Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/12—Polymers provided for in subclasses C08C or C08F
  • C08F290/124—Polymers of aromatic monomers as defined in group C08F12/00
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  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
  • C04B26/02—Macromolecular compounds
  • C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B26/06—Acrylates
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/04—Anhydrides, e.g. cyclic anhydrides
  • C08F222/06—Maleic anhydride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/36—Amides or imides
  • C08F222/40—Imides, e.g. cyclic imides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
  • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
  • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
  • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L35/06—Copolymers with vinyl aromatic monomers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
  • H01B3/442—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from aromatic vinyl compounds
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
  • H01B3/448—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from other vinyl compounds
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
  • C04B2111/00844—Uses not provided for elsewhere in C04B2111/00 for electronic applications
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
  • C04B2111/00896—Uses not provided for elsewhere in C04B2111/00 as prepregs
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2312/00—Crosslinking
  • C08L2312/04—Crosslinking with phenolic resin

Definitions

• thermosetting resin compositions that are useful in the chemical arts, such as in the manufacture of products, such as printed circuit boards.
• present disclosure pertains to novel compositions and processes for preparing certain low dielectric loss thermosetting resin polymers.
• the present disclosure relates to a low dielectric loss thermosetting resin composition
• a low dielectric loss thermosetting resin composition comprising a copolymer containing monomer units of vinyl-or vinyl derivatives, aliphatic unsaturated imides and a curing agent.
• the disclosure further relates to a prepreg and a metal clad laminate comprising the thermoset resin composition.
• the present disclosure also relates to the printed circuit boards comprising the prepreg and/ or metal clad laminate.
• Thermosetting resin compositions are known in the art. Thermosetting resins undergo a curing or crosslinking process that will crosslink polymer chains and thus connect the entire matrix together in a three-dimensional network. Once crosslinked, thermosetting resins cannot be remelted or reformed. Thermosetting resins tend to have high dimensional stability, high- temperature resistance, and good resistance to solvents because of their three-dimensional crosslinked structure (U.S. Congress, Office of Technology Assessment, June 1988).
• thermosetting resin compositions such as epoxy resins, phenolic resins, bismaleimide resins, polyamine formaldehyde resins and silicone resins are useful in electrical applications and electronic equipment such as in printed circuit boards (PCBs).
• Thermosetting resins are required to provide a long life and high reliability of electrically insulating properties.
• Such compositions are for example used as fiber reinforced prepregs, and in metal clad laminates such as copper-clad laminates (CCL) which are suitable for printed circuit boards (PCB).
• CCL play a role as a leading fundamentally raw material contributing to materials for PCB fabrication, performing four functions including conductivity, insulation, supporting and signal transmission and thereby determine a PCB 's performance, quality, fabrication level, fabrication cost and long-term reliability. Constant development of PCBs and increasing application demands of electronic products gradually bring forward new technological demands for CCL, simultaneously providing driving force to technological development and fabrication technology progress of CCL.
• Epoxy resins are commonly used for CCL. Curing agents for epoxy resins are for example phenolic, poly(styrene-co-maleic anhydride) (SMA), benzoxazine, active esters and cyanate esters.
• SMA poly(styrene-co-maleic anhydride)
• benzoxazine active esters
• cyanate esters cyanate esters.
• the epoxy resin formulations can however not meet the increasing need for lower dielectric loss. This is mainly due to the polar groups that are formed during the curing of the epoxy resins, which will negatively influence the dielectric loss.
• Fluorine-containing resins such as PTFE, can also be used for PCBs and show a low dielectric loss.
• fluorine-containing resins are expensive and not easy to work with and thus limited in use.
• thermosetting resin composition providing improved heat resistance and thus improved insulating properties whereby a thermoset resin composition is provided by mixing a styrene copolymer having a specific imide bond with a radical polymerization catalyst.
• the styrene copolymer preferably comprises styrene with maleic anhydride which undergoes an imidization reaction with for example allylamine.
