Ultra-low loss hydrocarbon resin composition

Abstract

Ultra low loss curable hydrocarbon resin compositions comprising vinylbenzyl compounds, processes for their preparation and their use for the manufacture of articles for use in the electrical / electronic industry.

Description

[0001] The present invention relates to vinylbenzyl-based resin compositions, their preparation and their use in various applications such as the production of prepregs, laminates for printed wiring boards, molding materials and adhesives.

[0002] The present invention relates to a resin composition which provides a cured product having high heat resistance, low water absorption and excellent dielectric properties. These favorable properties are required for organic insulating materials used in electronic devices such as communication devices. Prior Art

[0003] With the development of wireless networks and satellite communications, electronic products tend to require higher speeds, higher frequencies and greater capacity to transmit voice, video and data. In addition, as these electronic products become thinner and smaller, the complexity, density and multi-layer layering of circuit boards tend to increase. In order to maintain high transmission rates and signal integrity, printed circuit boards ("PCBs") require materials with low dielectric loss (also called loss factor or dissipation factor, Df), resulting in lower signal loss.

[0004] Polymer insulating materials are usually used as the base material of PCB. The laminate for PCB is made of polymer insulating materials alone or obtained by blending polymer insulating materials with glass, fiber, nonwoven fabric, inorganic filler, etc. Epoxy resins are traditionally used, due to their low cost and high heat resistance and chemical resistance during curing. However, due to their relatively high dielectric constant and high dielectric loss tangent, it is difficult to obtain suitable low loss factor under high-frequency signals. Polyphenylene ether (PPO) resin is also used in laminates due to its lower dielectric constant and loss properties, but the use of high-frequency signals in the new electronic field requires even lower dielectric loss constant and loss factor. Fluororesins represented by polytetrafluoroethylene (PTFE) usually have low dielectric constants and loss factors, but they are thermoplastic resins, and therefore experience large expansion and contraction during molding and processing, and are materials that are not easy to handle.

[0005] Other types of resins are known, but cannot achieve the low dielectric loss values ​​Df required for high frequency signal transmission requirements.

[0006] There is a need to provide curable polyvinyl benzyl compounds with improved properties, particularly in terms of Df, thermomechanical properties, moisture resistance, and which can be easily processed. There is a need to improve high-speed signal transmission while reducing power and interference issues in electronic applications. This requires a material composition with improved dielectric properties while maintaining the thermomechanical properties and ease of manufacture required for large-scale sustainable production of printed circuit boards and antennas.

[0007] US 2005 / 176909 discloses curable polyvinylbenzyl compounds obtained by reacting a fluorene compound with a vinylbenzyl halide and a dihalomethyl compound. However, the disclosed compositions are not completely satisfactory.

[0008] There remains a need for resin compositions that can be used in electronic devices and that provide a higher dissipation factor and / or a higher first G' onset and / or a higher decomposition temperature.

[0009] The object of the present invention is to overcome the above-mentioned disadvantages of prior art resin compositions. Summary of the invention

[0010] A first object of the present invention is a curable resin composition obtainable or obtained by a process comprising at least the following steps:

[0011] (i) mixing at least the following compounds (a), (b) and (c), and

[0012] (ii) reacting the compound in the presence of a base:

[0013] (a) one or more indene compounds represented by the following general formula 1:

[0014]

[0015] wherein each R1 is independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a thioalkoxy group having 1 to 5 carbon atoms, a thioaryloxy group having 6 to 14 carbon atoms, and an aryl group having 6 to 14 carbon atoms, and combinations thereof,

[0016] (b) one or more biphenyl compounds represented by the following general formula 2,

[0017]

[0018] in

[0019] Each X is independently selected from halogen atoms, tosylate, mesylate, triflate, and combinations thereof,

[0020] Each Q is independently selected from a hydrogen atom and a linear or branched C1-C6 alkyl group and combinations thereof, and

[0021] Each R2 is independently selected from a hydrogen atom, a linear or branched C1-C6 alkyl group, a halogen atom, and combinations thereof,

[0022] (c) one or more vinylbenzyl compounds represented by the following general formula 3:

[0023]

[0024] in

[0025] X' is selected from the group consisting of halogen atoms, tosylate, mesylate, triflate, and combinations thereof.

[0026] The above method is also an object of the present invention.

[0027] Another object of the present invention is a curable resin composition comprising at least:

[0028] (1) A compound having the following formula C1:

[0029]

[0030] wherein each R1 is independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a thioalkoxy group having 1 to 5 carbon atoms, a thioaryloxy group having 6 to 14 carbon atoms, and an aryl group having 6 to 14 carbon atoms, and combinations thereof, and

[0031] Each F1 is independently selected from a hydrogen atom and a vinylbenzyl group and combinations thereof, provided that at least one F1 is a vinylbenzyl group:

[0032]

[0033] (2) A compound having the following formula C2:

[0034]

[0035] wherein each R1 is independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a thioalkoxy group having 1 to 5 carbon atoms, a thioaryloxy group having 6 to 14 carbon atoms, and an aryl group having 6 to 14 carbon atoms, and combinations thereof, and

[0036] Each F2 is independently selected from a hydrogen atom, a vinylbenzyl

[0037]

[0038] Or a structure of formula F3, provided that at least one F2 is a structure of formula F3:

[0039]

[0040] in:

[0041] - n, p and p' may independently be 0 to 50, preferably 0 to 10,

[0042] - each R1 is independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a thioalkoxy group having 1 to 5 carbon atoms, a thioaryloxy group having 6 to 14 carbon atoms, and an aryl group having 6 to 14 carbon atoms, and combinations thereof,

[0043] - each F'2 is independently selected from a hydrogen atom, a vinylbenzyl group, provided that at least one F2 or at least one F'2 is a vinylbenzyl group,

[0044]

[0045] F4 is selected from a divalent group of formula F4 or a combination thereof:

[0046]

[0047] in:

[0048] Each Q is independently selected from a hydrogen atom and a linear or branched C1-C6 alkyl group or a combination thereof; and

[0049] Each R2 is independently selected from a hydrogen atom, a linear or branched C1-C6 alkyl group, a halogen atom, or a combination thereof.

[0050] The curable resin composition disclosed above comprises at least:

[0051] (1) a compound having the formula C1, and

[0052] (2) a compound having formula C2,

[0053] The composition is advantageously obtained by the method disclosed above, which comprises at least the following steps:

[0054] (i) mixing at least compounds (a), (b) and (c), and

[0055] (ii) reacting the compound in the presence of a base.

[0056] However, the curable resin composition comprising at least one compound C1 and at least one compound C2 can be obtained by other methods well known to those skilled in the art and is not limited to those obtained by the methods disclosed above. One of those methods is to mix compound C1 with compound C2.

[0057] The method comprises at least the following steps:

[0058] (i) mixing at least compounds (a), (b) and (c), and

[0059] (ii) reacting the compound in the presence of a base,

[0060] The resulting composition contains, in addition to the compound of formula C1 and the compound of formula C2, other compounds known to those skilled in the art.

[0061] The present invention further relates to a method for producing an article, comprising at least the following steps:

[0062] -Step 1:

[0063] Prepare a curable resin composition according to the method disclosed above, or

[0064] preparing a curable resin composition comprising at least a compound having formula C1 and a compound having formula C2, as disclosed above,

[0065] The composition optionally comprises one or more additives, including, for example, curing agents, curing accelerators, free radical inhibitors, fillers;

[0066] -Step 2:

[0067] to give shape to the composition,

[0068] -Step 3:

[0069] The composition is allowed to cure.

