount of reactive diluent can range from 0 to 30 wt.% of the organic polymer or reactive components thereof. Minimizing the reactive diluent can maximize the concentration of polyimide, which in turn can contribute to the adhesive having suitable dielectric properties.

[0139] However, when the (e.g., adhesive or coating) composition, electronic article or component thereof is subject to wet etching or exposure to organic solvent, acids, or bases; the composition may lack oxidizing agent, (methjacrylate, (meth)acrylamide, lactone and triazine curatives.

[0140] In some embodiments, the (e.g., adhesive or coating) composition comprises inorganic filler including for example siliceous filler (e.g., fumed and / or fused silica), alumina, titanium dioxide, calcium carbonate, graphite, boron nitride, fluoropolymers such as polytetrafluoro- ethylene, and mixtures thereof. In some embodiments, the composition lacks fluorinated resins and fillers. In some embodiments, the filler may be functionalized with an aromatic group such an phenyl, a vinyl group, or a hydrocarbon group having at least 4, 6, 8, 10, 12, 14, 16, or 18 carbon atoms. When present, the amount of (e.g., inorganic) filler is typically at least 5, 10, 15, 20, 25, or 30 wt.% of the total composition. The amount of (e.g., inorganic) filler is typically less than 50, 45, 40, 35, or 30 wt.% of the total composition. The inclusion of (e.g., silica) filler can be amenable to improving modulus, but when the concentration is too high it can be detrimental to adhesion.

[0141] The fdler may optionally comprise a silane coupling agent. For example, it is common to apply a silane coupling agent to an inorganic filler as a surface treatment. Various silane coupling agents are known including amino silanes and epoxy silane. In some embodiments, the amino silanes typically comprise an alkylene moiety with no greater than 3 carbon atoms. In other embodiments, the amino silane comprises an alkylene moiety with at least 4, 5, 6, 7, or 8 carbons atoms. In this embodiment, the same class of amino silanes can be utilized as both an adhesion promoting agent and as a surface treatment for an inorganic (e.g., siliceous) filler. Methods of Making Articles and Component Thereof

[0142] In one embodiment, the method of making an (e.g., electronic component) comprises providing a conductive metallic substrate; applying the (e,g., adhesive or coating) composition as described herein to the conductive metallic substrate; and curing the composition.

[0143] The adhesive composition can be used in various methods of bonding. The method generally comprises providing a first substrate, such as a conductive metallic substrate. The method further comprising providing a second substrate or layer, such as an insulating resin layer. The method further comprises providing an adhesive layer, as described herein, between the first substrate and second substrate or layer.

[0144] In some embodiments, a single layer of the adhesive is applied to the first (e.g., conductive metallic) substrate. In other embodiments, a single layer of the adhesive is applied to the second substrate (e.g., insulating resin layer). Although it is convenient to apply a single layer of adhesive, wherein the adhesive comprises all the requisite components, two-part or multiple layers of the adhesive composition are also contemplated. For example, an adhesive precursor comprising the amine compound may be applied to the first (e.g., conductive metallic) substrate and an adhesive precursor comprising the polyimide with maleimide moieties applied to the second substrate (e.g., insulating resin layer). The adhesive composition comprising both components is formed by contacting the adhesive precursors with each other.

[0145] In some embodiments, the polyimide with maleimide moieties, functionalized terpene compound, and other components of the composition are dissolved in a solvent such as a hydrocarbon solvent, an ester, an ether, or a ketone solvent. In some embodiments, the components are dissolved in a mixture of two or more solvents. The hydrocarbon solvent can be pentane, hexane, heptane, cyclohexane, benzene, toluene, xylene, petroleum ether, or kerosene. The ester solvent can be methyl acetate, ethyl acetate, propyl acetate or butyl acetate. The ketone solvent can be acetone, methyl ethyl ketone, methyl propyl ketone, 3 -pentanone, cyclopentanone, or cyclohexanone. The ether solvent can be diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, 1,3 -dioxolane, 1,4-dioxane, 1,2-dimethoxy ethane, or tetrahydropyran. In some embodiments, the solvent is a cyclic molecule containing at least one oxygen atom. This solvent-based (e.g., adhesive or coating) composition can be applied to a substrate or substrates.