• the resulting copolymer is heated in the presence of a known radical polymerization catalyst such as an organic peroxide to obtain the heat-resistant thermosetting resin.
• a disadvantage of this cured thermosetting resin is that it still has a relatively high dielectric loss even at the reported 1 MHz.
• the dielectric loss increases when the frequency increases, while higher frequencies, e.g., 1 GHz or above, are commonly used for the high speed PCB applications.
• the cured resin shows a relatively low decomposition temperature i.e., poor thermostability. Thermostability can influence the processability and the operation temperature. For instance, poor thermostability would lead to short delamination time during soldering process for PCB applications, and could also cause thermal reliability and signal integrity issues during operation.
• Thermosetting resins used in the high speed applications must thus satisfy a number of critical thermal, environmental, and electrical requirements to meet the required performance criteria for microelectronics applications. These desired attributes include thermal stability, low moisture uptake, copper adhesion, high breakdown voltage (low leakage current), low dielectric constant (Dk) and low dielectric loss (Df) which can be also called loss tangent.
• thermosetting resin composition with excellent dielectric properties such as low dielectric constant (Dk) and low dielectric loss (Df) combined with other properties such as high Tg, low coefficient of thermal expansion and low water absorption and high peel strength as required in the high speed PCBs.
• Dk dielectric constant
• Df dielectric loss
• thermosetting resin composition with improved dielectric and thermal properties, that can be used in electronic applications such as the high speed PCBs.
• improved dielectric properties is meant a low dielectric loss and low dielectric constant (Dk) or low Relative Permittivity combined with a better thermostability.
• the disclosure provides a thermosetting resin composition
• a copolymer comprising a monomer unit of Formula I Formula I wherein R1 represents a hydrogen or aliphatic group and R2 represents a hydrogen, an aliphatic or aromatic group, and an aliphatic unsaturated imide of Formula II Formula II wherein R3 is H or an alkyl group, R4 is an alkylidene group and R5 is an alkanediyl group; and at least one curing agent comprising maleimide, (meth)acrylate or vinyl groups.
• the disclosure provides a thermoset resin composition prepared by a process comprising the steps of (i) contacting a styrene-maleic anhydride copolymer (SMA) with an unsaturated aliphatic amine to prepare the styrene-maleimide copolymer and/or (ii) crosslinking a styrene-maleimide copolymer with an at least one curing agent.
• SMA styrene-maleic anhydride copolymer
• the disclosure provides a prepreg comprising a thermosetting resin composition or a thermoset resin composition as described herein, or a semi-cured product of a thermosetting resin composition or a thermoset resin composition as described herein; and a substrate.
• the disclosure provides a metal clad laminate comprising an insulating layer formed out of a cured product of a prepreg composition as described herein or a thermoset resin composition as described herein; and at least one metal layer formed on either or both surfaces of the insulating layer.
• the disclosure provides a printed circuit board comprising a prepreg composition as described herein, or a thermoset resin composition as described herein, or a metal clad laminate as described herein.
• thermosetting resin composition comprising a copolymer comprising a monomer unit of Formula I Formula I wherein R1 represents a hydrogen or aliphatic group and R2 represents a hydrogen, an aliphatic or aromatic group, and an aliphatic unsaturated imide of Formula II wherein R3 is H or an alkyl group, R4 is an alkylidene group and R5 is an alkanediyl group, and at least one curing agent comprising maleimide, (meth)acrylate or vinyl groups.
• thermosetting resin composition according to clause 2 whereby the polyfunctional maleimide is chosen from the group consisting of bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, biphenyl containing maleimide, meta-arylene containing maleimide or l,6-bismaleimide-(2,2,4-trimethyl)hexane.
• thermosetting resin composition according to any one of the clauses 1-2 whereby the curing agent comprising (meth)acrylate groups is a polyfunctional (meth)acrylate.
• thermosetting resin composition according to clause 4 whereby the polyfunctional (meth)acrylate is represented by Formula XI
• Formula XI n is an integer between 1-20.
