Bismaleimide compounds, method for the preparation of bismaleimide compounds, bismaleimide compound, curable resin composition, process for manufacturing an article, article, laminate, printed circuit board, and use of the resin composition.

Abstract

Bismaleimide compounds of the formula (I) wherein R1 is a divalent aliphatic radical and R2 is a divalent aromatic radical; And resin compositions comprising said bismaleimide compounds of the formula (I), having a low dielectric constant (Dk), a low dielectric dissipation factor (Df) and a high glass transition temperature (Tg).

Description

/ 39 Bismaleimide compounds, method for the preparation of bismaleimide compounds, compound of Bismaleamide, curable resin composition, process for manufacturing an article, article, laminate, printed circuit board, and use of the resin composition field.

[001] This description relates to new bismaleimide compounds and resin compositions comprising said compounds, their manufacturing process and their uses in various applications, such as in the production of a prepreg, a laminated sheet for printed circuit boards, a molding material and an adhesive. The resin compositions provide a cured product having high heat resistance, low water absorption and excellent dielectric properties. These advantageous properties are necessary for organic insulating materials for use in electronic equipment, such as communication equipment. BACKGROUND

[002] With the development of wireless networks and satellite communications, electronic products are tending to require higher speed, frequency, and greater capacity for voice, video, and data transmission. Furthermore, as these electronic products become thinner and smaller, electrical circuit boards tend to increase in complexity, density, and multilayer stratification. In order to maintain high transmission rates and signal integrity, printed circuit boards (“PCBs”) need materials with a low dielectric constant (Dk) and low dielectric loss (sometimes also called loss factor or dissipation factor, Df) resulting in less signal loss.

[003] Polymeric insulating materials are commonly used as substrate materials for PCBs. The PCB laminate is made either solely from the polymeric insulating material or from a mixture of polymeric insulating materials. Petition 870250073583, dated 08 / 20 / 2025, page 11 / 57 / 39 with glass, fiber, nonwoven fabric, inorganic filler or similar. Epoxy resins have traditionally been employed due to their low cost and high heat and chemical resistance properties when cured. However, due to their relatively high dielectric constant and high dielectric loss tangent, it is difficult to achieve an adequate low dissipation factor in high-frequency signals. Polyphenylene ether (PPE) resins have also been used in laminates due to their lower dielectric constants and dissipation properties, but the use of high-frequency signals in new electronic fields requires even lower dielectric loss constants and dissipation factors.Fluorinated resins, typically represented by polytetrafluoroethylene (PTFE), have low dielectric constants and dissipation factors, but they are thermoplastic resins and therefore undergo significant expansion and contraction during molding and processing, in addition to being difficult to handle.

[004] Other types of resins are known, but they cannot achieve a low dielectric loss value Df, which is necessary considering the demands in high-frequency signal transmissions.

[005] Bismaleimide compounds are well known in the formulation of electronic materials:

[006] Document EP 3135722 describes a heat-curable resin composition for use in the electrical and electronic industry, which is suitable as an underfill and for performing filler work. The heat-curable resin composition contains a heat-curable resin and a bismaleimide compound in liquid form at 25°C.

[007] US patent 7,884,174 describes imide-extended mono-, bis-, or polymaleimide compounds and their use for the preparation of thermosetting adhesive compositions that find application for a variety of purposes in the manufacture and assembly of semiconductor packages and microelectronic devices. Petition 870250073583, dated 08 / 20 / 2025, page 12 / 57 / 39

[008] US patent 3,856,752 describes aromatic polyimides with improved solubility in polar organic solvents and their use as adhesives, laminating resins, especially for printed circuit boards, fibers, coatings, for decorative and electrical purposes, films, wire enamels and molding compounds.

[009] However, bismaleimide and aromatic polyimide compounds of the prior art suffer from disadvantages due to limited solubility and sensitivity to moisture.

[0010] The need remained for a resin composition that could be used in electronic equipment and that provided a higher dissipation factor and / or a higher decomposition temperature.

[0011] The need remained to provide a curable bismaleimide compound that would give access to a resin composition with improved properties, particularly in terms of Df, thermomechanical properties, moisture resistance, and that could be easily processed. There is a need to improve high-speed signal transmission while reducing power and interference problems in electronic applications. This requires a material composition with enhanced dielectric properties while ensuring thermomechanical properties and ease of fabrication, necessary for the sustainable high-volume production of printed circuit boards and antennas.

[0012] One objective of the present invention is to overcome the aforementioned disadvantages of prior art resin compositions and to provide improved polymeric insulating materials that have sufficient thermomechanical properties, moisture resistance, low dielectric characteristics, and are easily processable to handle the ever-increasing high-frequency signal transmissions. SUMMARY

[0013] The invention relates to new bismaleimide compounds from Petition 870250073583, dated 08 / 20 / 2025, p. 13 / 57 4 / 39 following formula (I): Formula (I) where n is an integer, n ranges from 1 to 10, m is an integer, m ranges from 1 to 10, each Q, independently, is a tetravalent radical selected from C6-C50 hydrocarbons comprising at least one aromatic group and optionally one or more heteroatoms selected from O, N, S, F, Cl, Br, each R1, independently, is a divalent radical selected from C1-C60 aliphatic and aromatic hydrocarbons, linear or branched, optionally comprising one or more NH2 groups, or one or more NH bridges, each R2, independently, is a divalent radical selected from C6-C54 aromatic hydrocarbons, optionally comprising one or more halogen atoms, R is a divalent radical selected from R1 and R2, each Y, independently, being H or CH3.

[0014] The invention also relates to new bismaleimide compounds resulting from a method comprising the following steps: Petition 870250073583, dated 08 / 20 / 2025, p. 14 / 57 5 / 39 Formula (I) • Step 1: react a dianhydride (IV) with a diamine of formula (II) and a diamine of formula (III) to obtain an extended amine-terminated imide (V), • Step 2: react the extended amine-terminated imide resulting from step 1 with a maleic anhydride compound (VI). where n, m, Q, RI, R2, R and Y have the same definition as in formula (I) above, An and Am, respectively, represent the relative molar quantity of the diamine H2N-RI-NH2 and the diamine H2N-R2-NH2 introduced into the reaction medium in relation to the amount of dianhydride.

[0015] The present invention also relates to a curable resin composition comprising at least one bismaleimide compound as described above and at least one heat-curable resin.

[0016] The present invention further relates to a process for manufacturing an article, comprising at least the following steps: Step 1: prepare a curable resin composition comprising Petition 870250073583, dated 08 / 20 / 2025, page 15 / 57 / 39 at least one bismaleimide compound as described above and a heat-curable resin, Step 2: to shape the composition, Step 3: partially or completely cure the composition.

[0017] The invention also relates to articles obtained by said method, including a cured resin, a cured resin in sheet form, a laminated body, a pre-impregnated material, electronic components and single and multilayer circuit boards comprising the resin compositions of the present description.

[0018] The invention also relates to the use of the resin composition as defined above in a prepreg, a metal-plated laminate, a printed circuit board, a light-emitting diode, an electronic coating, a textile, a polymer molding compound, a medical molding compound, and an adhesive.