[0070] The invention also relates to a product obtained by said process. BRIEF DESCRIPTION OF THE DRAWINGS

[0071] Figure 1 The 1H-NMR spectrum of compound 1 of Example 1 is shown;

[0072] Figure 2 The 1H-NMR spectrum of Compound 2 of Example 2 is shown;

[0073] Figure 3 The 1H-NMR spectrum of compound 3 of Example 3 is shown;

[0074] Figure 4 The 1H-NMR spectrum of compound 4 of Example 4 is shown;

[0075] Figure 5 shows the 1H-NMR spectrum of Compound 5 of Example 5; and

[0076] Figure 6 The 1H-NMR spectrum of Compound 6 of Comparative Example 6 is shown. DETAILED DESCRIPTION

[0077] Throughout this specification, reference to "one embodiment" or "an embodiment" means that the specific features, structures, or characteristics described in conjunction with the embodiment are included in at least one embodiment of the present invention. Therefore, the phrases "in one embodiment" or "in an embodiment" appearing in various places throughout this specification do not necessarily all refer to the same embodiment, but may refer to the same embodiment. In addition, in one or more embodiments, specific features, structures, or characteristics may be combined in any suitable manner, as will be apparent to those skilled in the art from the present invention. In addition, although some embodiments described herein include some features included in other embodiments but not other features, the combination of features of different embodiments is intended to be within the scope of the present invention and to form different embodiments, as will be understood by those skilled in the art. For example, in the appended claims, any claimed embodiment may be used in any combination.

[0078] As used herein, the singular form "a," "an," and "the" include both singular and plural referents unless the context clearly dictates otherwise. For example, "halogen" means one halogen atom or more than one halogen atom.

[0079] As used herein, the term "comprising" is synonymous with "including" or "containing", and is inclusive or open-ended, and does not exclude additional, undescribed members, elements or method steps. It should be understood that as used herein, the term "comprising" includes the term "consisting of". This means that preferably the above terms such as "comprising", "containing", can be replaced with "consisting of".

[0080] Throughout this application, the term "about" is used to indicate that a value includes the standard deviation of error for the device or method being employed to determine the value.

[0081] As used herein, the terms "weight %", "wt %", "weight percent" or "percent by weight" are used interchangeably.

[0082] Numerical ranges expressed by endpoints include all integers and, where appropriate, fractions contained within the range (e.g., 1 to 5 may include 1, 2, 3, 4 when referring to, for example, the number of elements, and 1.5, 2, 2.75, and 3.80 when referring to, for example, measured values). The description of an endpoint also includes the endpoint value itself (e.g., 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range described herein is intended to include all subranges contained therein.

[0083] The term "CX-CY alkyl" refers to a straight chain or branched hydrocarbon group having from X to Y carbon atoms, and "substituted alkyl" refers to an alkyl group further bearing one or more substituents selected from the group consisting of hydroxy, alkoxy, mercapto, cycloalkyl, heterocyclic, aryl, heteroaryl, aryloxy, halogen, trifluoromethyl, cyano, nitro, nitrone, amino, amide, C(O)H, acyl, oxyacyl, carboxyl, carbamate, sulfonyl, sulfonamide and sulfonyl.

[0084] The term "cycloalkyl" refers to a divalent ring-containing group containing 3 to 8 carbon atoms, and "substituted cycloalkyl" refers to a cycloalkyl group further bearing one or more substituents selected from the group consisting of hydroxy, alkoxy, mercapto, cycloalkyl, heterocycle, aryl, heteroaryl, aryloxy, halogen, trifluoromethyl, cyano, nitro, nitrone, amino, amido, C(O)H, acyl, oxyacyl, carboxy, carbamate, sulfonyl, sulfonamide and sulfonyl.

[0085] The term "aryl" refers to a divalent aromatic group having 6 to 14 carbon atoms, and "substituted aryl" refers to an aryl group further bearing one or more substituents selected from the group consisting of hydroxy, alkoxy, mercapto, cycloalkyl, heterocyclyl, aryl, heteroaryl, aryloxy, halogen, trifluoromethyl, cyano, nitro, nitrone, amino, amide, C(O)H, acyl, oxyacyl, carboxyl, carbamate, sulfonyl, sulfonamide and sulfonyl.

[0086] The term "heteroaryl" refers to a divalent aromatic group containing one or more heteroatoms (e.g., N, O, S, etc.) as part of the ring structure and having 3 to 14 carbon atoms; and "substituted aryl" refers to an arylene group further bearing one or more substituents selected from the group consisting of hydroxy, alkoxy, mercapto, cycloalkyl, heterocyclyl, aryl, heteroaryl, aryloxy, halogen, trifluoromethyl, cyano, nitro, nitrone, amino, amide, C(O)H, acyl, oxyacyl, carboxyl, carbamate, sulfonyl, sulfonamide, and sulfonyl.

[0087] The term "halogen" refers to an atom selected from Cl, Br, I.

[0088] As used herein, the terms "dielectric dissipation factor (Df)" and "loss tangent" are synonymous and refer to the amount of energy (ie, electrical losses) dissipated into an insulating material when a voltage is applied to the circuit. Df represents the loss of a signal in a circuit.

[0089] As used herein, the terms "dielectric constant (Dk)" and "permittivity" are synonymous and refer to a measure of the relative capacitance of an insulating material relative to the relative capacitance of air or a vacuum. The dielectric constant determines the speed of electronic signals.

[0090] The entire contents of all references cited in this specification are hereby incorporated by reference. In particular, the teachings of all references specifically mentioned herein are incorporated by reference.

[0091] Unless otherwise defined, all terms used in disclosing the present invention, including technical and scientific terms, have the meanings commonly understood by ordinary technicians in the field to which the present invention belongs. By further guidance, term definitions are introduced to better understand the teachings of the present invention.

[0092] Throughout this application, different aspects of the present invention are defined in more detail. Unless there is a clear contrary indication, each aspect defined can be combined with any other one or more aspects. Specifically, any feature indicated as preferred or advantageous can be combined with any other one or more features indicated as preferred or advantageous. Although preferred embodiments of the present invention have been disclosed for illustrative purposes, it will be appreciated by those skilled in the art that various modifications, additions or substitutions are possible without departing from the scope and spirit of the present invention disclosed in the appended claims.

[0093] Compound

[0094] According to an advantageous embodiment of the invention, a curable composition comprising at least compound C1 and at least compound C2 is obtained by reacting one or more indene compounds represented by the general formula 1 above with one or more dimethylbiphenyl compounds of formula 2 and one or more vinylbenzyl compounds of formula 3 in the presence of a base. Optionally, a fluorene compound may be part of the reaction mixture. The reaction may be carried out according to known conditions for vinylbenzylation reactions. Vinylbenzylation reactions are described, for example, in US 2005 / 0176909.

[0095] According to the invention, in formula 1 representing the indene compound and / or in compound C1 and / or compound C2, the R1 group is located on the phenyl part of the indene bicyclic ring.

[0096] According to an advantageous embodiment, in the general formula 1 representing the indene compound and / or in compound C1 and / or compound C2:

[0097] - all R1 groups represent H, or

[0098] - one R1 group is a halogen atom, or an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and the other R1 group represents H.

[0099] According to the most advantageous embodiment, all R1 groups represent H and the compound of formula 1 is indene.

[0100] According to an advantageous embodiment, in the general formula 2 representing the biphenyl compound, X is selected from halogen atoms, toluene sulfonates, mesylates, trifluoromethanesulfonates and combinations thereof, more preferably halogen atoms, advantageously Cl or Br. Preferably all X are the same. Even more preferably all X are Cl.