• thermosetting resin composition according to any one of the clauses 1-2 whereby the curing agent comprising vinyl group is a polyfunctional vinyl containing curing agent.
• thermosetting resin composition according to clause 6 whereby the polyfunctional vinyl curing agent is selected from the group consisting of polybutadiene, polybutadiene -co-styrene, divinylbenzene, bis-vinylphenyl ethane, polyfunctional vinyl aromatic copolymer, vinyl cyclic olefin resin or a poly(arylene ether).
• the polyfunctional vinyl curing agent is selected from the group consisting of polybutadiene, polybutadiene -co-styrene, divinylbenzene, bis-vinylphenyl ethane, polyfunctional vinyl aromatic copolymer, vinyl cyclic olefin resin or a poly(arylene ether).
• Formula XII n is an integer between 1-20
• thermosetting resin composition according to any one of the clauses 1-8 further comprising a radical initiator.
• thermosetting resin composition according to clause 1 whereby the molar ratio of monomer unit of Formula I versus the unsaturated imide monomer unit of Formula II varies from 1:1 to 9:1.
• R6 is chosen from saturated aliphatic or aromatic groups.
• thermosetting resin composition according to clause 11 whereby the molar ratio unsaturated imide monomer unit of Formula II versus the saturated imide monomer unit of Formula III varies from 1:0 to 1:2.
• thermosetting resin composition according to any one of the clauses 1-12 further comprising at least one additive selected from flame retardants, fillers, coupling agents and any combination thereof.
• thermosetting resin composition according to any one of the clauses 1-13 or a semi-cured product of the resin composition and a substrate.
• Metal clad laminate comprising an insulating layer formed out of a cured product of the prepreg of clause 14 and at least one metal layer formed on either or both surfaces of the insulating layer.
• Printed circuit board comprising the metal clad laminate according to clause 15.
• thermoset resin composition prepared by a process comprising the step of
• thermoset resin composition of clause 17, further comprising the step of (i) contacting a styrene-maleic anhydride copolymer (SMA) with an unsaturated aliphatic amine to prepare the styrene-maleimide copolymer.
• SMA styrene-maleic anhydride copolymer
• thermoset resin composition of clause 17 or 18, wherein the styrene-maleimide copolymer comprises a monomer unit of Formula I (Formula I) wherein R1 is a hydrogen or an aliphatic group, and R2 is a hydrogen, an aliphatic group, or an aromatic group; and an aliphatic unsaturated imide of Formula II wherein R3 is H or an aliphatic group, R4 is an alkylidene group, and R5 is an alkylene group.
• the at least one curing agent comprises one or more maleimide group, (meth)acrylate group, and/or vinyl group.
• the polyfunctional maleimide is selected from bisphenol A diphenyl ether bismaleimide, 3, 3'-dimethyl-5,5'-diethyl-4, d'diphenylmethane bismaleimide, biphenyl containing maleimide, meta-arylene containing maleimide, and l,6-bismaleimide-(2,2,4-trimethyl)hexane.
• thermoset resin composition of clause 26, wherein the polyfunctional vinyl containing curing agent is selected from polybutadiene, polybutadiene-co-styrene, divinylbenzene, bis- vinylphenyl ethane, polyfunctional vinyl aromatic copolymer, vinyl cyclic olefin resin, and poly(arylene ether).
• Formula XII (Formula XII) wherein n is an integer between 1-20.
• thermoset resin composition of clause 30, wherein the azo compound is azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4,4-trimethylpentane, 2,2'-azobis(N-butyl-2-methylpropionamide.
• the organic peroxide is selected from the group consisting of benzoyl peroxide, t-butyl hydroperoxide, dicumyl peroxide, t-butyl perbenzoate, methylethyl ketone peroxide, cyclohexanone peroxide, acety
• thermoset resin composition of clause 38 prepared by a process comprising contacting the thermoset resin composition with one or more metal layers prior to completion of step (ii).