[0146] In one embodiment, the composition in solvent may be applied (e.g., doctor bladed) onto a continuous moving substrate (e.g., thin copper sheet or prepreg) on a (e.g., heated) conveyor belt. On a continuous line, a second substrate (e.g., sheet of copper or prepreg) is applied on top of the adhesive composition followed by lamination between hot rollers to form a 3-layer laminate.

[0147] The prepreg typically comprises a fibrous material impregnated with epoxy resin. The fibrous material may be woven or nonwoven. The fibrous material typically comprises organic fibers such as polyimide fiber, polyaramide fiber, polyester fiber, and / or inorganic fibers such as glass fiber, carbon fiber, or other inorganic fibers. The fibrous material may have a thickness of at least 5 or 10 microns. This thickness is typically no greater than 100 or 50 microns. Various insulating layers have been described in the literature. Insulating resin layers typically comprises at least 40, 50, 60 or 70 wt.% of inorganic filler including siliceous filler, fused silica, and boron nitride. In some embodiments, the insulting layer comprises an epoxy resin.

[0148] Various insulating layers, including those made from epoxy resin are known. See for example US 10,501,620; incorporated here by reference.

[0149] Various epoxy resins are known such as a cresol novolac type epoxy compound, phenol novolac type epoxy compound, aliphatic chain epoxy compound, glycidyl ester type epoxy compound, glycidyl amine type epoxy compound, biphenyl type epoxy compound, and epoxy-modified rubber.

[0150] In some embodiments, the epoxy resin comprises a bisphenol type epoxy compound, i.e. an epoxy derived from bisphenol, such as bisphenol A, bisphenol F, bisphenol AF, bisphenol S, bisphenol M, bisphenol E, bisphenol P, bisphenol AP, and bisphenol Z, etc. Depending on what compound is reacted with the hydroxy group of the bisphenol, the bisphenol type epoxy compound can include various divalent linking groups between the oxygen atom of the former -OH group and the epoxy group.

[0151] In some embodiments, the epoxy resin may comprise one or more cycloaliphatic groups. In some embodiments, the epoxy resin may comprise two or more (e.g., fused) cycloaliphatic groups such as norbomane, norbomene, norbomadiene, dicyclopentadiene, adamantane, or dicyclopentadiene.

[0152] In other embodiments, the solvent-based adhesive composition can also be coated onto a release (e.g., PET) film, dried, and wound into rolls forming a transfer tape / film. The rolls of poly imide are then cut to size and sandwiched between (e.g., copper foil) substrates or between a first (e.g., copper foil) and second different (e.g., insulating) layer. The polyimide film can be laminated onto the substrate with heat and / or pressure.

[0153] The (e.g., adhesive or coating) composition can be thermally cured at temperatures up to about 170°C. The heat causes polymerization of the maleimide or alkene moieties. Other reactions may also occur.

[0154] Articles and Components Thereof

[0155] Various articles can be formed from the (e.g., adhesive or coating) composition including printed circuit board and integrated circuit of electronic articles and intermediate components thereof. Illustrative electronic articles include for examples a mobile phone, PHS, laptop PCs, PDAs (personal digital assistants), mobile TV phones, PCs, super computers, servers, routers, liquid crystal projectors, engineering work stations (EWS), pagers, word processors, televisions, viewfinder type or monitor direct viewing type video tape recorders, electronic handheld devices, electronic desktop computers, car navigation systems, POS terminals, devices provided with touch panels, and other various electronic equipment.

[0156] With reference to FIG. 1, various two-layer articles 100 can be formed. Such two-layer articles generally comprise a layer of the (e.g., adhesive or coating) composition 130, as described herein, disposed on a substrate 120. The (e.g., adhesive or coating) composition layer typically has a thickness of at least 0.25, 0.5, 1, 1.5, or 2 microns. In some embodiments, the composition has a thickness no greater than 100, 50 or 25 microns.

[0157] In some embodiments, the substrate is a (e.g., PET) release liner. In this embodiment, the article may be a transfer tape or transfer film. In other embodiments, the substrate is a conductive metallic substrate (e.g., copper) or an insulating layer, such as an epoxy prepreg. In these embodiments, the articles may be components of an electronic article.