[0101] According to an advantageous embodiment, in the general formula 2 representing the biphenyl compound, in formula F4, each Q is independently selected from H, CH 3 , C 2 H 4 and combinations thereof, more preferably each Q is independently selected from H, CH 3 and combinations thereof. Preferably all Q are the same. According to the most preferred embodiment, all Q are H.

[0102] According to an advantageous embodiment, in the general formula 2 representing the biphenyl compound, R2 is independently selected from H, CH 3 and combinations thereof. Preferably all R2 are the same. Preferably all R2 are H.

[0103] According to an advantageous embodiment, the compound (b) of formula 2 is 4,4'-bis(chloromethyl)biphenyl.

[0104] According to the most advantageous embodiment, the compound (b) of formula 1 is indene, and the compound (b) of formula 2 is 4,4'-bis(chloromethyl)-biphenyl.

[0105] According to an advantageous embodiment, in the general formula 3 representing the vinylbenzyl compound, X' is selected from Cl, Br, I, tosylate, mesylate, triflate and combinations thereof, more preferably selected from Br, Cl and combinations thereof. 2 The -X' group may be located in the ortho, meta or para position of the aromatic ring, or may be a mixture of positional isomers.

[0106] According to the most advantageous embodiment, the vinylbenzyl compound represented by formula 3 is selected from 2-vinylbenzyl chloride, 3-vinylbenzyl chloride, 4-vinylbenzyl chloride, 2-vinylbenzyl bromide, 3-vinylbenzyl bromide, 4-vinylbenzyl bromide and mixtures thereof.

[0107] More preferably, the vinylbenzyl compound represented by Formula 3 is a mixture of 10 to 50% by weight of 2-vinylbenzyl chloride, 0 to 10% by weight of 3-vinylbenzyl chloride and 50 to 80% by weight of 4-vinylbenzyl chloride.

[0108] More preferably, in compound C2, F'2 is a vinylbenzyl compound corresponding to a mixture of 10-50 wt% 2-vinylbenzyl substituents, 0-10 wt% 3-vinylbenzyl substituents and 50-80 wt% 4-vinylbenzyl substituents.

[0109] Preferably, in compound C2, each F3 independently has n+p of 0 to 50, preferably 0 to 10.

[0110] Preferably, in compound C2, each F2 is independently selected from a hydrogen atom, a vinylbenzyl group or a structure of formula F3 wherein p=0.

[0111] In the method according to the present invention, the molar ratio of the indene compound of Formula 1 to the dimethylbiphenyl compound of Formula 2 is selected so that gelation or precipitation is not caused by the dimethylbiphenyl compound of Formula 2. When the amount of the vinylbenzyl compound of Formula 3 is too low, curability is deteriorated, and physical properties such as heat resistance of the cured product are deteriorated.

[0112] The preferred molar ratio of all halomethyl groups (preferably chloromethyl groups, if present) in compounds (b) and (c) to reactive sites in compound (a) is 0.95 or less. In this context, a "halomethyl group" (also referred to as a "methyl halide group") means a methyl group substituted with a halogen atom, which is obtained if Q = H and X = halogen in Formula 2, and X' = halogen in Formula 3. In this context, a "reactive site" means a carbon atom with an acidic hydrogen in a 5-membered indene ring, which can be deprotonated by the base used in step (ii).

[0113] The molar ratio of the indene compound of Formula 1 to the dimethylbiphenyl compound of Formula 2 is preferably 1.8 / 1 to 3 / 1.

[0114] The molar ratio of the indene compound of Formula 1 to the vinylbenzyl compound of Formula 3 is preferably 1 / 1 to 1 / 2, preferably 1 / 1.75, most preferably 1 / 1.5.

[0115] Preferably at least two, most preferably all three, of the above conditions for the ratio of compounds should be met to achieve optimal results.

[0116] reaction

[0117] The reaction (ii) of compounds (a), (b) and (c) in the presence of a base is advantageously carried out under the following conditions:

[0118] Advantageously, the reaction is carried out in a solvent. Suitable reaction solvents include non-polar solvents such as toluene, dimethylbenzene, or aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-Methylpyrrolidone, dioxane, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, 1,3-dimethoxypropane, 1,2-dimethoxypropane, tetramethylene sulfone, hexamethylphosphoramide, methyl ethyl ketone, methyl isobutyl ketone, acetone, pimelinketone and their mixture, preferably toluene, dimethylbenzene, methyl ethyl ketone and their mixture. The solvent can be selected from the list according to the type of raw material and reaction conditions so that the reaction mixture is completely dissolved in the solvent.

[0119] Examples of bases useful in the present invention include alkali metal or alkaline earth metal alkoxides, hydrides, hydroxides and combinations thereof, such as sodium hydroxide, sodium methoxide, sodium ethoxide, sodium hydride, sodium borohydride, potassium hydride and potassium hydroxide. The base is introduced into the reaction mixture in the form of an aqueous solution.

[0120] The amount of the base is preferably 1 to 3 equivalents, based on the sum of the X group and the X' group in the compound of formula 2 and the compound of formula 3 introduced into the reaction mixture. When the amount is less than 1 equivalent, the reaction rate becomes very low, and the reaction cannot be carried out completely, which is harmful to the physical properties of the cured product. When the amount of the base exceeds 3 equivalents, the conditions for removing the residual base (such as cleaning) are more cumbersome and costly.

[0121] Preferably, an onium salt-based catalyst is introduced into the reactant mixture of step (i). Advantageously, the onium salt-based catalyst is selected from tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium hydrogen sulfate, benzyltrimethylammonium chloride and trioctylmethylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium hydrogen sulfate, benzyltrimethylammonium chloride and trioctylmethylammonium chloride. Benzyltriphenyl chloride Tetraphenyl chloride Tetraphenyl bromide Benzyltetramethylenesulfonium bromide and mixtures thereof.

[0122] The reaction temperature and reaction time may vary depending on the type of raw material compound and the desired physical properties of the curable composition. As a general indication, the temperature of the reaction mixture may be 30° C. to 100° C. When the reaction temperature is too high, other unpreferable reactions such as thermal polymerization may occur. When the reaction temperature is too low, the reaction proceeds at a slow rate, which is disadvantageous from an industrial and economic point of view. As a general indication, the duration of the reaction may be 0.5 hours to 20 hours.

[0123] Curable resin composition

[0124] In this chapter, percentages are expressed as the weight of compound C1 and compound C2 relative to the total weight of the resin, which total weight may include other products formed by the reaction of compounds (a), (b) and (c), but does not include optional additives described in detail below.

[0125] Advantageously, in the resin composition, the amount of compound(s) C1 is from 1 to 50% by weight, based on the total weight of the resin composition.

[0126] Advantageously, in the resin composition, the amount of compound(s) C2 is from 50 to 99% by weight, based on the total weight of the resin composition.

[0127] The following characteristics of the resin composition according to the present invention relate to the mixture of C1 and C2 or the product formed by the process disclosed above.

[0128] Advantageously, the resin composition according to the invention has a weight average molecular weight of Mw = 500 to 10000 g / mol, more preferably 500 to 5000 g / mol, measured by GPC by method ISO 13885-1:2020.

[0129] Advantageously, the resin composition according to the invention has a polydispersity of from 2.01 to 5, more preferably from 2.01 to 3, measured by GPC by method ISO 13885-1:2020.

[0130] Additional components

[0131] Before curing, the curable resin composition can be mixed with various additives selected according to the target application and the expected properties. These additives are described in detail in a non-limiting manner below. In this chapter, the percentage is expressed as the weight of the additional compound relative to the total weight of the resin composition containing the additive. The amount does not include a mixture of compounds C1 and C2, and / or does not include the compound formed by the reaction of compounds (a), (b) and (c).