[0019] The bismaleimide compounds according to the invention exhibit optimized thermomechanical (glass transition) performance with low dielectric constant and low loss at high frequencies, improved solubility in solvents such as MEK (methyl ethyl ketone), cyclohexanone, toluene, xylene, along with processing characteristics suitable for formulating electronic materials to improve dielectric and thermomechanical properties. DETAILED DESCRIPTION

[0020] The present description is generally directed to new bismaleimide compounds and to resin compositions obtained from these new bismaleimide compounds, said resins having a low dielectric constant (Dk), a low dielectric dissipation factor (Df) and excellent thermomechanical properties, such as high thermal stability, good Petition 870250073583, dated 08 / 20 / 2025, page 16 / 57 / 39 processability, high peel resistance, good moisture resistance and / or a high glass transition temperature (Tg). In attempting to achieve the objectives of the present description, it was surprisingly found that when a resin composition is made with the bismaleimide compounds described above, a significant reduction in Df can be achieved compared to a resin composition containing prior art resins, even though it has a high Tg. The new resin composition, as a whole, exhibits a low Dk and a low Df (typically Df < 0.003) in the gigahertz range (e.g., 1 to 10 GHz), allowing it to meet the stringent industrial standards required in a variety of applications, such as prepregs, metal-clad laminates, printed circuit boards, light-emitting diodes and electronic coatings.It exhibits high thermomechanical performance (high Tg) and high solubility (> 50% by weight in typical CCL (copper-clad laminate) solvents, such as toluene, MEK).

[0021] The new bismaleimide compounds and resin compositions can also be used in chip design (integrated circuit (IC) packaging), coatings, Chemical Vapor Deposition (CVD), and photochemistry. Furthermore, they can be used for the preparation of high-performance membranes, filters and coatings, fiber-reinforced composites, and adhesives. The new bismaleimide compounds can also be used as intermediates for radical and condensation polymerization formulators.

[0022] The following terms will have the following meanings: The term “comprising” and derivatives thereof are not intended to exclude the presence of any additional component, step, or procedure, whether or not it is described herein. For the avoidance of doubt, all compositions claimed herein by use of the term “comprising” may include any additive, adjuvant, or... Petition 870250073583, dated 08 / 20 / 2025, page 17 / 57 / 39 additional compound, unless otherwise indicated. In contrast, the term “essentially consisting of”, if it appears here, excludes from the scope of any subsequent recitation any other component, step or procedure, except those that are not essential to operability, and the term “consisting of”, if used, excludes any component, step or procedure not specifically outlined or listed. The term “or”, unless otherwise indicated, refers to the members listed individually, as well as in any combination.

[0023] The articles “a” and “an” are used here to refer to one or more than one (i.e., at least one) of the grammatical objects of the article. As an example, “a reticulator” means one reticulator or more than one reticulator. The phrases “in a modality,” “according to a modality,” and the like generally mean that the specific feature, structure, or resource following the phrase is included in at least one modality of the present description and may be included in more than one modality of the present description. It is important to note that such phrases do not necessarily refer to the same aspect. If the descriptive report states that a component or feature “may,” “could,” or “might” be included in or have a feature, that specific component or feature need not be included in or have the feature.

[0024] The term “about”, as used herein, may allow for a degree of variability in a value or range, for example, it may be within 10%, within 5%, or within 1% of a stated value or a stated limit of a range.

[0025] Values ​​expressed in a range format should be interpreted flexibly to include not only the explicitly recited numerical values ​​as the range boundaries, but also to include all individual numerical values ​​or subranges encompassed within that range, as if each numerical value and subrange were explicitly recited. Petition 870250073583, dated 08 / 20 / 2025, page 18 / 57 / 39 For example, a range, such as 1 to 6, should be considered as having specifically described sub-ranges, such as 1 to 3, 2 to 4, 3 to 6, etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the range's width.

[0026] The terms “preferred” and “preferably” refer to modalities that may provide certain benefits under certain circumstances. However, other modalities may also be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred modalities does not imply that other modalities are not useful and is not intended to exclude other modalities from the scope of this description.

[0027] The term “in the range” or “within a range” (and similar statements) includes the endpoints of the stated range.

[0028] When substituent groups are specified by their conventional chemical formula, written from left to right, they equally encompass chemically identical substituents that would result from writing the structure from right to left, for example, -CH2O- is equivalent to -OCH2-.

[0029] The term “optional” or “optionally” means that the event or circumstance described below may or may not occur, and that the description includes cases in which the said event or circumstance occurs and cases in which it does not occur.

[0030] The term “alkyl” refers to a linear or branched hydrocarbyl radical having 1 to 50 carbon atoms, and “substituted alkyl” refers to an alkyl containing additionally one or more substituents selected from, but not limited to, hydroxy, alkoxy, mercapto, cycloalkyl, heterocyclic, aryl, heteroaryl, aryloxy, halogen, trifluoromethyl, cyano, nitro, nitrone, amino, amido, C(O)H, acyl, oxyacyl, carboxyl, carbamate, sulfonyl, sulfonamide and sulfuryl.

[0031] The term “alkenyl” refers to a linear hydrocarbyl radical. Petition 870250073583, dated 08 / 20 / 2025, p. 19 / 57 / 39 or branched having from 2 to 50 carbon atoms and at least one carbon-carbon double bond.

[0032] The term “alkynyl” refers to a linear or branched hydrocarbyl radical having from 2 to 50 carbon atoms and at least one carbon-carbon triple bond.

[0033] The term “aromatic” refers to a hydrocarbyl radical having 6 to 50 carbon atoms that contains at least one ring with delocalized pi electrons, such as a benzene ring.

[0034] The term “aralkyl” refers to any univalent radical derived from an alkyl radical by the substitution of one or more hydrogen atoms by aryl groups.

[0035] The terms “dielectric dissipation factor (Df)” and “loss tangent”, as used in this document, are synonymous and refer to the amount of energy dissipated (i.e., electrical loss) in an insulating material when a voltage is applied to the circuit. Df represents the signal loss in the circuit.

[0036] The terms “dielectric constant (Dk)” and “permittivity”, as used in this document, are synonymous and refer to a measurement of the relative capacitance of an insulating material with respect to air or vacuum. The dielectric constant determines the speed of the electronic signal.

[0037] The term “glass transition temperature” or “Tg”, as used herein, means the temperature at which the amorphous domains of a polymer assume the characteristic properties of the glassy state: brittleness, stiffness, and firmness. The term also means the temperature at which cured resins undergo a change from a glassy state to a softer, more elastic state. Bismaleimide compounds

[0038] According to a first aspect, the invention relates to new bismaleimide compounds of the following formula (I): Petition 870250073583, dated 08 / 20 / 2025, page 20 / 57 11 / 39 Formula (I) wherein n is an integer, n ranges from 1 to 10, preferably n ranges from 1 to 5, m is an integer, m ranges from 1 to 10, preferably n ranges from 1 to 5, each Q, independently, is a tetravalent radical selected from C6-C50 hydrocarbons comprising at least one aromatic group and optionally one or more heteroatoms selected from O, N, S, F, Cl, Br, each R1, independently, is a divalent radical selected from C1-C60 aliphatic and aromatic hydrocarbons, linear or branched, optionally comprising one or more NH2 groups, or one or more NH bridges, each R2, independently, is a divalent radical selected from C6-C54 aromatic hydrocarbons, optionally comprising one or more halogen atoms, R is a divalent radical R1 or R2, Y represents H or CH3. Preferably, Y is H.

[0039] Q is the tetravalent radical present in the aromatic dianhydride that reacted with the diamine H2N-RI-NH2 and the diamine H2N-R2-NH2.

[0040] Examples of radical Q structures include the following: Petition 870250073583, dated 08 / 20 / 2025, p. 21 / 57 / 39 with Q', a divalent radical that may be selected from C1-C38 hydrocarbons optionally comprising one or more heteroatoms selected from O, N, S, F, Cl, Br.

[0041] For example, Q' can be -CO-, -CO-NH-, -CO-O-, -O-CO-O, -NH-CO-NH-, a divalent C1-C40 alkyl radical, a divalent C1-C40 alkenyl radical, a divalent C1-C40 alkynyl radical, the so-called alkyl, alkenyl or alkynyl radical optionally comprising one or more -O- bridges, one or more -NH- bridges, one or more substituents selected from -OH, NH2, COOH, CONH2, -SH, -SO3H, a halogen atom.