[0158] With reference to FIG. 2, various three-layer articles 200 can be formed generally comprising the adhesive layer 230 disposed between a first 221 and second substrate or layer 222.

[0159] The presently described adhesive compositions are suitable for bonding to substrates such a metal (e.g., copper) and suitable for bonding to (e.g., epoxy resin) insulating layers. Bonding to such substrates is of importance for the manufacture of electronic telecommunication articles. As used herein, electronic refers to devices using the electromagnetic spectrum (e.g., electrons, photons); whereas telecommunication is the transmission of signs, signals, messages, words, writings, images and sounds or information of any nature by wire, radio, optical or other electromagnetic systems. Electronic telecommunication articles include for example copper-clad laminates, printed circuit boards, integrated circuits, antennas, and optical cables.

[0160] The adhesive composition and transfer tape film are particularly useful for bonding to metals, such as copper, for use for copper-clad laminates, printed circuit boards (PCBs), and bonding packaged integrated circuits to a PCB.

[0161] In some embodiments, the metallic substrate (e.g., copper) has a surface roughness (Ra orRz) of less than 10 or 5 microns. In some embodiments, the metallic substrate (e.g., copper) has a surface roughness (Ra) of less than 2, 1, 0.5, 0.1, or 0.01 microns. The (e.g., adhesive or coating) may be suitable for bonding metallic substrate (e.g., copper) having an even lower surface roughness (e.g., less than 0.001). Copper having a roughness of 0.15 nmto 1.1 nm has been described in the literature. As the surface roughness decreases, the surface is more difficult to bond to. However, the composition can also be utilized with metallic substrates having a greater surface roughness.

[0162] A printed circuit board, or PCB, is used to mechanically support arid electrically connect electronic components using conductive pathways, tracks or signal traces etched from (e.g.. copper) metal sheets laminated onto a non-conductive substrate. Such boards are typically made from an insulating layer such as glass fiber reinforced (fiberglass) epoxy resin or paper-reinforced phenolic resin. The pathways for electricity' are typically made from a negative photoresist. An insulating layer is disposed on the surface of the (e.g., copper) metal substrate. Portions of insulating layer are removed to form the conductive (e.g., copper) pathways. The insulting layer (e.g., photoresist) remains present, disposed between the conductive (e.g.. copper) pathways of the printed circuit board. Solder is used to mount components on the surface of these boards.

[0163] Numerous PCB and IC constructions are described in the literature.

[0164] One illustrative cross-section of a portion of an integrated chip 300 is depicted in Fig. 3. In this embodiment, an adhesive layer 330 is being utilized to bond smooth copper to a first insulating layer 323, e.g., an epoxy (e.g., build up) material. Such epoxy build up material comprises high concentration of silica and thus is difficult to bond to. The opposing surface of the copper may be bonded to a second insulting layer 324, such as an epoxy or polyimide prepeg. The adhesive may also be used to bond the copper to this second insulting layer.

[0165] Prior to (e.g., thermal) curing, the adhesive can sufficiently flow and fdl around copper traces up to an order of about 2 microns. After (e.g., thermal) curing, the adhesive layer can be removed along with the insulating layer using various patterning techniques including laser ablation, wet etching, dry etching, and electroless copper reception. Before and after (e.g., thermal) curing the adhesive can have high bond strength to copper and (e.g., fdled) epoxy substrate.

[0166] Methods of Wet Etching

[0167] To make electrical connections between two or more circuit layers on opposite sides of a (e. g., double-sided) circuit board, “ through holes” are formed through the two conducting circuit layers and the insulator board. In some embodiments, the through holes are at least 0.025 or 0.05 mm and often no greater than 5 or 6 mm. Multilayer circuit boards also use holes to complete circuits between opposite sides of the insulating layer, as well as intermediate layers. When intermediate conductive layers are electrically connected the holes do not extend through the entire circuit board, yet may still be characterized as “through holes” since the holes extend through a portion of the layers. The through holes can be formed by chemical treatment such as photolithography or by physical treatment such as drilling, laser irradiation, and plasma etching.