[0132] The use of a co-curing agent in the resin composition can reduce the curing temperature or promote the curing reaction. According to an advantageous embodiment, the composition of the present invention includes at least one co-curing agent, which can be selected from, for example, polyphenylene ether derivatives, maleimide, bismaleimide, styrene, divinylbenzene, trivinylcyclohexane, isocyanuric acid trialenyl ester compounds such as isocyanuric acid triallyl ester (TAIC) and mixtures thereof.

[0133] Polyphenylene ether derivatives are commercially available. Examples are Noryl TMSA9000 resin, and OPE-2ST 1200 and OPE-2ST 2200 manufactured by Mitsubishi Gas Chemical Company, Inc.

[0134] The amount of the co-curing agent used is adjusted according to the type and content of unsaturated groups contained in the curable resin composition, the selection of a specific co-curing agent, its half-life temperature and the desired stability. In one embodiment, the composition of the present invention may include co-curing agents and mixtures thereof in an amount ranging from about 1 wt % to about 90 wt % or from about 5 wt % to about 50 wt %, based on the total weight of the composition containing the additive.

[0135] Although the resin composition of the present invention can be cured by heating alone, a curing catalyst that generates cationic or free radical substances may be added to improve the curing efficiency. Examples of such curing catalysts include, but are not limited to, diaryliodonium salts, triarylsulfonium salts, and aliphatic sulfonium salts, which contain BF 4 PF 6 , AsF 6 or SbF 6 As the counter anion, benzoin-type compounds such as benzoin and benzoin methyl, acetophenone-type compounds such as acetophenone and 2,2-dimethoxy-2-phenylacetophenone, etc.; thioxanthone-type compounds such as thioxanthone and 2,4-diethylthioxanthone; bis-azide compounds such as 4,4'-diazide chalcone, 2,6-bis(4-azidobenzylidene)cyclohexanone and 4,4'-diazide benzophenone, azo compounds such as azobisisobutyronitrile, 2,2-azobispropane and 2,2'-azobis(2,4,4-trimethylpentane), organic peroxides such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3 and dicumyl peroxide.

[0136] The composition of the present invention may contain a curing catalyst in an amount of about 0.1-10 wt %, or about 0.3-7 wt %, or about 0.5-5 wt %, or about 1-3 wt %, wherein the wt % is based on the total weight of the composition including the additive.

[0137] In another embodiment, an inhibitor may be optionally added to the composition to improve storage stability. Examples include quinones, phenols, catechols, phenothiazines, (2,2,6,6-tetramethylpiperidin-1-yl)oxys and hydroxylamines and their corresponding salts, such as hydroquinone, p-benzoquinone, 2,6-di-tert-butyl-4-methylphenol, phenothiazines, (2,2,6,6-tetramethylpiperidin-1-yl)oxys and 4-tert-butylcatechol. The composition may include about 0.0005-5% by weight of the inhibitor (when present), wherein the weight % is based on the total weight of the composition containing the additive.

[0138] In particularly preferred embodiments, the resin composition may optionally include an inorganic filler, an organic filler, or a mixture thereof. The filler contemplated for use in the practice of the present invention may be in any of a variety of forms, such as angular, flaky, spherical, amorphous, sintered, fired, powdered, flake, crystallized, ground, crushed, milled, etc., or a mixture of any two or more thereof. The currently preferred particulate fillers contemplated for use herein are substantially spherical.

[0139] Such fillers may optionally be thermally conductive. Fillers in both powder and flake form may be used in the resin compositions of the present invention. Fillers having a wide range of particle sizes may also be used in the practice of the present invention.

[0140] Particle sizes of about 500 nm to about 300 microns may be used, with particle sizes less than about 100 microns being preferred, and particle sizes of about 5 to about 75 microns being particularly preferred.

[0141] A variety of fillers can be used in the practice of the present invention, such as soft fillers (e.g., uncalcined talc), naturally occurring minerals (e.g., aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, magnesium oxide, silica, alumina, aluminum silicate, etc.), calcined naturally occurring minerals (e.g., enstatite), synthetic fused minerals (e.g., cordierite), treated fillers (e.g., silane-treated minerals), organic polymers (e.g., polytetrafluoroethylene), hollow spheres, microspheres, powdered polymer materials, etc.

[0142] Exemplary fillers include talc, mica, calcium carbonate, calcium sulfate, aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, magnesium oxide, silicon dioxide, aluminum oxide, TiO 2 , aluminum silicate, aluminum zirconium silicate, cordierite, silane-treated minerals, polytetrafluoroethylene, polyphenylene sulfide, etc.

[0143] Thermally conductive fillers contemplated for optional use in the practice of the present invention include, for example, aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, magnesium oxide, silicon dioxide, aluminum oxide, zirconium silicate, etc. Preferably, the particle size of these fillers is about 20 microns. If aluminum nitride is used as a filler, it is preferably passivated by an adherent conformal coating (e.g., silicon dioxide, etc.).

[0144] Preferably, the filler is a silane-treated filler, more preferably a silane-treated amorphous silica. When a filler is present, the additive-containing resin composition may contain up to about 75 wt%, or up to about 50 wt%, or up to about 25 wt%, or up to about 10 wt% of the filler, wherein the wt% is based on the total weight of the additive-containing composition.

[0145] The resin composition of the present invention may optionally include one or more additives such as toughening agents, antioxidants, dyes, pigments, surfactants, defoamers, silane coupling agents, dispersants, thixotropic agents, processing aids, flow modifiers, curing accelerators, strength enhancers, toughening agents, UV protectants (especially UV blocking dyes suitable for realizing automatic optical inspection (AOI) of circuits), flame retardants, etc., and mixtures of any two or more thereof.

[0146] Tougheners (also known as plasticizers) contemplated for use in certain embodiments of the present invention include compounds that reduce the brittleness of the formulation, such as branched polyalkanes or polysiloxanes that reduce the glass transition temperature of the composition. Such plasticizers include, for example, polyethers, polyesters, polythiols, polysulfides, polybutadiene, styrene-based block copolymers, polybutadiene polystyrene copolymers such as those based on Poly and When used, plasticizers are generally present at about 0.5% to about 30% by weight of the additive-containing composition.

[0147] Antioxidants contemplated for use in the practice of the present invention include hindered phenols (e.g., BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), TBHQ (tert-butylhydroquinone), 2,2'-methylenebis(6-tert-butyl-p-cresol), etc.), hindered amines (e.g., diphenylamine, N,N'-bis(1,4-dimethylpentyl-p-phenylenediamine, N-(4-anilinophenyl)methacrylamide, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, etc.), phosphites, etc. When used, the amount of antioxidant is generally about 100 to 2000 ppm relative to the weight of the composition containing the additive.

[0148] Dyes contemplated for use in certain embodiments of the present invention include nigrosine, olanthol blue GN, phthalocyanines, fluorescent dyes (e.g., fluorescent green gold dyes, etc.), etc. When used, organic dyes provide contrast in relatively low amounts (i.e., amounts less than about 0.2% by weight relative to the weight of the composition containing the additive).

[0149] Pigments contemplated for use in certain embodiments of the present invention include any particulate material added for the sole purpose of imparting color to the formulation, such as carbon black, metal oxides (e.g., Fe 2 O 3 , titanium oxide), etc.

[0150] When present, pigments are generally present at about 0.5 wt % to about 5 wt % relative to the weight of the resin composition containing the additive.

[0151] Tougheners contemplated for use in the practice of the present invention are materials that impart enhanced impact resistance to various articles. Exemplary tougheners include synthetic rubber-containing compounds such as Hypro, Hypox, and the like.