[0042] According to a favorite modality, Q is selected from the following radicals: Petition 870250073583, dated 08 / 20 / 2025, page 22 / 57 / 39 Each R1, independently, is a divalent radical selected from C1-C60 aliphatic and aromatic hydrocarbyls, linear or branched, optionally comprising one or more NH2 groups, one or more NH bridges. Preferably, each R1, independently, is a divalent radical selected from C1-C60 alkyl, C2-C60 alkenyl, C2-C60 alkynyl, C6-C60 aralkyl, optionally comprising one or more NH2 groups, one or more NH bridges.

[0043] Each R1, independently, can be linear or branched.

[0044] Advantageously, each R1, independently, is selected from C1-C60 alkyl, alkenyl or aralkyl, optionally comprising one or more NH2 groups, one or more NH bridges, preferably from C12-C60 alkyl, alkenyl or aralkyl, optionally comprising one or more NH2 groups, one or more NH bridges.

[0045] More advantageously, each R1 is independently selected from dimeric and trimeric hydrocarbon groups with a total number of C atoms from 12 to 60, and mixtures thereof.

[0046] Advantageously, R1 is selected from linear, branched or cyclic alkyl or alkenyl, or aromatic hydrocarbons with a total number of C atoms from 12 to 60, and mixtures thereof.

[0047] Each R2, independently, is a divalent radical selected from C6-C54 aromatic hydrocarbons.

[0048] Preferably, R2 is a C6-C54 aromatic divalent radical comprising a phenylindane group.

[0049] Advantageously, R2 is selected from radicals Petition 870250073583, dated 08 / 20 / 2025, p. 23 / 57 14 / 39 divalents of the formula (ΠΙΑ) Formula (IHA) in which Y1, Y2, independently, represent H, a C1-C5 alkyl group; each Y3, Y4, independently, represents H, a halogen, a C1-C4 alkyl group.

[0050] When Y3 and / or Y4 is a halogen, preferably it is Cl.

[0051] Preferably, in formula (IIIA), all Y3 and Y4 represent H.

[0052] Preferably, in formula (ΠΙΑ), Yl, Y2, independently, represent H or a methyl group. According to one embodiment, Yl and Y2 represent CH3.

[0053] Preferably, in formula (IIIA), the radical substituents are located in positions 5' or 6' and in position 4'. Preparation of the bismaleimide compound

[0054] The invention also relates to new bismaleimide compounds resulting from a method comprising the following steps: Petition 870250073583, dated 08 / 20 / 2025, p. 24 / 57 15 / 39 • Step 1: react a dianhydride (IV) with a diamine of formula (II) and a diamine of formula (III) to obtain an extended amine-terminated imide (V), • Step 2: react the extended amine-terminated imide (V) resulting from step 1 with a maleic anhydride compound (VI). where n, m, Q, RI, R2, R and Y have the same definitions and preferred modalities as formula (I) above, An and Am, respectively, represent the relative molar amounts of diamine H2N-RI-NH2 (II) and diamine H2N-R2-NH2 (III) introduced into the reaction medium in relation to the amount of dianhydride (IV).

[0055] As examples of aromatic dianidride (IV), we can mention: pyromellitic dianidride; 1,4,5,8-naphthalenetetracarboxylic dianidride; 2,3,6,7-naphthalenetetracarboxylic acid dianidride; 1,2,4,5-naphthalenetetracarboxylic acid dianidride; 1,2,5,6naphthalenetetracarboxylic acid dianidride; benzene-1,2,3,4tetracarboxylic acid dianidride; pyrazine-2,3,5,6-tetracarboxylic acid dianidride; thiophene-2,3,4,5-tetracarboxylic acid dianidride; dianidride 3,4,9,10Petição 870250073583, of 20 / 08 / 2025, page 25 / 57 / 39 perylene-tetracarboxylic acid; dianidride of 2,3,9,10-perylene-tetracarboxylic acid; dianidride of 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid; dianidride of 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid; dianidride of 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid; dianidride of phenanthrene-1,8,9,10-tetracarboxylic acid;

[0056] 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride; 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride; 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride; 2,2',3,3'-biphenyltetracarboxylic acid dianhydride; 4,4'-oxyphthalyl anhydride; 3,3'-oxyphthalic anhydride; 4,4'-isopropylidenediphthalic anhydride; 3,3'-isopropylidenediphthalic anhydride; 3,3',4,4'-diphenylsulfone tetracarboxylic acid dianhydride; 4,4'-sulfonyldipthalic anhydride; 4,4'-methylenediphthalic anhydride; 4,4'-thiodiphthalic anhydride; 4,4'-ethylidene diphthalic anhydride; 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; 4,4'-bisphenol A dipthalic anhydride; ethylene glycol bis(trimelitate anhydride); hydroquinone dipthalic anhydride.

[0057] According to a favorite embodiment, the aromatic dianhydride (IV) is pyromellitic dianhydride or 3,3',4,4'-benzophenone tetracarboxylic dianhydride.

[0058] Amines of formula (II) are commercially available. Examples of diamines (II), NH2-R1-NH2, that can be used according to the invention include: 1,10-diaminodecane; 1,12-diaminododecane; 1,18-diamino-6,8-dialkylene; dimer diamine such as C36-alkylene diamines; trimeric amines such as C54 trimeric amine; 1,2-diamino-2-methylpropane; 1,2-diaminocyclohexane; 1,2-diaminopropane; 1,3-diaminopropane; 1,4-diaminobutane; 1,5-diaminopentane; 1,7-diaminoheptane; 1,8-diaminomentane; 1,8-diaminooctane; 1,9-diaminononane; 3,3'-diamino-N-methyldipropylamine; 1,3-diaminopentane; 1,3-bisaminomethylcyclohexane; polyoxyalkylenediamines (e.g., Huntsman's Jeffamine D230, D400, D-2000 and D-4000 products); 1,3-cyclohexanebis(methylamine); bis(4 Petition 870250073583, dated 08 / 20 / 2025, page 26 / 57 / 39 amino-3-methylcyclohexyl)methane; 1,2-bis(2-aminoethoxy)ethane; 3(4),8(9)bis(aminomethyl)tricyclo(5.2.1.0<2,6> )decane.

[0059] Examples of amines include mixtures of amines marketed by Croda under the reference Priamine 1075 (mainly dimeric amine) or Priamine 1071 (includes a mixture of C36 dimeric amine and C54 trimeric amine).

[0060] Other examples of amines from which the R1 group can be obtained, being amines derived from dimerized fatty acids, are illustrated in the scheme below: _____ ,. nh2

[0061] Preferably, diamines (II), NH2-R1-NH2, are selected from aliphatic C12-C60 dimeric diamines, C12C60 trimer triamines and mixtures thereof.