[0168] In some embodiments, the insulating layer further comprises a second cured adhesive layer on the opposite planar surface as the i) conductive metallic substrate. In other words the adhesive composition described herein is applied to both major surfaces of the insulating layer and cured. In this embodiment, the cured adhesive layer can protect the insulating layer from exposure to the liquid(s) during wet etching.

[0169] When a through hole is formed, a residue (also referred to as a “smear”) of insulating material remains on the exposed (inside surfaces) of the hole, including the conductive surface within the hole. As used herein, “residue” refers to a small amount of something that remains (after the main part has gone or been taken or used). This residue is removed prior to positioning or depositing the conductive material in the through hole. In typical embodiments, the residue is removed by wet etching (“wet desmear”). Such a method involves contacting at least the residual insulating material of the article with at least one liquid. Common liquids include liquids comprising an organic solvent, alkaline liquids, or acidic liquids. One common method includes three chemical steps. In the first step, an organic solvent is applied to soften the residual insulating material. In the second step, a permanganate compound or other oxidizing agent is applied to remove the swelled resin. In a third step, a neutralizer (also described as a “reducer”) is applied to neutralize and remove the permanganate from the resin surface. Rinsing steps carried out by flooding, dipping, or spraying are often conducted between each step. Further, the steps may be conducted at temperatures greater than room temperature. For example, one or more steps may be conducted at a temperature of at least 30, 40, 50, 60, 70, or 80°C. The process steps may be performed with conveyor equipment and / or dip tanks as known in the art.

[0170] Various aqueous solutions comprising organic solvents, (e.g., permanganate) oxidizers and (e.g., acidic) neutralizers are described in the art. See for example, US 6,454,868; incorporated herein by reference; as well as the three chemical steps of the forthcoming examples.

[0171] Common organic solvents for softening the residual insulating material include for example propylene glycol ethers, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and tripropylene glycol methyl ether. In some embodiments, a mixture of at least two organic solvents may be utilized. The first solvent may be gamma-butyrolactone, ethyl-3-ethoxy -propionate, N-ethyl-2-pyrrolidone, N-(2-hydroxyethyl)-2 -pyrrolidone, N-cyclohexyl-2 -pyrrolidone, N-octyl-2-pyrrolidone, and mixtures thereof. The second organic solvent may be N-methyl-2 -pyrrolidone, 2-pyrrolidone, tetrahydrofuran, N-ethy 1-2 -pyrrolidine, N-cyclohexyl-2 -pyrrolidone, N-dodecyl-2 -pyrrolidone, and mixtures thereof. Surfactants, including fluorochemical surfactants may be included with the organic solvent(s). Permanganate oxidizers include alkaline solutions of sodium, potassium or lithium permanganate. Neutralizers include oxalic acid or aqueous acidic solutions such as dilute sulfuric acid, hydrochloric acid, acidified stannous chloride, hydroxylamine hydrochloride, or formaldehyde.

[0172] When an insulating layer is bonded to a conductive metallic substrate or layer with an adhesive as described herein, the adhesive needs to be resistant to the wet etching process. As evident by the forthcoming examples, the cured adhesive layer disposed on a conductive metallic substrate(s) has a cross hatch adhesion of at least 2B, 3B, 4B, or 5B before and after contact with at least one, two, or all three the wet etching liquids.

[0173] It is appreciated that since the composition described herein has been found to be resistant to all three of these steps, the composition is also resistant to methods that comprise any one of these steps or combination of two steps without the third step. Thus, the composition is resistant to organic solvents, such as those previously described. The composition is also resistant to alkaline liquids. Alkaline liquids have a pH greater than 7, such as a pH of at least 8, 9, 10, 11, or 12. The composition is also resistant to acidic liquids. Acidic liquids have a pH of less than 7, such as a pH of no greater than 6, 5, 4, 3, or 2. The composition is also water resistant (i.e., neutral pH).

[0174] After the insulating resin residue is removed (e.g., desmeared), the inside wall surfaces of the holes are filled with conductor material. In some embodiments, a second metallic layer is formed on the insulating layer concurrently with filling the desmeared holes. When the cured adhesive layer is disposed on both sides of the insulating layer, the method may further comprise applying a second conductive metallic layer to the second cured adhesive layer by electroless plating, electrolytic plating, or a combination thereof. EXAMPLES

[0175] Table 1.