[0152] UV protectants contemplated for use in certain embodiments of the present invention include compounds that absorb incident ultraviolet (UV) radiation, thereby reducing the negative effects of such exposure on the resin or polymer system into which the protectant is added. Exemplary UV protectants include bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, silicon, powdered metal compounds, hindered amines (referred to in the art as "HALS"), and the like.

[0153] Defoamers contemplated for use in certain embodiments of the present invention include materials that inhibit the formation of foam or bubbles when a liquid solution is stirred or sheared during processing. Exemplary defoamers contemplated for use herein include n-butanol, silicon-containing defoamers, and the like.

[0154] Exemplary silane coupling agents contemplated for use in the practice of the present invention include materials that form a bridge between the inorganic surface and the reactive polymer component, including materials such as epoxy silanes, amino silanes, and the like.

[0155] Exemplary thixotropic agents contemplated for use in the practice of the present invention include materials that impart enhanced flow properties to a liquid when shear is applied, including materials such as high surface area fillers (e.g., fumed silica) having particle sizes of about 2-3 microns or even submicron sizes.

[0156] Curing

[0157] After the curable resin composition has been prepared, for example, by carrying out a process comprising mixing compounds (a), (b) and (c) and reacting them in the presence of a base, or alternatively by mixing one or more compounds C1 and one or more compounds C2, or by any other process, the resin is separated from the reaction medium. The resin obtained can be used for various applications. In particular, the resin is used as such or mixed with one or more additives (such as those cited above as examples) before curing to produce a cured article.

[0158] The resin composition of the present invention can be prepared by appropriately mixing the above components, that is, mixing a mixture of C1 / C2, or a product formed by the reaction of compounds (a), (b) and (c) with the additives disclosed above (co-curing agent, filler, antioxidant, catalyst, etc.), and kneading or mixing by a kneading device (e.g., a three-roll mill, a ball mill, a pearl mill or a sand mill) or a stirring device (such as a high-speed rotary mixer, a super mixer or a planetary mixer) as needed.

[0159] In another embodiment, the composition can be dissolved or dispersed in an organic solvent to form a resin composition varnish before curing. The amount of the solvent is not limited, but is generally used in an amount sufficient to provide a solid concentration of at least 30% by weight to no more than 90% by weight solids, or about 50-85% by weight solids, or about 55-75% by weight solids in the solvent.

[0160] There is no particular restriction on the organic solvent, and it can be ketone, aromatic hydrocarbon, ester, amide or alcohol. More specifically, the example of the organic solvent that can be used includes acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate, N-methylpyrrolidoneformamide, N-methylformamide, N,N-dimethylacetamide, methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether and their mixture.

[0161] The curable resin composition of the present invention can be cured by a known method such as heat, light or electron beam.

[0162] When the resin is cured by heat, the curing temperature varies depending on the type of polymerizable unsaturated group and the type and amount of the curing agent used. Generally, the curing temperature is 20°C to 250°C, preferably 50°C to 250°C.

[0163] application

[0164] According to yet another embodiment of the present invention, there is provided an article comprising a partially or fully cured layer of the above composition, preferably bonded to a substrate.

[0165] The cured product can be suitably used for organic insulating materials and the like, for electronic equipment such as communication equipment, and particularly for the production of high-frequency laminates.

[0166] It has been found that using the compositions of the present invention it is possible to achieve ultra-low loss factors Df in the gigahertz range (eg, 1-10 GHz, well below 0.00179 at 10 GHz), which is unexpected in light of the prior art.

[0167] Specifically, the article obtained after curing of the curable resin composition according to the present invention has a dielectric loss factor (Df) of less than 0.00100 measured on a separate dielectric resonator (SPDR) at a frequency of 10 GHz. It is important to note that the maximum uncertainty of the dielectric loss factor of the organic film characterized by SPDR is 10%, with the error usually in the 4th decimal place. In addition, it is known in the art that it can be challenging to reduce the loss factor of hydrocarbon materials to below 0.00100 due to defects that are usually introduced into the polymer structure.

[0168] According to advantageous embodiments, articles formed by curing the compositions of the present invention have a dielectric constant (Dk) of less than about 3, or less than about 2.9, or less than about 2.8 at 10 GHz.

[0169] The selection of the biphenyl compound of formula 2 and / or the biphenyl of formula F4 provides a special effect for the composition. This ultra-low loss resin can be used to manufacture copper-clad laminate (CCL), which is also used to manufacture printed circuit boards (PCB). The PCB obtained by the resin composition according to the present invention shows improvements relative to existing material solutions, particularly in processing, dielectric properties, thermomechanical properties and reduced water sensitivity. The composition of the present invention imparts the main final properties of PCB. The composition of the present invention can provide a resin showing higher thermomechanical properties and higher moisture resistance. The effect from the composition of the present invention is also related to higher thermal decomposition temperature (Td2 / Td5), higher thermal properties (G' start) and lower loss (dissipation) factor (Df).

[0170] The present invention relates to a method for manufacturing an article, said method comprising at least the steps of preparing a curable resin composition, shaping the composition and curing the composition.

[0171] In the context of the present invention, preparing a curable resin composition means:

[0172] Prepare a curable resin composition according to the method disclosed above, or

[0173] preparing a curable resin composition comprising at least the compound having formula C1 and the compound having formula C2 disclosed above,

[0174] The composition optionally comprises one or more additives, such as a catalyst curing agent, a crosslinking curing agent, a curing accelerator, a free radical inhibitor, a filler.

[0175] Shaping includes structuring the composition by giving it a desired shape, and / or combining the composition with another material (eg, a support material, also referred to as a substrate or support article). Shaping may include the step of dissolving the resin composition in a solvent.

[0176] Several variants of the method for manufacturing an article according to the present invention are described in detail below:

[0177] The present invention also relates to a method for manufacturing an article, such as a high frequency laminate, comprising at least the following steps:

[0178] - Step 1: preparing a curable resin composition,

[0179] - step 2: dissolving the curable resin composition of step 1 in a solvent to form a varnish, and applying the varnish to a supporting article,

[0180] - Step 3: Allowing the composition to cure.

[0181] Applying the varnish to the support article may be performed by any method known to those skilled in the art, such as brushing the curable resin composition onto the support article, spraying the curable resin composition onto the support article, or spin coating the curable resin composition onto the support article.

[0182] The present invention further relates to a method for manufacturing an article, in particular a high frequency laminate, comprising at least the following steps:

[0183] - Step 1: preparing a curable resin composition,

[0184] - step 2: impregnating a support material, in particular a fibrous material, with the composition of step 1,

[0185] - Step 3: Allowing the composition to cure.

[0186] Impregnation of the fiber material with the curable resin composition can be carried out by any method known to those skilled in the art, such as immersing the fiber material in a solution of the curable resin composition, spraying the curable resin composition on the fiber material, or spin coating the curable resin composition on the fiber material. These methods may require dissolving the curable resin composition in a solvent to form a varnish.

[0187] The present invention further relates to a method for manufacturing an article, comprising at least the following steps:

[0188] - Step 1: preparing a curable resin composition,

[0189] - Step 2: introducing the composition of step 1 into the mold,

[0190] - Step 3: Allowing the composition to cure.

[0191] The invention also relates to an article obtained by a process comprising at least a step of curing the composition according to the invention.

[0192] The compositions of the present invention can provide products that can be used in a variety of applications, such as prepregs, metal clad laminates (eg, copper clad laminates), printed circuit boards, light emitting diodes, and electronic coatings.

[0193] In particular, the present invention relates to a prepreg obtained by impregnating a fiber material with a curable resin composition according to the present invention and curing the resin.