• thermoset resin composition of clause 53 wherein the radical polymerization initiator comprises an azo compound or an organic peroxide.
• thermoset resin composition of clause 54 wherein the azo compound is azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4,4-trimethylpentane, 2,2'-azobis(N-butyl-2-methylpropionamide.
• thermoset resin composition of clause 61 wherein the styrene-maleimide copolymer is not completely crosslinked by the least one curing agent, to provide a prepreg composition of the thermoset resin composition.
• thermoset resin composition of clause 61 or 62 comprising one or more metal layers on the thermoset resin composition.
• Fig. 1 is a graph of a TGA curve for Example 3 and Comparative example 3.
• aliphatic includes a composition of hydrocarbons that can be saturated, or unsaturated. Aliphatic compositions are not aromatic and do not possess alternating double bonds, e.g., pi-electron conjugation. Aliphatic compositions can comprise straight, branched, or cyclic hydrocarbons. Cyclic aliphatic compositions are not aromatic.
• Alkyl may be substituted or unsubstituted.
• alkenyl and “alkynyl” refer to unsaturated aliphatic chains of carbon atoms.
• thermosetting resin composition comprising a copolymer comprising monomer units of Formula I and an aliphatic unsaturated imide of Formula II and at least one curing agent comprising maleimide, (meth)acrylate or vinyl groups.
• R1 represents a hydrogen or aliphatic group
• R2 represents a hydrogen, an aliphatic or aromatic group, preferably R1 is methyl or H, R2 is H.
• R3 is H or an alkyl group
• R4 is an alkyl group
• R5 is an alkyl group.
• R3 is H or a C1-C8 alkyl group
• R4 is a C1-C4 alkylidene group
• R5 is a C1-C4 alkanediyl group. More preferably R3 is H, R4 is CH2, R5 is CH2.
• thermostability is meant that high thermal decomposition temperature of the cured resin systems, such as the thermal decomposition temperature is above 350 °C at which the mass of the cured sample is 5.0% less than its mass measured at 50°C via thermogravimetric analysis (TGA), i.e., Td 5%.
• TGA thermogravimetric analysis
• the glass transition temperature (T g ) of the cured resin compositions according to the present disclosure is at least above 110 °C, preferably above 150 °C and more preferably is above 170 °C.
• the Tg of the cured resin composition can be measured via Differential scanning calorimetry (DSC), Dynamic mechanical analysis (DMA) or Thermomechanical Analysis (TMA).
• thermosetting resin composition of the present disclosure the copolymer of monomer units of Formula I and aliphatic unsaturated imide monomer units of Formula II may optionally be combined with a saturated imide monomer unit Formula III.
• the introduction of saturated imide monomer unit of Formula III may change the thermal and dielectric properties of the copolymer depending on the choice of R6.
• n:m range from 1:1 to 9: 1.
• Curing agents comprising vinyl groups may contain one or more vinyl groups per molecule.
• polyfunctional vinyl containing curing agents are used.
• polyfunctional vinyl containing curing agents are polybutadiene, polybutadiene -co-styrene, divinylbenzene, bis-vinyl-phenyl ethane, polyfunctional vinyl aromatic copolymer, vinyl cyclic olefin resin and poly(arylene ether).
• the poly(arylene ether) is not particularly limited but preferably contains two or more vinyl groups per molecule such as OPE-2St which is commercially available from MGC and represented in Formula XII.
• Examples of flame retardants are ethylene- 1 ,2-bis(penta-bromo-phenyl) known as SAYTEX 8010 available from Albemarle and ethylene-bis-tetra-bromo-phthalimide known as SAYTEX BT93(W) available from Albemarle.
• An example of a halogen free flame retardant is bis (DOPO) derivative XP7866 from Albemarle.
• the "semi-cured" state refers to an intermediate stage (Stage B).
• the intermediate stage is a stage between a stage in the uncured resin composition (Stage A) and a stage in a fully cured state (Stage C). Heating the prepreg allows the resin compositions to be cured fully to turn into a cured product.
