Resin composition and application thereof

Abstract

A resin composition includes (A) a compound having a structure of formula (I); and # imgabs 0 # (B) a component having an ethylenically unsaturated double bond selected from the group consisting of a compound having the structure of formula (II), a compound having the structure of formula (III), and combinations thereof, # imgabs 1 # wherein Z, A, R, X, Y, m, and n are as defined herein.

Description

Technical Field

[0001] The present invention relates to a resin composition, and more particularly to a resin composition comprising a compound having a specific structure and a component having an ethylenically unsaturated double bond. The resin composition of the present invention can be used with a reinforcing material to form a prepreg, or can be used as an adhesive for metal foil to prepare a metal-clad laminate and a printed circuit board (PCB). Background Art

[0002] As the application of electronic products gradually enters the high-frequency field, signal transmission is becoming more high-frequency and high-speed, electronic components are becoming smaller, and substrate circuits are becoming more dense, and the requirements for the characteristics of electronic materials are also increasing. Traditional resin compositions with epoxy resin as the main component are difficult to meet the demand, and are replaced by resin compositions with polypheylene ether (PPE) as the main component. For example, in U.S. Patent No. 6,352,782 B2 (Applicant: General Electric (GE)), a thermosetting polyphenylene ether resin composition is disclosed, which includes a terminal-modified unsaturated functional group type polyphenylene ether resin (mPPE) and a cross-linkable unsaturated monomer compound. In this document, triallylisocyanurate (TAIC) is used as a monomer cross-linking agent, and together with acrylate-terminated modified polyphenylene ether, a thermosetting composition is formed to meet the requirements of high-frequency electrical properties.

[0003] However, the electrical properties of existing PPE resins are still insufficient and need to be further improved. In addition, today's electronic products must be able to transmit high-frequency signals quickly and in large quantities, and the signal will generate a lot of heat during the transmission process, which will cause loss or delay in signal transmission. The heat resistance provided by existing PPE resins is gradually unable to meet industry needs. Summary of the invention

[0004] In view of the above technical problems, the present invention provides a resin composition, which uses a compound with a specific structure and a specific component with ethylenically unsaturated double bonds in combination. The electronic material obtained after the resin composition is cured can have a high glass transition temperature (Tg), a low thermal expansion coefficient (CTE), a low dielectric constant (Dk) value, a low dielectric loss factor (Df), good anti-aging properties (expressed by changes in Df values), good heat resistance after moisture absorption, good processing stability (expressed by filling and adhesion properties), good adhesion to metal layers (high tear strength), and low water absorption.

[0005] Therefore, an object of the present invention is to provide a resin composition comprising

[0006] (A) a compound having the structure of formula (I); and

[0007]

[0008] (B) a component having an ethylenically unsaturated double bond, which is selected from the following group: a compound having a structure of formula (II), a compound having a structure of formula (III), and a combination thereof,

[0009]

[0010] in,

[0011] Z is a divalent organic group;

[0012] A is independently -O-, -S-, or -N(R1)-, wherein R1 is a hydrogen atom, a C1 to C20 hydrocarbon group, a C1 to C20 halogenated hydrocarbon group, or a group formed by substituting a portion of the hydrocarbon group or halogenated hydrocarbon group with at least one selected from an oxygen atom and a sulfur atom;

[0013] R is an unsubstituted or substituted divalent nitrogen-containing heteroaromatic ring, and each R may be the same as or different from each other;

[0014] X is Each X may be the same as or different from each other, wherein R2 and R3 are each independently a direct bond or a C1 to C4 alkylene group, Ar1 and Ar2 are each independently an unsubstituted or substituted divalent aromatic hydrocarbon group, and L is a direct bond, -O-, -S-, -N(R4)-, -C(O)-O-,

[0015] -C(O)-NH-, -S(O)-, -S(O)2-, -P(O)-, C1 to C20 alkylene, C1 to C20 halogenated alkylene, a divalent cardo structure, or an unsubstituted or substituted divalent C5 to C30 alicyclic hydrocarbon group, R4 is a hydrogen atom, a C1 to C20 hydrocarbon group, or a C1 to C20 halogenated hydrocarbon group, p is an integer from 0 to 5, and when p is 2 or more, each Ar1 may be the same as or different from each other;

[0016] Y is a group containing an ethylenically unsaturated double bond, and each Y may be the same as or different from each other;

[0017] m is an integer from 1 to 100; and

[0018] n is an integer from 1 to 100.