[0194] The present invention also provides a laminated sheet which can be used as a high-frequency laminate, wherein the laminated sheet comprises the prepreg defined above and a conductive material layer located on at least one surface of the prepreg.

[0195] The present invention also relates to a printed wiring board produced by forming a conductive pattern on the surface of the laminated sheet defined above.

[0196] As will be readily appreciated by those skilled in the art, a variety of fiber materials are suitable as substrate / support articles for use in the practice of the present invention, such as polyesters, liquid crystal polymers, polyamides (e.g., aromatic polyamides), polyimides, polyamide-imides, polyolefins, polyphenylene ethers, polyphenylene sulfides, polybenzoxazines, conductive materials (e.g., conductive metals), and the like, and combinations of any two or more thereof.

[0197] When a conductive metal substrate is used as the support article, materials such as silver, nickel, gold, cobalt, copper, aluminum, alloys of these metals, and the like are contemplated for use herein.

[0198] According to another embodiment of the present invention, there is provided a method for making the above-mentioned article (i.e., an article comprising a composition according to the present invention on a substrate / supporting article), the method comprising applying the resin composition to a substrate and, if an organic solvent is optionally used to facilitate such application, removing substantially all of the organic solvent therefrom. The resin composition may be applied to the substrate by dipping, impregnation, spraying, etc.

[0199] According to a further embodiment of the present invention, there is provided a prepreg produced by impregnating a porous substrate with a composition according to the present invention and, if an organic solvent is optionally used to facilitate such impregnation, subjecting the resulting impregnated substrate to conditions suitable for removing substantially all of the organic solvent therefrom.

[0200] As those skilled in the art will readily appreciate, a variety of porous substrates can be used to prepare the prepreg blanks of the present invention. The porous substrate can be woven or non-woven. The thickness of such substrates is not particularly limited, and can be, for example, about 0.01 mm to 0.3 mm.

[0201] Examples of porous substrates may include, but are not limited to, woven glass, nonwoven glass, woven aramid fibers, nonwoven aramid fibers, woven liquid crystal polymer fibers, nonwoven liquid crystal polymer fibers, woven synthetic polymer fibers, nonwoven synthetic polymer fibers, randomly dispersed fiber reinforcements, expanded polytetrafluoroethylene (PTFE) structures, and combinations of any two or more thereof.

[0202] Specifically, the material expected to be used as the porous substrate may include, but is not limited to, glass fiber, quartz, polyester fiber, polyamide fiber, polyphenylene sulfide fiber, polyetherimide fiber, cyclic olefin copolymer fiber, polyalkylene fiber, liquid crystal polymer, poly(p-phenylene-2,6-benzobisoxazole), copolymer of polytetrafluoroethylene and perfluoromethyl vinyl ether (MFA), and combinations of any two or more thereof.

[0203] According to still another embodiment of the present invention, there is provided a laminated sheet produced by laminating and molding a prescribed number of sheets of the above-mentioned prepreg.

[0204] The laminated sheet according to the present invention has many particularly beneficial properties, such as low dielectric constant, low loss factor, high thermal decomposition temperature, etc. In a preferred embodiment, the laminated sheet according to the present invention has a nominal dielectric constant of ≤3.0 and a loss factor of ≤0.002 at 10 GHz, and has a glass transition temperature of at least 100°C or at least 150°C.

[0205] In one aspect of the invention, the laminated sheet described herein may optionally further comprise one or more conductive layers. Such optional conductive layers are selected from metal foils, metal plates, conductive polymer layers, etc. In one embodiment, the metal may be copper, silver, nickel, gold, cobalt, aluminum, and alloys of these metals.

[0206] In another embodiment, a method of forming a laminate is provided. The method comprises contacting a porous substrate with a varnish bath comprising a resin composition of the present invention dissolved and intimately mixed in a solvent or solvent mixture. The contact occurs under conditions such that the porous substrate is coated with the resin composition. Thereafter, the coated porous substrate is passed through a heating zone having a temperature sufficient to evaporate the solvent but below a temperature at which the resin composition undergoes significant curing during its residence time in the heating zone to form a prepreg.

[0207] The residence time of the porous substrate in the bath is preferably from 1 second to 300 seconds, more preferably from 1 second to 120 seconds and most preferably from 1 second to 30 seconds. The temperature of this bath is preferably from 0° C. to 100° C., more preferably from 10° C. to 40° C. and most preferably from 15° C. to 30° C. The residence time of the coated porous substrate in the heating zone is from 0.1 minute to 15 minutes, more preferably from 0.5 minute to 10 minutes and most preferably from 1 minute to 5 minutes.

[0208] The temperature of this zone is sufficient to volatilize any remaining solvent, but not so high as to cause the components to fully cure during the residence time. The preferred temperature of this zone is 80°C to 250°C, more preferably 100°C to 225°C and most preferably 150°C to 210°C. Preferably there is a means for removing the solvent in the heating zone, which removes the solvent by passing an inert gas through the oven or drawing a slight vacuum on the oven. In many embodiments, the coated substrate is exposed to the zone with elevated temperature. The first zone is designed to volatilize the solvent so that the solvent can be removed. The subsequent zone is designed to partially cure the resin composition (B-staging).

[0209] Preferably, one or more prepreg sheets are optionally processed into a laminate together with one or more conductive materials such as copper sheets. In this further processing, one or more sections or parts of the coated porous substrate are contacted with each other and / or with a conductive material. Afterwards, the contacted parts are exposed to an elevated pressure and temperature sufficient to cure the components, wherein the resin on the adjacent parts reacts to form a continuous resin matrix between the porous substrates. Before curing, the parts can be cut and stacked or folded and stacked into parts with a desired shape and thickness. The pressure used can be any pressure from 1psi to 1000psi, wherein 10psi to 800psi is preferred. The temperature of the resin composition used in the cured parts or laminates depends on the specific residence time, the pressure used, and the components used. The preferred temperature that can be used is 100°C to 250°C, more preferably 120°C to 220°C, and most preferably 170°C to 200°C. The residence time is preferably 10 minutes to 120 minutes and more preferably 20 minutes to 90 minutes.

[0210] In one embodiment, the method is a continuous method, wherein the porous substrate is taken out of the oven and appropriately arranged into the desired shape and thickness and pressed at a very high temperature for a short time. Specifically, this high temperature is 180°C to 250°C, more preferably 190°C to 210°C, and the time is 1 minute to 10 minutes and 2 minutes to 5 minutes. This high speed pressing allows for more efficient use of processing equipment. In this embodiment, the preferred reinforcing material is a glass mesh or a woven cloth.

[0211] In some embodiments, it is desirable to subject the laminate or final product to post-curing outside the press. This step is designed to complete the curing reaction. The post-curing is typically performed at 130° C. to 220° C. for a period of 20 minutes to 200 minutes. The post-curing step may be performed in a vacuum to remove any components that may volatilize.

[0212] Therefore, according to yet another embodiment of the present invention, there is provided a method of manufacturing a laminated sheet, the method comprising stacking and molding a prescribed number of sheets of the prepreg according to the present invention.

[0213] According to another embodiment of the present invention, there is provided a printed wiring board produced by forming a conductive pattern on the surface of the above-mentioned laminated sheet. The conductive pattern can be formed by, for example, forming a resist pattern on the surface of the laminated sheet, removing unnecessary parts of the sheet by etching, removing the resist pattern, forming a desired through hole by drilling, forming a resist pattern again, electroplating to connect the through hole, and finally removing the resist pattern.

[0214] According to another embodiment of the present invention, there is provided a multilayer printed wiring board produced by stacking and molding a specified number of sheets of the above-mentioned patterned laminate layer, bonding them together with one or more layers of prepreg, and preparing a printed wiring board layer from the prepreg.