[0062] Examples of aromatic diamines (III), NH2-R2-NH2, which can be used according to the invention include DAPI (4',5-6-Diamino-1,3,3-trimethyl-1-phenylindane); 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-diaminoanthraquinone; 2,6-diaminotoluene; 2,3 Petition 870250073583, dated 08 / 20 / 2025, page 27 / 57 / 39 diaminotoluene; 1,8-diaminonaphthalene; 2,4-diaminotoluene; 2,5-diaminotoluene; 1,4-diaminoanthraquinone; 1,5-diaminoanthraquinone; 1,5-diaminonaphthalene; 1,2-diaminoanthraquinone; 2,4-cumenediamine; 1,3-bisaminomethylbenzene; 2-chloro-1,4-diaminobenzene; 1,4-diamino-2,5-dichlorobenzene; 1,4-diamino-2,5-dimethylbenzene; 4,4'-diamino-2,2'-bistrifluoromethylbiphenyl; bis(amino-3-chlorophenyl)ethane; bis(4-amino-3,5-dimethylphenyl)methane; bis(4-amino-3,5-diethylphenyl)methane; bis(4-amino-3-ethyldiaminofluorene; 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'-diaminophenylsulfone; 3,3'-diaminophenylsulfone; 2,2-bis(4,-(4-aminophenoxy)phenyl)sulfone; 2,2-bis(4-(3-aminophenoxy)phenyl)sulfone; 4,4'-oxidianiline; 4,4'-diaminodiphenyl sulfide; 3,4'-oxidianiline; 2,2-bis(4-(4-aminophenoxy)phenyl)propane; 1,3-bis(4-aminophenoxy)benzene; 4,4'-bis(4-aminophenoxy)biphenyl;4,4'-diamino-3,3'-dihydroxybiphenyl; 4,4'-diamino-3,3'-dimethylbiphenyl; 4,4'-diamino-3,3' dimethoxybiphenyl; 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; 1,4-bis(4aminophenoxy)butane; 1,5-bis(4-aminophenoxy)butane; 2,3,5,6-tetramethyl-1,4phenylenediamine; 3,3',5,5'-tetramethylbenzidine; 4,4'-diaminobenzanilide; 2,2bis(4-aminophenyl)hexafluoropropane; m-xylylenediamine; p-xylylenediamine.;

[0063] Some phenylindane amines are commercially available. Others can be prepared by methods described in US patent document 3,856,752, the contents of which are incorporated herein by reference.

[0064] Preferably, diamines (III), NH2-R2-NH2, are selected from DAPI(4',5-6-Diamino-1,3,3-trimethyl-1-phenylindane).

[0065] Preferably, according to the invention, the ratio of the sum of amines (Am + An) to dianhydride compound varies from about 5:1 to about 1.05:1, more preferably from about 3:1 to about 1.1:1, still Petition 870250073583, dated 20 / 08 / 2025, p. 28 / 57 / 39, more preferably from about 2:1 to about 1.2:1, and according to a preferred embodiment of about 1.5:1.

[0066] Preferably, according to the invention, the molar ratio Am / An, of aromatic amine(s) to aliphatic amine(s), varies from about 20:1 to about 1:1, more preferably from about 10:1 to about 2:1, even more preferably from about 5:1 to about 3:1, advantageously about 4:1.

[0067] Preferably, the maleic anhydride (VI) compound is maleic anhydride.

[0068] The amount of maleic anhydride compound is selected in order to obtain a product whose ends are covered by the maleimide group at both ends.

[0069] According to a preferred embodiment, the first step of the method for preparing the bismaleimide compound of formula (I) occurs in two substeps: • Substep 1a: reaction of the dianhydride (IV) with the aliphatic diamine of formula H2N-R1-NH2(II), • Substep 1b: the reaction of the product resulting from Substep 1a with the aromatic diamine H2N-R2-NH2, resulting in an extended imide terminated in amine (V).

[0070] Advantageously, the method for preparing the bismaleimide compound of formula (I) is implemented in a single container, without isolating intermediate compounds, such as the amine-terminated extended imide (V).

[0071] The reaction mixture comprises a mixture of compounds of formula (I), where R1, R2, Y, n, m may vary according to the parameters selected to carry out the reaction. One skilled in the art is familiar with the preparation of bismaleimide compounds and understands that other products may be present in the reaction mixture besides those Petition 870250073583, dated 20 / 08 / 2025, p. 29 / 57 / 39 compounds of formula (I) according to the invention and intermediate compounds. For example, the mixture may comprise some compounds of formula (I) where n = 0, and some compounds of formula (I) where m = 0. The curable resin composition

[0072] The bismaleimide compound of formula (I) and / or the bismaleimide compound resulting from the method described above advantageously represents from about 20 to about 99%, more preferably from about 30 to about 98%, by weight of the total weight of the resin composition.

[0073] In addition to the bismaleimide compound of formula (I) and / or the bismaleimide compound resulting from the method described above, the resin composition advantageously comprises a heat-curable co-curing agent or resin.

[0074] Using a heat-curing agent in the resin composition allows reducing the curing temperature or promoting the curing reaction. According to a favorite embodiment, the composition of the invention includes at least one heat-curing agent or resin, which can be selected from, for example, polyphenylene ether derivatives, maleimides, styrenes, divinylbenzenes, trivinylcyclohexanes, trialkenyl isocyanurate compounds and mixtures thereof.

[0075] Advantageously, the curing agent is selected from trialkenyl isocyanurate compounds, such as trialyl isocyanurate (TAIC).

[0076] The amount of curing agent used is adapted according to the type and content of unsaturated groups contained in the curable resin composition, the choice of a specific curing agent, its half-life temperature and required stability. In one embodiment, the curable resin composition of the present invention may include the curing agent and mixtures. Petition 870250073583, dated 08 / 20 / 2025, page 30 / 57 / 39 of the same in an amount within a range of about 1% to about 50% by weight or within a range of about 2% to about 20% by weight based on the total weight of the additive composition. Additional components

[0077] Before curing, the curable resin composition can be mixed with various additives selected according to the intended application and expected properties. Such additives are detailed below in a non-limiting manner. In this chapter, percentages are expressed as the weight of the additional compounds relative to the total weight of the additive resin composition.

[0078] Although the resin composition of the present description can be cured by mere heating, a curing catalyst that generates a free radical species can be added to improve the curing efficiency. Examples of such curing catalysts include, but are not limited to, benzoin-type compounds, such as benzoin and methyl benzoin, acetophenone-type compounds, such as acetophenone and 2,2-dimethoxy-2-phenylacetophenone and the like; Thioxanthone-type compounds, such as thioxanthone and 2,4-diethylthioxanthone, bisazide compounds, such as 4,4'-diazidochalcone, 2,6-bis(4-azidobenzal)cyclohexanone and 4,4'-diazidobenzophenone, azo compounds, such as azobisisobutyronitrile, 2,2-azobispropane, m.m'-azoxystyrene and hydrazone, organic peroxides, such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 and dicumyl peroxide.

[0079] The resin composition may contain the curing catalyst in an amount of about 0.1% to 10% by weight, or about 0.3% to 7% by weight, or about 0.5% to 5% by weight, or about 1% to 3% by weight, wherein the % by weight is based on the total weight of the resin composition.

[0080] In another embodiment, a polymerization inhibitor may optionally be added to the resin composition to increase the Petition 870250073583, dated 08 / 20 / 2025, page 31 / 57 / 39 storage stability. Examples include quinones and aromatic diols, such as hydroquinone, p-benzoquinone, chloranil, trimethylquinone and 4-t-butylpyrocatechol. The resin composition may include from about 0.0005% to 5% by weight of the polymerization inhibitor when present, where the % by weight is based on the total weight of the resin composition.

[0081] In another embodiment, the resin composition may optionally include an inorganic filler, an organic filler, or a mixture thereof. The fillers contemplated for use in the practice of the present invention may be any of a variety of morphologies, for example, angular, platelet-like, spherical, amorphous, sintered, burnt, powdered, flaked, crystalline, ground, crushed, milled, and the like, or mixtures of any two or more of these. The currently preferred particulate fillers contemplated for use in this document are substantially spherical.

[0082] These fillers may optionally be thermally conductive. Both powder and flake forms of filler may be used in the resin compositions of the present invention. Fillers with a wide range of particle sizes may also be employed in the practice of the present invention. Particle sizes ranging from about 500 nm to about 300 micrometers may be employed, with particle sizes smaller than about 100 micrometers being preferred, and particle sizes in the range of about 5 to about 75 micrometers being particularly preferred.