[0176]

[0177]

[0178] Nuclear Magnetic Resonance (NMR) Spectroscopy

[0179] NMR samples were analyzed as solutions in deuterated chloroform. NMR spectroscopy was conducted using a Bruker AVANCE III 500 MHz NMR spectrometer equipped with a CPBBO gradient cryoprobe, a Broker B-ACS 60 autosampler, and Bruker Topspin 3.04 software. Spectra were analyzed using Advanced Chemistry Development software (Toronto, Canada). Analysis of the chemical shifts and integrals in the proton spectra confirmed the formation of BCA by loss of the exo-presented alkene (4.75 ppm), retention of the internal alkene (5.25 ppm), and the appearance of two new methylene groups associated with the target thiol-ene product (2.75 ppm and 3.00 ppm)

[0180] Addition Polymerized Norbomene

[0181] See Curable and Cured Thermosetting Compositions, W02024100476A1 (3M).

[0182] Synthesis of P-carophyllene amine (ACA 3)

[0183] A mixture of cysteamine (0.16g, 7.91 mmol) and P-carophyllene (1.62 g, 7.91 mmol) in ethanol (3 mL) was gently heated to form a solution, TPO-L was added (0.04g, 2 wt% relative to reagents) and the solution was stirred while exposed to UV (Clearstone CF1000 UV LED system, 395 nm, 100% intensity corresponding to 319 mW / cm2for 15 minutes at a distance of 10 cm from the flask). Ethanol was removed in vacuo to give the crude product as a pale yellow odorless oil. The oil was dissolved in chloroform and a fine white precipitate of unreacted cysteamine was removed by filtration. Chloroform was removed in vacuo to isolate the target product as a pale yellow oil.

[0184]

[0185] Figure 4. Synthesis of amino -functionalized (3-carophyllene Formulations and Coating

[0186] Table 2. Components (pph)

[0187]

[0188] Adhesion control agents (ACAs) were added to the formulations above at a loading of 2 wt% relative to total solids. The formulations were coated onto glass substrates (silicon nitride substrates or copper substrates (smooth electro-deposited copper with a surface roughness of Ra 0.01). Substrates were washed with IPA prior to coating. 0.5 mL of formulation was pipetted onto the substrate and allowed to spread into a circle ~2 cm in diameter. Formulations 1 and 2 were cured at 150° for 2 hrs. Formulations 3-5 were cured at 130°C for 30 mins and 170°C for a further 30 mins.

[0189] Crosshatch Adhesion & Wet Etch

[0190] Crosshatch adhesion tests on cured samples were performed as described in ASTM D3359-09 (Standard Test Methods for Measuring Adhesion by Tape Test) where a grid of 25 squares is cut, tape and pressure via roller are applied on top of the grid, the construction is left to dwell for two mins, the tape is peeled off, and the state of the grid and the residue on the tape are inspected. A crosshatch value of 0B denotes poor adhesion (greater than 65% of grid area detached upon tape removal) through a range of IB (35-65% lost), 2B (15-35% lost), 3B (5-15% lost), 4B (< 5% lost) up to 5B which denotes the best adhesion (no detachment, no damage to scored crosshatch lines and no residue on tape upon tape removal). The term ‘zero adhesion’ denotes that it was not possible to conduct a crosshatch tape peel because the coating was detached from the substrate; hence ‘zero adhesion’ denotes worse adhesion performance than a 0B value. The crosshatch testing was conducted using 3M SCOTCH 232 Tape. Two grids / tests were run for a given formulation.

[0191] After the first crosshatch adhesion test, the copper constructions coated with the crosshatched layers underwent wet etch treatment through the following three baths based on Atotech Securiganth®MV concentrates (a 2-(2butoxyethoxy)ethanol and ethylene glycol based sweller, a NaMnO4-based oxidizing etch and a hydroxylamine sulfate-based reducer). Step 1 - Atotech Securiganth®MV Sweller concentrate (367.20 g), 25 wt% sodium hydroxide (1.13g), deionized water (539.1 g) / 60°C / 10 mins

[0192] Step - 2 - Atotech Securiganth®MV P-Etch concentrate (183.6 g), 25wt% sodium hydroxide (162.0 g), deionized water (661.5 g) / 80 °C / 20 mins

[0193] Step 3 - Atotech Securiganth®MV Reduction Conditioner concentrate (56.0 g), 50 wt% sulphuric acid (62.78 g), deionized water (405.0 g) / H2SO4 / 50 °C / 5 mins

[0194] After completion of wet etch and drying, tape was applied to the crosshatched areas, a second tape peel was performed under the ASTM-D3359-09 conditions above, and any further damage and / or residue left on the tape was observed and recorded.