[0215] According to still another embodiment of the present invention, there is provided a method of manufacturing a printed wiring board, the method comprising forming a conductive pattern on a surface of the laminated sheet according to the present invention.

[0216] According to another embodiment of the present invention, a multilayer printed wiring board is provided, which is produced by stacking and molding a specified number of sheets of the above-mentioned prepreg to obtain a printed wiring board for an inner layer, and stacking the prepreg on the printed wiring board for an inner layer to form a conductive pattern on its surface.

[0217] Therefore, the prepreg and printed wiring board of the present invention can be used as components of printed circuit boards for various electrical and electronic devices (such as mobile communication devices or base station devices thereof that process high-frequency signals of GHz or higher) and network-related electronic devices (such as servers and routers) and networks in large computers.

[0218] The invention will now be further described with reference to the following non-limiting examples.

[0219] Examples

[0220] Materials and methods

[0221] Tetrabutylammonium bromide (99+%) Supplier: Thermo Fisher Scientific, Belgium.

[0222] Vinylbenzyl chloride (mixture of ortho / meta / para isomers). Supplier: AK Scientific, Inc., USA.

[0223] Indene (90%, technical grade, stabilized). Supplier: Thermo Fisher Scientific, Belgium.

[0224] 4,4'-Bis(chloromethyl)biphenyl (>95%) Supplier: Tokio Chemical Industry Co., LTD., Belgium.

[0225] α,α'-Dichloro-p-xylene (98%). Supplier: Merck KGaA, Germany.

[0226] TGA stands for thermogravimetric analysis according to ISO 11358.

[0227] DMA stands for Dynamic Mechanical Analysis - ISO 6721.

[0228] GPC stands for gel permeation chromatography.

[0229] 1H-NMR: 1H-nuclear magnetic resonance spectrum.

[0230] G'onset: The storage modulus G' is a measure of the elastic behavior of the sample. G'onset refers to the temperature at which the cured resin undergoes a change from a glassy state to a softer, more rubbery state.

[0231] Td2 / Td5: Td2 is the temperature when the weight loss of the sample reaches 2%. Td5 is the temperature when the weight loss of the sample reaches 5%.

[0232] Examples 1-5 - According to the present invention

[0233] Example 1

[0234] 32.8 g (0.131 mol) of 4,4'-bis(chloromethyl)biphenyl, 25.0 g (0.209 mol) of indene, 3.4 g (0.010 mol) of tetrabutylammonium bromide and 41.1 g (0.269 mol) of vinylbenzyl chloride were dissolved in 500 mL of toluene under continuous stirring at an internal temperature of 40°C in a 1.5-liter reaction flask equipped with a mechanical stirrer, a cooling condenser and a dropping funnel to prepare a homogeneous solution. 140 mL (2.610 mol) of a 50 wt % aqueous solution of NaOH was added dropwise over 30 minutes. After the addition was complete, the internal temperature was raised to 50°C by external heating. After a reaction time of 9 hours, the mixture was diluted with water and the two layers were separated. Toluene was removed by distillation to obtain 69.7 g (88% yield) of the yellow solid material of Example 1.

[0235] The obtained compound 1 of Example 1 was analyzed by its 1H-NMR spectrum ( Figure 1 ) and GPC measurements. GPC showed a weight average molecular weight Mw = 2886 g / mol and a polydispersity of 2.8. The molar ratio of all chloromethyl groups to indene reactive sites was 0.85.

[0236] Example 2

[0237] The same synthetic procedure as in Example 1 was used, except that another molar ratio was used: indene (1 molar equivalent), 4,4'-bis(chloromethyl)biphenyl (0.50 molar equivalent) and vinylbenzyl chloride (1.13 molar equivalent). Compound 2 was obtained as a yellow solid material in 86% yield, and its 1H-NMR spectrum ( Figure 2 ) and GPC measurements. GPC showed a weight average molecular weight Mw = 1411 g / mol and a polydispersity of 2.6. The molar ratio of all chloromethyl groups to indene reactive sites was 0.71.

[0238] Example 3

[0239] The same synthetic procedure as the one described in Example 1 above was used, except that different molar ratios were used: indene (1 molar equivalent), 4,4'-bis(chloromethyl)biphenyl (0.40 molar equivalent) and vinylbenzyl chloride (1.34 molar equivalent). Compound 3 was obtained as a yellow solid material in 87% yield, and its 1H-NMR spectrum ( Figure 3 ) and GPC measurements. GPC showed a weight average molecular weight Mw = 1091 g / mol and a polydispersity of 2.3. The molar ratio of chloromethyl groups to indene reactive sites was 0.71.

[0240] Example 4

[0241] The same synthetic procedure as described in Example 1 was used, except that different molar ratios were used: indene (1 molar equivalent), 4,4'-bis(chloromethyl)biphenyl (0.44 molar equivalent) and vinylbenzyl chloride (1.47 molar equivalent). Compound 4 was obtained as a yellow solid material in 83% yield, and its 1H-NMR spectrum ( Figure 4 ) and GPC measurements. GPC showed a weight average molecular weight Mw = 1216 g / mol and a polydispersity of 2.1. The molar ratio of all chloromethyl groups to indene reactive sites was 0.78.

[0242] Example 5

[0243] The same synthetic procedure as the one shown in Example 1 was used, but with different molar ratios: indene (1 molar equivalent), 4,4'-bis(chloromethyl)biphenyl (0.51 molar equivalent) and vinylbenzyl chloride (1.73 molar equivalent). Compound 5 was obtained as a yellow solid material in 88% yield, and Example 5 was confirmed by its 1H-NMR spectrum ( Figure 5 ) and GPC measurements. GPC showed a weight average molecular weight Mw = 1726 g / mol and a polydispersity of 2.4. The molar ratio of all chloromethyl groups to indene reactive sites was 0.92.

[0244] Table 1 below shows the compositions disclosed above when mixed with fillers for Examples 1 to 5.

[0245] Table 1

[0246]

[0247] a) SC2300-SVJ (Admatechs)

[0248] Application Examples

[0249] -Application on metal film

[0250] The compounds mentioned in Table 1 were dissolved in toluene at a concentration of 40% by weight at room temperature, and then silica fillers were added to produce a uniform resin composition varnish. The uniform resin composition was cast onto a metal plate under ambient conditions, and toluene was evaporated overnight. The pre-dried resin film was placed in an oven and gradually cured using the following curing cycle under nitrogen: 1 hour at 70°C, 1 hour at 90°C, 1 hour at 140°C, and 2 hours at 200°C. At a frequency of 10Ghz, the dielectric constant (Dk) and loss factor (Df) of the resulting plate having a thickness of about 0.5mm were evaluated on a separate dielectric resonator (SPDR), and the results are shown in Table 2 below.

[0251] Table 2

[0252]

[0253] a) SPDR, at 10GHz (25°C, 50% relative humidity)

[0254] b) TGA, 25°C to 800°C at 10K / min under nitrogen (w / o silica)

[0255] c) DMA ISO 6721, 25°C to 300°C at 5K / min (with 0.5% dicumyl peroxide)

[0256] -Preparation of prepreg:

[0257] After dissolving all the components shown in Table 1 in toluene at room temperature, a silica filler was added to produce a uniform resin composition varnish having a concentration of 50-60 wt % solid. A glass fabric (E2116NE glass) was dipped into the varnish, then placed upright in an oven, and dried at 150° C. for 3 minutes to produce a prepreg sheet.

[0258] - Preparation of laminate:

[0259] The sheets of the above prepreg were press cured at 220°C for 2 hours, with the resin content in the final laminate being about 45 wt% to about 50 wt%.