• the resin composition including an organic solvent is called a resin varnish.
• the organic solvent is not particularly restricted as long as it the dissolves the copolymer, the curing agent and the like.
• examples are ketone-based solvents such as acetone, 2-butanone (MEK) and cyclohexanone and hydrocarbon based solvents for example toluene, xylene and anisole. These organic solvents may be used singly or concurrently as a mixture of two or more of them.
• Non-soluble additives such as silica particles and potentially additive based flame retardant can be dispersed in the resin varnish.
• thermosetting resin composition according to embodiment 1 whereby the maleimide curing agent is a polyfunctional maleimide is a polyfunctional maleimide.
• thermosetting resin composition according to any one of the embodiments 1-2 whereby the curing agent comprising (meth)acrylate groups is a polyfunctional (meth)acrylate.
• Formula XI n is an integer between 1-20.
• thermosetting resin composition according to any one of the embodiments 1-2 whereby the curing agent comprising vinyl group is a polyfunctional vinyl containing curing agent.
• thermosetting resin composition according to embodiment 6 whereby the polyfunctional vinyl curing agent is selected from the group consisting of polybutadiene, polybutadiene -co- styrene, divinylbenzene, bis-vinylphenyl ethane, polyfunctional vinyl aromatic copolymer, vinyl cyclic olefin resin or a poly (arylene ether).
• thermosetting resin composition according to embodiment 7 whereby the poly(arylene ether) is represented by Formula XII.
• thermosetting resin composition according to embodiment 1 whereby the molar ratio of monomer unit of Formula I versus the unsaturated imide monomer unit of Formula II varies from 1:1 to 9:1.
• Metal clad laminate comprising an insulating layer formed out of a cured product of the prepreg of embodiment 14 and at least one metal layer formed on either or both surfaces of the insulating layer.
• Printed circuit board comprising the metal clad laminate according to embodiment 15.
• Xylene was supplied by Carl Roth. Allylamine, acetone, and MEK were supplied by Sigma Aldrich. Noryl SA9000 is available from SABIC. XIRAN EF-grades are available from Polyscope. BMI-5100 is available from Daiwa Kasei. RICON® 181 is available from Cray Valley.
• Size exclusion chromatography was using a PSS WinGPC system from PSS.
• a Precolumn guard of 5 pm, 8.0 mm x 50 mm was used followed by three columns of 1000 A, 8.0 mm x 300 mm, 8.0 mm x 300 mm.
• a differential refractometer (RID) was used as detector.
• the eluent was THF with 5 % acetic acid.
• An injection volume of 100 pL and the flow rate was 1.0 ml/min.
• the sample concentration was 5 g/L.
• the temperature was 23 °C.
• the molecular weight was calculated by using calibrated polystyrene molar mass standards.
• the Dk and Df were measured at 5.1 GHz at room temperature using a split post dielectric resonator (SPDR) equipped with a Microwave Frequency Q-Meter (5 GHz) from QWED.
• SPDR split post dielectric resonator
• the neat resin castings were measured directly after post baking at 200 °C for 1 hour.
• DSC Differential scanning calorimetry
• METTLER TOLEDO Differential scanning calorimetry
• the DSC measurements were carried out on the prepared neat resin castings from 30 °C to 220 °C using a heating rate of 20 °C/min and a cooling rate of 10 °C/min under a nitrogen flow of 50 mL/min).
• the second heating rate was carried out at 20 °C/min from 30 to 250 °C.
• the sample weight was approximately 10 mg.
• Data analysis was performed using STARe software.
• the cross-linked Tg values of the prepared neat resin castings were determined using the midpoint function with the data of the second heating run.
• Thermogravimetric analysis was performed using a TGA 2 STARe from METTLER TOLEDO.