[0195] Table 3. Crosshatch adhesion on glass substrates

[0196]

[0197] Table 4. Crosshatch adhesion on silicon nitride substrates

[0198]

[0199] Table 5. Crosshatch adhesion on copper substrates before and after wet etch exposure

[0200]

Claims

What is claimed is:

1. A composition comprising:an organic polymer; andat least 0.25 wt.% of a compound comprising a terpene moiety comprising at least 8 carbon atoms and a functional group selected from amine, anhydride, imide or carboxylic acid.

2. The composition of claim 1 wherein the terpene moiety comprises no greater than 40 carbon atoms.

3. The composition of claims 1-2 wherein the organic polymer has a Tg of at least 50°C.

4. The composition of claims 1-3 wherein the organic polymer is a thermoset or a cured thermoset resin.

5. The composition of claims 1-4 wherein the organic polymer is a polyimide comprising maleimide moieties.

6. The composition of claim 5 wherein the polyimide has the formula:where R1is hydrogen or methyl; andQ and R are independently organic linking groups.

7. The composition of claims 1-4 wherein the organic polymer comprises a cyclic olefin polymer.

8. The composition of claim 7 wherein the organic polymer comprises norbornene moieties.

9. The composition of claims 1-7 further comprising a curing agent.

10. The composition of claims 1-9 further comprising inorganic filler including siliceous filler.

11. The composition of claims 1-10 wherein the organic polymer or composition has a Dielectric Constant (Dk) @20 GHz of less than 2.7, 2.6, 2.5, 2.4, 2.3 or 2.2.

12. An article or component thereof comprising:at least one conductive metallic substrate or metallic layer comprising the composition according to claims 1-11; wherein the composition is cured.

13. The article of claim 12 wherein the cured composition is a) a coating or b) an adhesive that bonds the conductive metallic substrate or metallic layer to an insulating resin layer.

14. The article of claims 12-13 wherein the article is an electronic article including a component of a printed circuit board or integrated circuit.

15. The article of claims 12-14 wherein the conductive metallic substrate(s) comprises copper including copper traces.

16. The article of claim 15 wherein the copper has a surface roughness (Ra) of less than 2, 1, 0.5, or 0.1 microns.

17. A method of wet-etching comprising:providing an article comprising:i) a conductive metallic substrate;ii) an insulating resin layer; andiii) an adhesive composition according to claims 1-11 disposed between the conductive metallic substrate and insulating resin layer wherein the adhesive composition is cured;contacting the article with at least one liquid, wherein the liquid comprises an organic solvent, an alkaline solution, or an acidic solution.

18. The method of claim 17 wherein the article is a component of a printed circuit board or integrated circuit comprising holes and residual insulating resin within the holes.

19. The method of claim 18 wherein the step of contacting the article with at least one liquid removes the residual insulating resin from the holes.

20. The method of claims 17-19 wherein the conductive metallic substrate(s) comprises copper including copper traces having a surface roughness (Ra) of less than 2, 1, 0.5, or 0.1 microns.

21. The method of claims 17-20 wherein the cured adhesive layer disposed on the conductive metallic substrate has a cross hatch adhesion of at least 2B, 3B, 4B, or 5B before and after contact with the at least one liquid.

22. A functionalized terpene compound comprising the reaction product of:a cyclic terpene moiety wherein a carbon atom of the ring comprises a pendent =CH2group; and a compound comprising a thiol group and an amine group.

23. A functionalized terpene having the formula:Cyc-CH2-S-R-NR2R3wherein Cyc is a cyclic terpene moiety;R is a C1-C24 hydrocarbon group; andR2and R3are independently hydrogen or a C1-C4 alkyl group.

24. The functionalized terpene of claims 22-23 having the formula:R is a C1-C24 hydrocarbon group.

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