[0260] Comparative Example 6

[0261] The same synthesis procedure as disclosed in Example 1 was carried out, except that 4,4'-bis(chloromethyl)biphenyl was replaced by an equal molar amount of α,α'-dichloro-p-xylene. Compound 6 (Comparative Example) was obtained as a yellow solid material with a yield of 87%, and its 1H-NMR spectrum ( Figure 6 ) and GPC measurements. GPC showed a weight average molecular weight Mw = 2062 g / mol and a polydispersity of 2.5.

[0262] The compounds were further processed as disclosed above (see Table 3) and the results are shown in Table 4 below.

[0263] Table 3

[0264] Components Comparative Example 6 (pbw) Compound 6 100 <![CDATA[Fumed silica a) > 25

[0265] a) SC 2300-SVJ (Admatechs)

[0266] Table 4

[0267]

[0268] a) SPDR, at 10GHz (25°C, 50% relative humidity)

[0269] b) TGA, 25°C to 800°C at 10K / min under nitrogen (w / o silica)

[0270] c) DMA ISO 6721, 25°C to 300°C at 5K / min (with 0.5% dicumyl peroxide).

Claims

1. A curable resin composition comprising at least: (1) A compound having the following formula C1: wherein each R1 is independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a thioalkoxy group having 1 to 5 carbon atoms, a thioaryloxy group having 6 to 14 carbon atoms, and an aryl group having 6 to 14 carbon atoms, and combinations thereof, and Each F1 is independently selected from a hydrogen atom and a vinylbenzyl group and combinations thereof, provided that at least one F1 is a vinylbenzyl group: (2) A compound having the following formula C2: wherein each R1 is independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a thioalkoxy group having 1 to 5 carbon atoms, a thioaryloxy group having 6 to 14 carbon atoms, and an aryl group having 6 to 14 carbon atoms, and combinations thereof, and Each F2 is independently selected from a hydrogen atom, a vinylbenzyl Or a structure of formula F3, provided that at least one F2 is a structure of formula F3: in: - n, p and p' may independently be 0 to 50, preferably 0 to 10, - each R1 is independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a thioalkoxy group having 1 to 5 carbon atoms, a thioaryloxy group having 6 to 14 carbon atoms, and an aryl group having 6 to 14 carbon atoms, and combinations thereof, - each F'2 is independently selected from a hydrogen atom, a vinylbenzyl group, provided that at least one F2 or at least one F'2 is a vinylbenzyl group, F4 is selected from the divalent groups of formula F4 and combinations thereof: in: Each Q is independently selected from a hydrogen atom and a linear or branched C1-C6 alkyl group or a combination thereof; and Each R2 is independently selected from a hydrogen atom, a linear or branched C1-C6 alkyl group, a halogen atom, or a combination thereof.

2. The composition according to claim 1, wherein one or more of the following conditions are met: - each Q is independently selected from H, CH3 and combinations thereof, - all R1 groups represent H, - all R2 groups represent H, - All R3 groups represent H.

3. The composition according to claim 1 or 2, further comprising one or more fillers, preferably silane-treated fillers, more preferably silane-treated amorphous silica.

4. The composition of claim 3, wherein the one or more fillers comprise 10 to 40 weight percent, based on the total weight of the resin composition including the additive.

5. A method for preparing a curable resin composition, comprising at least the following steps: (i) mixing at least compounds (a), (b) and (c), and (ii) reacting the compound in the presence of a base: in Compound (a) is one or more indene compounds represented by the following general formula 1: wherein each R1 is independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a thioalkoxy group having 1 to 5 carbon atoms, a thioaryloxy group having 6 to 14 carbon atoms, and an aryl group having 6 to 14 carbon atoms, and combinations thereof, Compound (b) is one or more biphenyl compounds represented by the following general formula 2, in Each X is independently selected from halogen atoms, tosylate, mesylate, triflate, and combinations thereof, Each Q is independently selected from a hydrogen atom and a linear or branched C1-C6 alkyl group and combinations thereof, and Each R2 is independently selected from a hydrogen atom, a linear or branched C1-C6 alkyl group, a halogen atom, and combinations thereof, Compound (c) is one or more vinylbenzyl compounds represented by the following general formula 3: in X' is selected from the group consisting of halogen atoms, tosylate, mesylate, triflate, and combinations thereof.

6. A process according to claim 5, wherein the molar ratio of all halomethyl groups, preferably chloromethyl groups, in compounds (b) and (c), if present, to reactive sites in compound (a) is 0.95 or less.

7. The method according to claim 5 or 6, wherein the molar ratio of the indene compound (a) of Formula 1 to the biphenyl compound (b) of Formula 2 is 1.8 / 1 to 3 / 1.

8. The method according to any one of claims 5 to 7, wherein the molar ratio of the indene compound (a) of formula 1 to the vinylbenzyl compound (c) of formula 3 is 1 / 1 to 1 / 2, preferably 1 / 1.75, most preferably 1 / 1.

5.

9. The method according to any one of claims 5 to 8, wherein one or more of the following conditions are met: - each Q is independently selected from H, CH3 and combinations thereof, - all R1 groups represent H, - all R2 groups represent H, - All R3 groups represent H.

10. The method according to any one of claims 5 to 9, wherein the vinylbenzyl compound represented by the general formula 3 is selected from 2-vinylbenzyl chloride, 3-vinylbenzyl chloride, 4-vinylbenzyl chloride, 2-vinylbenzyl bromide, 3-vinylbenzyl bromide, 4-vinylbenzyl bromide and mixtures thereof, preferably the vinylbenzyl compound represented by the general formula 3 is a mixture of 10-50 wt% of 2-vinylbenzyl chloride, 0-10 wt% of 3-vinylbenzyl chloride and 50-80 wt% of 4-vinylbenzyl chloride.

11. The process according to any one of claims 5 to 10, wherein compound (b) is 4,4'-bis(chloromethyl)biphenyl.

12. The method according to any one of claims 5 to 11, wherein the method further comprises adding a Salt catalysts: tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium hydrogen sulfate, benzyltrimethylammonium chloride and trioctylmethylammonium chloride, tetra-n-butylammonium bromide Benzyltriphenyl chloride Tetraphenyl chloride Tetraphenyl bromide Benzyltetramethylenesulfonium bromide and mixtures thereof.

13. The method according to any one of claims 5 to 12, wherein the method further comprises adding a free radical inhibitor selected from the group consisting of quinones, phenols, catechols, phenothiazines, (2,2,6,6-tetramethylpiperidin-1-yl)oxy, hydroxylamines and their corresponding salts and mixtures thereof.

14. Curable resin composition obtainable or obtained by a method according to any one of claims 5 to 13.

15. A method of manufacturing an article, comprising at least the following steps: -Step 1: Preparing a curable resin composition according to any one of claims 1 to 4, comprising at least a compound having formula C1 and a compound having formula C2, or preparing a curable resin composition according to claim 14, The composition optionally comprises one or more additives, -Step 2: shaping the composition, -Step 3: The composition is allowed to cure.

16. An article obtained by carrying out the method of claim 15.

17. The article of claim 16 having a dielectric loss factor (Df) less than 0.00100 measured on a split dielectric resonator (SPDR) at a frequency of 10 GHz.

18. An article according to claim 16 or claim 17 which is a prepreg obtained by impregnating a fibre material with a composition according to any one of claims 1 to 4 or 14.

19. A high-frequency laminate comprising the prepreg according to claim 18 and a conductive material layer on at least one surface of the prepreg.

20. A printed wiring board produced by forming a conductive pattern on a surface of the laminated sheet according to claim 19.

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