[0083] A wide variety of fillers can be employed in the practice of the present invention, for example, soft fillers (e.g., uncalcined talc), natural minerals (e.g., aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, magnesia, silica, alumina, aluminum silicates and the like), calcined natural minerals (e.g., enstatite), fused synthetic minerals (e.g., Petition 870250073583, dated 08 / 20 / 2025, page 32 / 57 / 39 example, cordierite), treated fillers (e.g., silane-treated minerals), organic polymers (e.g., polytetrafluoroethylene), hollow spheres, microspheres, powdered polymeric materials and the like.

[0084] Examples of fillers include talc, mica, calcium carbonate, calcium sulfate, aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, magnesia, silica, alumina, TiO2, aluminum silicate, aluminum-zirconium silicate, cordierite, silane-treated mineral, polytetrafluoroethylene, polyphenylene sulfide and the like.

[0085] 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, magnesia, silica, alumina, zirconium silicate and the like. Preferably, the particle size of these fillers will be about 20 micrometers. If aluminum nitride is used as a filler, it is preferable that it be passivated by means of an adherent and conforming coating (e.g., silica or the like).

[0086] When fillers are present, the resin composition may contain up to about 75% by weight, or up to about 50% by weight, or up to about 25% by weight, or up to about 10% by weight of filler, wherein the % by weight is based on the total weight of the resin composition.

[0087] In another embodiment, the resin composition may be dissolved or dispersed in an organic solvent to form a resin composition varnish. The amount of solvent is not limited, but is normally sufficient to provide a solids concentration in the solvent of at least about 30% by weight to not more than about 90% by weight of solids, or between about 50% and 85% by weight of solids, or between about 55% and 75% by weight of solids.

[0088] The organic solvent is not specifically limited and may be a ketone, an aromatic hydrocarbon, an ester, an amide, or a Petition 870250073583, dated 08 / 20 / 2025, page 33 / 57 / 39 alcohol. More specifically, examples of organic solvents that can be used include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate, N-methylpyrrolidone formamide, 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, and mixtures thereof.

[0089] The resin composition of the present invention may optionally include one or more additives, such as flexibilizers, antioxidants, dyes, pigments, surfactants, antifoaming agents, silane coupling agents, dispersing agents, thixotropic agents, processing aids, flow modifiers, cure accelerators, strength enhancers, hardening agents, UV protectors (especially UV-blocking dyes suitable for enabling Automatic Optical Inspection (AOI) of Circuit Assemblies), flame retardants and the like, as well as mixtures of any two or more of the same.

[0090] The flexibilizers (also called plasticizers) contemplated for use in certain embodiments of the present invention include compounds that reduce the brittleness of the formulation, such as, for example, branched polyalkanes or polysiloxanes that lower the glass transition temperature of the compositions. Such plasticizers include, for example, polyethers, polyesters, polythiols, polysulfides, polybutadienes, such as those sold under the brand names Poly BD® and RICON®. The plasticizers, when employed, are normally present in the range of about 0.5% by weight to about 30% by weight of the resin composition.

[0091] The antioxidants contemplated for use in the practice of the present Petition 870250073583, dated 20 / 08 / 2025, p. 34 / 57 / 39 inventions include hindered phenols (e.g., BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), TBHQ (tert-butylhydroquinone), 2,2'-methylenebis(6-tert-butyl-p-cresol) and the like), hindered amines (e.g., diphenylamine, N,N'-bis(1,4-dimethylpentyl-p-phenylenediamine, N-(4-anilinophenyl)methacrylamide, 4,4'-bis(a,a-dimethylbenzyl)diphenylamine and the like), phosphites and the like.

[0092] The dyes contemplated for use in certain embodiments of the present invention include nigrosin, Orasol Blue GN, phthalocyanines, fluorescent dyes (e.g., Fluoral Green Gold dye and the like) and the like. When used, organic dyes in relatively low amounts (i.e., amounts less than about 0.2% by weight) provide contrast.

[0093] The pigments contemplated for use in certain embodiments of the present description include any particulate material added solely for the purpose of imparting color to the formulation, for example, carbon black, metal oxides (e.g., Fe2O3, titanium oxide) and the like. When present, the pigments are normally present in the range of about 0.5% by weight to about 5% by weight, relative to the weight of the resin composition.

[0094] The hardening agents contemplated for use in the practice of the invention are materials that impart greater impact resistance to various articles. Example hardening agents include compounds containing synthetic rubber, such as Hypro, Hypox, and the like.

[0095] The UV protectors 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 to which the protector was applied. Petition 870250073583, dated 08 / 20 / 2025, page 35 / 57 / 39 added. Examples of UV protectors include bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, silicon, powdered metal compounds, hindered amines (known in the art as “HALS”) and the like.

[0096] The antifoaming agents 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 agitated or sheared during processing. Example antifoaming agents contemplated for use in this document include n-butyl alcohol, silicon-containing antifoaming agents, and the like.

[0097] Silane coupling agents contemplated for use in the practice of the present invention include materials that form a bridge between inorganic surfaces and reactive polymeric components, including materials such as epoxy silanes, amino silanes and the like.

[0098] The thixotropic agents contemplated for use in the practice of the present invention include materials that cause liquids to have enhanced flow properties when shear is applied, including materials such as high surface area fillers (e.g., fumed silica) having particle sizes in the range of about 2 to 3 micrometers, or even submicron size.

[0099] The resin composition of the present description can be prepared by suitably mixing the above components and also kneading or mixing, as necessary, by a kneading means such as a 3-roll mill, a ball mill, a sphere mill or a sand mill, or a stirring means such as a high-speed rotary mixer, a super mixer or a planetary mixer. Furthermore, by adding one or a mixture of the organic solvents mentioned above, a resin composition varnish can also be prepared as described above. The amount of solvent is not limited, but is normally used in a quantity... Petition 870250073583, dated 08 / 20 / 2025, pp. 36 / 57 / 39 sufficient to provide a solids concentration in the solvent of at least 30% by weight to no more than 90% by weight of solids, or between about 50% and 85% by weight of solids, or between about 55% and 75% by weight of solids. Curing

[00100] According to another embodiment of the present description, articles are provided comprising a partially or fully cured layer of the resin composition described above. According to a preferred embodiment, the articles provided comprise a partially or fully cured layer of the resin composition described above on a substrate.

[00101] When the resin is heat-cured, the curing temperature differs according to the resin composition and the type and amount of curing agent used. Generally, the curing temperature ranges from about 20°C to about 250°C, preferably from about 50°C to about 250°C. Applications

[00102] According to another embodiment of the present invention, articles are provided comprising a partially or fully cured layer of the composition described above, preferably in association with a substrate.

[00103] The cured article can be used appropriately in organic insulating materials, etc., for use in electronic equipment, such as communication equipment, especially for the manufacture of a high-frequency laminate.

[00104] The selection of diamines (II) and (III), dianhydride (IV), their ratios and the selection of parameters that result in bismaleimide compounds of formula (I) provide resin compositions with improved properties in relation to processing, dielectric properties, thermomechanical properties and reduced sensitivity to water.

[00105] The invention relates to a method for manufacturing an article, the Petition 870250073583, dated 08 / 20 / 2025, page 37 / 57 / 39 said method comprising at least the steps of preparing a curable resin composition as described above, molding the composition and curing the composition.

[00106] Molding involves structuring the composition by giving it the expected shape and / or associating the composition with another material, for example, a support material, also referred to as a substrate or support article. Molding may include a step of dissolving the resin composition in a solvent. Several variants of the method according to the invention for manufacturing an article are detailed below: The present invention further relates to a process for manufacturing an article, for example, a high-frequency laminate, comprising at least the following steps: - Step 1: Prepare a curable resin composition as described above. - Step 2: Dissolve the curable resin composition from Step 1 in a solvent to form a varnish and apply the varnish to a support article. - Step 3: Cure the composition.