• the TGA samples were first dried using the TGA by a heating rate of 10 °C/min from 30 °C to 200 °C under nitrogen flow of 50 mL/min. Subsequently, the dried sample was measured in the TGA using a heating rate of 10 °C/min from 30 °C to 700 °C under nitrogen flow of 50 mL/min. Data analysis was performed using STARe software.
• the Step Horizon Function (start temperature of 50 °C) was used to determine the thermal decomposition temperature at 5 mass percentage weight loss and the residue at 600 °C.
• XIRAN EF80 (0.201 mol anhydride) was added to a 1000 mL four-necked round bottom flask equipped with a Dimroth condenser, a mechanical stirrer, a nitrogen inlet and pressure equalizing dropping funnel. 360 g of xylene was charged into the round bottom flask. 0.221 mol allylamine was slowly added. The reaction temperature was increased to 40 °C for 1.5 hours to form the amic acid. Subsequently, 0.050 mol of triethylamine (TEA) was added and the reaction mixture was heated to reflux. The solution was refluxed for 12 hours and cooled down to room temperature. An additional 0.060 mol of allylamine was added.
• TAA triethylamine
• the reaction mixture was increased to 40 °C for 1.5 hours. 0.004 mol TEA was added and the solution was refluxed for an additional 12 hours. The solution was cooled down to room temperature and the solvent was removed in a rotary evaporator and the obtained resin powder was dried further overnight in a vacuum oven at 80 °C.
• FT-IR analysis indicated the presence of imide groups and allyl groups.
• the modified polymer is soluble in commonly used solvents including acetone, MEK, toluene, xylene and anisole. As indicated by SEC measurements, no chain extension or crosslinking of the modified polymer occurred.
• XIRAN EF40 (0.321 mol anhydride) was added to a 1000 mL four-necked round bottom flask equipped with a Dimroth condenser, a mechanical stirrer, a nitrogen inlet and pressure equalizing dropping funnel. 394 g of xylene was charged into the round bottom flask. 0.353 mol allylamine was slowly added. The reaction temperature was increased to 40 °C for 1.5 hours to form the amic acid. Subsequently, 0.064 mol of triethylamine (TEA) was added and the reaction mixture was heated to reflux. The solution was refluxed for 12 hours and cooled down to room temperature. An additional 0.060 mol of allylamine was added.
• TAA triethylamine
• varnishes are prepared by dissolving the components in MEK according to the formulations presented in Tables 1 and 3. Once all the components were dissolved, the solvent was removed overnight at 65 °C under vacuum in an oven to obtain a resin powder. The obtained resin powder is used to make neat resin casting using a vacuum hot press with a hot press curing schedule of 1.5 hours at 220 °C.
• Example 4 was thermally cross-linked without an initiator using a hot press curing schedule of 1.5 hours at 240 °C.
• the neat resin castings were removed from the mold and post-baked for an additional 1 hour at 200 °C in a vacuum oven.
• the neat resin castings thickness is approximately 1 mm.
• Table 1 refers to examples (Ex) 1-5 and comparative examples (CE) 1-3 comprising the indicated formulations.
• Ex 1-5 show excellent dielectric properties with Df values ranging from 0.0012-0.0038.
• the allyl modified copolymers can thermally cross-link with maleimide without a radical initiator (Ex 4) and this resulted into a reduced dielectric loss value compared to Ex 1.
• the dielectric loss of CE2 is surprisingly high with a Df value 0.0121.
• the dielectric properties of CE 1 with the addition RICON181 is better than CE 2, however the Dk and Df values are still higher compared to those of the examples Ex 1-5.
• Dielectric properties of CE3 could not be measured due to the deformation of the neat resin casting during the post-cure in the vacuum oven.
• Table 3 Dielectric properties and Tg of neat resin castings Table 3 refers to examples 6-8 comprising the indicated formulations.
• the formulations containing Xiran EL419 have the Df below 0.003. With increasing of BMI 5100 proportion in the formulations, Df values of the cured resin systems have little changes, but the T g values increase with increasing in BMI 5100.

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