[00107] Applying varnish to a substrate can be implemented by any method known to those skilled in the art, such as, for example, painting the curable resin composition onto the substrate with a brush, spraying the curable resin composition onto the substrate, or applying a coating by centrifugation to the curable resin composition on the substrate.

[00108] The present invention further relates to a process for manufacturing an article, especially a high-frequency laminate, comprising at least the following steps: - Step 1: Prepare a curable resin composition as described above. - Step 2: Impregnate a support material, especially a Petition 870250073583, dated 08 / 20 / 2025, page 38 / 57 / 39 fibrous material, with the composition of step 1, - step 3: curing the composition.

[00109] Impregnating a fibrous material with the curable resin composition can be implemented by any method known to those skilled in the art, such as immersing the fibrous material in a solution of the curable resin composition, or spraying the curable resin composition onto the fibrous material, or applying a coating by centrifuging the curable resin composition onto the fibrous material. This method may require dissolving the curable resin composition in a solvent to form a varnish.

[00110] The present invention further relates to a process for manufacturing an article, comprising at least the following steps: - Step 1: Prepare a curable resin composition as described above. - Step 2: Introduce the composition from Step 1 into a mold. - Step 3: Partially or fully cure the composition.

[00111] The present invention also relates to an article obtained by a method comprising at least one step of curing a composition according to the invention.

[00112] The compositions of the present invention make it possible to provide products that can be used in a variety of applications, such as pre-impregnated materials, metal-clad laminates (e.g., copper-clad laminates), printed circuit boards, light-emitting diodes, and electronic coatings.

[00113] In particular, the present invention relates to a prepreg obtained by impregnating a fibrous material with a curable resin composition according to the invention and curing said resin.

[00114] The present invention also provides a laminated sheet, which can be used as a high-frequency laminate, wherein said sheet Petition 870250073583, dated 08 / 20 / 2025, page 39 / 57 / 39 laminated comprises the pre-impregnated material as defined above and a layer of an electrically conductive material disposed on at least one surface of the pre-impregnated material.

[00115] The invention is also directed to a printed circuit board produced by forming a conductive pattern on the surface of the laminated sheet, as defined above.

[00116] As readily recognized by those skilled in the art, a variety of substrates are suitable for use in the practice of the present description, for example, polyesters, liquid crystalline polymers, polyamides (e.g., aramids), polyimides, polyamide-imides, polyolefins, polyphenylene oxides, polyphenylene sulfides, polybenzoxazines, conductive materials (e.g., conductive metals) and the like, as well as combinations of any two or more of the same. When conductive metallic substrates are employed, materials such as silver, nickel, gold, cobalt, copper, aluminum, alloys of such metals and the like are contemplated for use herein.

[00117] According to another embodiment of the present invention, methods are provided for manufacturing the articles described above (i.e., articles comprising the composition according to the present invention on a substrate / support article), wherein the methods comprise applying the resin composition to a substrate and, if an organic solvent is optionally employed to facilitate such application, substantially removing all of the organic solvent from it. The resin composition can be applied to the substrate by immersion, impregnation, spraying, and the like.

[00118] According to another embodiment of the present description, pre-impregnated materials are provided produced by impregnating a porous substrate with a resin composition according to the present description and, if an organic solvent is optionally employed to facilitate such Petition 870250073583, dated 08 / 20 / 2025, page 40 / 57 / 39 impregnation, subject the resulting impregnated substrate to suitable conditions to substantially remove all organic solvent from it.

[00119] As readily recognized by those skilled in the art, a variety of porous substrates can be employed for the preparation of prepregs of the invention. The porous substrate can be woven or nonwoven. The thickness of this substrate is not particularly limited and can vary, for example, from about 0.01 mm to 0.3 mm.

[00120] Examples of porous substrates may include, but are not limited to, braided glass, non-braided glass, braided aramid fibers, non-braided aramid fibers, braided liquid crystal polymer fibers, non-braided liquid crystal polymer fibers, braided synthetic polymer fibers, non-braided synthetic polymer fibers, randomly dispersed fiber reinforcements, expanded polytetrafluoroethylene (PTFE) structures, and combinations of any two or more thereof.Specifically, materials contemplated for use as a porous substrate may include, but are not limited to, fiberglass, quartz, polyester fiber, polyamide fiber, polyphenylene sulfide fiber, polyetherimide fiber, cyclic olefin copolymer fiber, polyalkylene fiber, liquid crystalline polymer, poly(p-phenylene-2,6-benzobisoxazole), polytetrafluoroethylene and perfluoromethylvinyl ether (MFA) copolymers, and combinations of any two or more thereof.

[00121] According to another embodiment of the present invention, laminated sheets are provided produced by layering and molding a prescribed number of sheets of the pre-impregnated material described above.

[00122] The rolled sheets according to the present invention have many particularly beneficial properties, such as, for example, low dielectric constant, low dissipation factor, high thermal decomposition temperature and the like. In a preferred embodiment, the Petition 870250073583, dated 08 / 20 / 2025, p. 41 / 57 / 39 rolled sheets according to the present description have a nominal dielectric constant of ^4.0 and a dissipation factor of ^0.004 at 10 GHz, and a glass transition temperature of at least 100°C, or better, at least 150°C, and even better, at least 200°C.

[00123] In one aspect of the present invention, laminated sheets as described herein may optionally further comprise one or more conductive layers. Such optional conductive layers are selected from the group consisting of metal sheets, metal plates, electrically conductive polymer layers and the like. In one embodiment, the metal may be copper, silver, nickel, gold, cobalt, aluminum and alloys of these metals.

[00124] In another embodiment, a method is provided for forming a laminated sheet. The method includes placing the porous substrate in contact with a varnish bath comprising the resin composition of the present invention dissolved and intimately mixed in a solvent or a mixture of solvents. The contact occurs under conditions such that the porous substrate is coated with the resin composition. After that, the coated porous substrate is passed through a heated zone at a temperature sufficient to cause the solvent to evaporate, but below the temperature at which the resin composition undergoes significant curing during the residence time in the heated zone to form a pre-impregnated form.

[00125] The porous substrate preferably has a residence time in the bath of about 1 second to about 300 seconds, more preferably about 1 second to about 120 seconds, and most preferably about 1 second to about 30 seconds. The temperature of such a bath is preferably about 0°C to about 100°C, more preferably about 10°C to about 40°C, and most preferably about 15°C to about 30°C. The residence time of the coated porous substrate in the heated zone is about 0.1 minutes to about 15 minutes. Petition 870250073583, dated 20 / 08 / 2025, p. 42 / 57 / 39 more preferably from about 0.5 minutes to about 10 minutes and, more preferably, from about 1 minute to about 5 minutes.

[00126] The temperature of such a zone is sufficient to cause the volatilization of any remaining solvents, but not so high as to result in complete curing of the components during the dwell time. Preferred temperatures in this area are from about 80°C to about 250°C, more preferably from about 100°C to about 225°C, and even more preferably from about 150°C to about 210°C. Preferably, there is a means in the heated zone to remove the solvent, either by passing an inert gas through the oven or by applying a slight vacuum in the oven. In many embodiments, the coated substrate is exposed to zones of increasing temperature. The first zones are designed to cause the solvent to volatilize so that it can be removed. The later zones are designed to result in partial curing of the resin composition (stage B).

[00127] One or more sheets of pre-impregnated material are preferably processed into laminates, optionally with one or more sheets of electrically conductive material, such as copper. In such further processing, one or more segments or parts of the coated porous substrate are brought into contact with each other and / or with the conductive material. After this, the parts in contact are exposed to high pressures and temperatures, sufficient to cause the curing of the components, in which the resin in the adjacent parts reacts to form a continuous resin matrix between the porous substrates. Before curing, the parts can be cut and stacked or bent and stacked into a part with the desired shape and thickness. The pressures used can vary from 6894.76 Pa to 6894757.2932 Pa (1 psi to 1000 psi), with the preferred range being 68947.572932 Pa to 5515805.8345 Pa (10 psi to 800 psi).The temperature used to cure the resin compound on parts or laminates depends on the specific dwell time, the pressure used, and the components used. For example... Petition 870250073583, dated 20 / 08 / 2025, p. 43 / 57 / 39 Preferred temperatures that can be used are between about 100°C and about 250°C, more preferably between about 120°C and about 220°C, and even more preferably between about 170°C and about 200°C. Dwell times are preferably from 10 minutes to 120 minutes and, more preferably, from about 20 minutes to about 90 minutes.

[00128] In one embodiment, the process is continuous, wherein the porous substrate is removed from the oven and suitably arranged in the desired shape and thickness and pressed at very high temperatures for short periods. In particular, such high temperatures are from about 180°C to about 250°C, more preferably from about 190°C to about 210°C, for times of about 1 minute to about 10 minutes and from about 2 minutes to about 5 minutes. Such high-speed pressing allows for more efficient use of the processing equipment. In such embodiments, the preferred reinforcing material is a glass blanket or a woven cloth.

[00129] In some embodiments, it is desirable to subject the laminate or the final product to post-curing outside the press. This step is designed to complete the curing reaction. Post-curing is generally carried out between 130°C and 220°C for a period of 20 to 200 minutes. This post-curing step can be carried out in a vacuum to remove any components that may volatilize.

[00130] Thus, according to another embodiment of the present invention, methods are provided for manufacturing a laminated sheet, wherein said method comprises overlapping and shaping a prescribed number of sheets of a pre-impregnated material according to the present invention.

[00131] According to another embodiment of the present invention, printed circuit boards are provided produced by forming conductive patterns on the surface of the laminated sheet(s) described above. Forming the conductive patterns can be accomplished, for example, by forming a resistance pattern on the surface of the laminated sheet(s) by removing parts Petition 870250073583, dated 08 / 20 / 2025, page 44 / 57 / 39 unnecessary plate by means of chemical attack, removing the resistance pattern, forming the necessary through holes by means of drilling, forming the resistance pattern again, galvanizing to connect the through holes and, finally, removing the resistance pattern.

[00132] According to another embodiment of the present invention, multilayer printed circuit boards are provided produced by overlapping and molding a prescribed number of sheets of the standardized laminated layers described above, joined with one or more layers of pre-impregnated material from which the printed circuit board layer was prepared.

[00133] According to another embodiment of the present invention, methods are provided for manufacturing printed circuit boards, wherein said methods comprise forming conductive patterns on the surface of a laminated sheet according to the present invention.

[00134] According to another embodiment of the present invention, multilayer printed circuit boards are provided produced by overlapping and molding a prescribed number of sheets of the prepreg described above, to obtain a printed circuit board for an inner layer, and overlapping the prepreg on the printed circuit board for an inner layer that forms conductive patterns on the surface.

[00135] Consequently, the prepreg and printed circuit boards of the present invention can be usefully used as a component of a printed circuit board for a network for use in various electrical and electronic devices, such as mobile communication devices that handle a high-frequency signal of GHz or more, or their base station device, and network-related electronic devices such as servers and routers, and large computers.

[00136] In some embodiments, the resin compositions of Petition 870250073583, dated 08 / 20 / 2025, page 45 / 57 / 39 The present invention may have a dielectric dissipation factor (Df) that is flat over a wide frequency range, such that a component manufactured from them can operate efficiently at various different processing speeds. This is important since many prior art electronic devices can operate over a range of frequencies and therefore it is desirable that electronic components maintain proper operation across that entire frequency range.

[00137] It has been verified that the use of the present composition of the invention allows achieving an ultra-low loss factor Df in the gigahertz range (e.g., 1 to 10 GHz, well below 0.005 to 10 GHz), which is unexpected in view of the prior art.

[00138] Specifically, the curable resin compositions according to the invention provide access, after curing, to articles that have a dielectric dissipation factor (Df) measured on a Split-Pole Dielectric Resonator (SPDR) at a frequency of 10 GHz below 0.005, preferably below 0.004, more preferably below 0.0035.

[00139] According to a favorite embodiment, the articles resulting from the curing compositions of the present description have a dielectric constant (Dk) at 10 GHz of less than about 4 or less than about 3.5.

[00140] Specifically, the curable resin compositions according to the invention provide access, after curing, to articles having a Tg greater than or equal to about 100°C, preferably greater than or equal to about 150°C, more preferably greater than about 200°C.

[00141] The present invention will now be described in more detail with reference to the following non-limiting examples. Examples Materials:

[00142] Priamine 1075 ®: an aliphatic C36 dimer diamine marketed by CRODA Petition 870250073583, dated 08 / 20 / 2025, pages 46 / 57 / 39

[00143] DAPI: an aromatic amine (Diamino-1,3,3-trimethyl-1-phenylindane) marketed by

[00144] HUNTSMAN. Pyromellitic Dianhydride is marketed by CABB Group (formerly JAYHAWK). Example 1 - Preparation of bismaleimide compounds

[00145] Example 1a - Preparation of the bismaleimide compound according to the invention: A 2 L reaction flask equipped with a stirrer and a Dean-Stark siphon was charged with 0.2734 mol of Pyromellitic Dianhydride in 550 ml of Toluene and 220 ml of N-methylpyrrolidone, and the mixture was heated to 90–95°C. 0.082 mol of Priamine 1075® in 120 ml of toluene was introduced and reacted for 20 minutes under reflux conditions. 0.328 mol of 4',5-6-diamino-1,3,3-trimethyl-1-phenylindane (DAPI) in 110 ml of toluene and 130 ml of N-methylpyrrolidone was introduced. The temperature was increased to 125°C and the reaction continued for 2 hours under reflux conditions. The reaction mixture was cooled to 100°C and 0.3034 moles of maleic anhydride and 0.0802 moles of p-toluenesulfonic acid monohydrate were introduced. The temperature was increased to 125°C, and the reaction continued for 5 hours under reflux conditions. The solution was washed with brine, and the toluene was removed under vacuum.The solid is then purified by dissolution in N-methylpyrrolidone, followed by precipitation in methanol and vacuum drying. The mass yield is 70%. The analyses performed are 1H, 1C NMR, HPLC, GC and GPC and confirm the structure of the expected products in the reaction mixture.

[00146] Example 1b - Preparation of the comparative bismaleimide compound: follow the protocol of example 1a in which Priamine 1075 ® is replaced by DAPI.

[00147] Example 1c - Preparation of the comparative bismaleimide compound: follow the protocol of example 1a in which DAPI is replaced by Priamine 1075 ®. Petition 870250073583, dated 08 / 20 / 2025, page 47 / 57 / 39 Example 2 - Preparation of inventive and comparative resin compositions

[00148] The components identified in Table 1 were dissolved at room temperature in toluene to produce a homogeneous resin composition varnish with a concentration of 50 to 60% by weight of solids (compositions C1a, C1b and C1c). Table 1 Component Ex. C1a (pbw) Ex. C1b (pbw) (comparative) Ex. C1c (pbw) (comparative) Bismaleimide from example 1a 100 - - Bismaleimide from example 1b - 100 - Bismaleimide from example 1c - - 100 Triallyl isocyanurate 10 10 10 Dicumyl peroxide 1 1 1 Example 3 - Application - preparation of pre-impregnated and laminated

[00149] Glass fabric (E2116NE glass) was immersed in varnish, then placed vertically in an oven and dried for 2 minutes at 140°C to produce pre-impregnated sheets.

[00150] The above pre-impregnated sheets were pressure cured for 2 hours at 220°C with a resin content of approximately 45% by weight to approximately 50% by weight in the final laminate.

[00151] The resulting laminates with an approximate thickness of 0.5 mm were evaluated for dielectric constant (Dk) and dissipation factor (Df) in a Split-Pole Dielectric Resonator (SPDR) at a frequency of 10 GHz, and the glass transition was measured in the oscillation mode at 1 Hz from 23°C to 300°C at 2°C / min. The glass transition was determined by the onset of G' and delta tan as maxima. Table 2 Property Ex. C1a Ex. C1b (comparative) Ex. C1c (comparative) Dielectric constant (Dk) (10 GHz) 3.34 (+ / - 0.05) 3.40 (+ / - 0.02) 3.23 (+ / - 0.007) Dielectric loss (Df) (10 GHz) 0.0034 (+ / - 0.0004) 0.0074 (+ / - 0.0005) 0.0028 (+ / - 0.0003) Glass transition (Tg initial G' / Tan delta)°C 220 / 275 >300 / >300 <25 / 50

[00152] The result clearly shows the effect of using a Petition 870250073583, dated 20 / 08 / 2025, p. 48 / 57 / 39 mixture of aromatic and aliphatic amines. The dielectric loss of fully aromatic bismaleimide (Ex. Comp. 1b) is significantly increased compared to Ex. 1a, while aliphatic amine-based bismaleimide (Ex. Comp. 1c) has a significantly shorter glass transition than Ex. 1a.

[00153] Although the manufacture and use of various embodiments of the present invention have been described in detail above, it should be recognized that the present invention provides many applicable inventive concepts that can be incorporated into a wide variety of specific contexts. The specific embodiments discussed here are merely illustrative of specific ways of making and using the invention and do not delimit the scope of the invention. Petition 870250073583, dated 08 / 20 / 2025, pp. 49 / 57

Claims

1 / 6 CLAIMS 1. Bismaleimide compounds, characterized in that they are represented by formula (I): Formula (I) wherein n is an integer, n ranges from 1 to 10, m is an integer, m ranges from 1 to 10, each Q, independently, is a tetravalent radical selected from C6-C50 hydrocarbons comprising at least one aromatic group and optionally one or more heteroatoms selected from O, N, S, F, Cl, Br, each R1, independently, is a divalent radical selected from C1-C60 aliphatic and aromatic hydrocarbyls, linear or branched, optionally comprising one or more NH2 groups, one or more NH bridges, each R2, independently, is a divalent radical selected from C6-C54 aromatic hydrocarbons, optionally comprising one or more halogen atoms, R is a radical divalent R1 or R2, Y represents H or CH3.

2. Bismaleimide compounds according to claim 1, characterized in that Q is selected from the structures: Petition 870250073583, dated 20 / 08 / 2025, page 50 / 57 2 / 6 with Q', a divalent radical selected from C1-C38 hydrocarbons optionally comprising one or more heteroatoms selected from O, N, S, F, Cl and Br.

3. Bismaleimide compounds according to claim 1 or 2, characterized in that each R1 is independently selected from C12-C60 alkyl, alkenyl or aralkyl groups, optionally comprising one or more NH2 groups, one or more NH bridges.

4. Bismaleimide compounds according to any one of claims 1 to 3, characterized in that each R2 independently is selected from divalent radicals of formula (IIIA) Petition 870250073583, 20 / 08 / 2025, p. 51 / 57 3 / 6 Formula (IHA) wherein Y1, Y2 independently represent H, a C1-C5 alkyl, each Y3, Y4 independently represents H, a halogen, a C1-C4 alkyl.

5. Method for the preparation of bismaleimide compounds as defined in any one of claims 1 to 4, characterized in that said method comprises the following steps: • Step 1: reacting a dianhydride (IV) with a diamine of formula (II) and a diamine of formula (III) to obtain an extended amine-terminated imide (V), • Step 2: reacting the extended amine-terminated imide (V) resulting from step 1 with a maleic anhydride compound (VI), wherein Petition 870250073583, dated 20 / 08 / 2025, p. 52 / 57 4 / 6 n, m, Q, R1, R2, R and Y have the same definition as in formula (I), An and Am, respectively, represent the relative molar quantity of diamine H2N-R1-NH2 and diamine H2N-R2-NH2 introduced into the reaction medium in relation to the quantity of dianhydride (IV).

6. Method according to claim 5, characterized in that the ratio of the sum of the amounts of amines (Am + An) to the dianhydride compound varies from about 5:1 to about 1.05:

1.

7. Method according to claim 5 or 6, characterized in that the molar ratio Am / An, of aromatic amine(s) (III) to aliphatic amine(s) (II), varies from about 20:1 to about 1:1, more preferably from about 10:1 to about 2:1, even more preferably from about 5:1 to about 3:1, advantageously about 4:

1.

8. Method according to any one of claims 5 to 7, characterized in that the first step of the method proceeds in two substeps: • Substep 1a: the reaction of the dianhydride (IV) with the aliphatic diamine of formula H2N-R1-NH2 (II), • Substep 1b: the reaction of the product resulting from Substep 1a with the aromatic diamine H2N-R2-NH2, resulting in an extended imide terminated in amine (V).

9. A method according to any one of claims 5 to 8, characterized in that the method is implemented in a single container.

10. Bismaleamide compound, characterized in that it is produced by the method as defined in any one of claims 5 to 9.

11. Curable resin composition, characterized in that it comprises at least one bismaleimide compound of formula (I) Petition 870250073583, dated 20 / 08 / 2025, page 53 / 57 5 / 6 as defined in any of claims 1 to 4 or as defined in claim 10 and at least one curing agent.

12. Curable resin composition according to claim 11, characterized in that the curing agent is selected from polyphenylene ether derivatives, maleimides, styrenes, divinylbenzenes, trivinylcyclohexanes, trialkenyl isocyanurate compounds and mixtures thereof, preferably trialkenyl isocyanurate compounds, such as trialyl isocyanurate.

13. Curable resin composition according to claim 11 or 12, characterized in that the bismaleamide compound represents from about 20 to about 99%, more preferably from about 30 to about 98%, by weight of the total weight of the resin composition, and the curing agent represents from about 1% to about 50%, preferably from about 2% to about 20%, by weight based on the total weight of the composition.

14. Process for manufacturing an article, characterized in that it comprises at least the following steps: - Step 1: preparing a curable resin composition as defined in any one of claims 11 to 13, - Step 2: molding the composition, - Step 3: partially or fully curing the composition.

15. Article, characterized by the fact that it is produced by the method as defined in claim 14.

16. Article according to claim 15, characterized in that it has a dielectric dissipation factor (Df) measured on a Split Pole Dielectric Resonator (SPDR) at a frequency of 10 GHz below 0.005, preferably below 0.004, more preferably below 0.0035, a dielectric constant (Dk) at 10 GHz less than about 4 or less than about 3.5, and a Tg greater than or equal to 100°C, preferably greater than or equal to 150°C, more preferably greater than 200°C.

17. Article according to claim 15 or 16, characterized in that it is a pre-impregnated material obtained by impregnating a fibrous material with a composition as defined in any one of claims 1 to 4 or 10.

18. Laminate, characterized in that it comprises the pre-impregnated material as defined in claim 17 and a layer of an electrically conductive material disposed on at least one surface of the pre-impregnated material.

19. Printed circuit board, characterized in that it is produced by forming a conductive pattern on the surface of the laminate as defined in claim 18.

20. Use of the resin composition as defined in any one of claims 1 to 4 or 10, characterized by being in a prepreg, a metal-clad laminate, a printed circuit board, a light-emitting diode, an electronic coating, a textile, a polymer molding compound, a medical molding compound, and an adhesive. Petition 870250073583, dated 20 / 08 / 2025, pp. 55 / 57