[0019] In some embodiments of the present invention, the component (B) having an ethylenically unsaturated double bond is selected from the following group: a compound having a structure of formula (IIa), a compound having a structure of formula (IIIa), and a combination thereof.

[0020]

[0021]

[0022] in,

[0023] R, A and Y in formula (IIa) and (IIIa) have the same definitions as R, A and Y in formula (II) and (III), respectively;

[0024] X1 and X2 each independently have the same definition as X in formula (II) and (III), and X1 and X2 are different from each other;

[0025] X' is X1 or X2;

[0026] n1 and n2 are each independently an integer from 0 to 50, and the sum of n1 and n2 is less than 100; and

[0027] m1 and m2 are each independently an integer of 0 to 50, but m1 and m2 are not 0 at the same time.

[0028] In some embodiments of the present invention, Z in formula (I) is

[0029]

[0030] -CH2-, or Here, k is an integer from 1 to 5.

[0031] In some embodiments of the present invention, R in formula (II), (III), (IIa), and (IIIa) is each independently an unsubstituted or substituted divalent nitrogen-containing heteroaromatic ring, and the nitrogen-containing heteroaromatic ring is a pyrrole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, a phthalazine ring, a quinazoline ring, a naphthyridine ring, a carbazole ring, an acridine ring, or a phenazine ring, preferably a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, or a triazine ring.

[0032] In some embodiments of the present invention, Ar1 and Ar2 are each independently an unsubstituted or substituted divalent aromatic hydrocarbon group, and the aromatic hydrocarbon group is phenyl, naphthyl, anthracenyl, or biphenyl, and each Ar1 may be the same or different.

[0033] In some embodiments of the present invention, L is C1 to C10 alkylene, C1 to C10 halogenated alkylene, or an unsubstituted or substituted divalent C5 to C30 alicyclic hydrocarbon group,

[0034] in,

[0035] R5 and R6 are each independently a fluorine atom or a C1 to C20 chain hydrocarbon group;

[0036] R7 and R8 are each independently a direct bond, an unsubstituted or substituted chain hydrocarbon group, or an unsubstituted or substituted alicyclic hydrocarbon group; and

[0037] j is an integer from 0 to 4.

[0038] In some embodiments of the present invention, Y in formula (II), (III), (IIa), and (IIIa) is independently 2-isopropenylphenyl, 3-isopropenylphenyl, 4-isopropenylphenyl, 2-allylphenyl, 3-allylphenyl, 4-allylphenyl, 2-methoxy-4-allylphenyl, 4-(1-propenyl)-2-methoxyphenyl, 4-vinylbenzyl, 3-vinylbenzyl, 2-vinylbenzyl, allyl, acrylic, methacrylic, or methallyl.

[0039] In some embodiments of the present invention, the weight ratio of the compound (A) having the structure of formula (I) to the component (B) having an ethylenically unsaturated double bond is 1:9 to 1:1.

[0040] In some embodiments of the present invention, the resin composition further comprises an additive selected from the following group: a catalyst, a crosslinking agent, an elastomer, a filler, a dispersant, a toughening agent, a viscosity modifier, a flame retardant, a plasticizer, a coupling agent, and combinations thereof.

[0041] The catalyst may be selected from the group consisting of diisopropyl peroxide, tertiary butyl peroxybenzoate, di-tert-amyl peroxide (DTAP), isopropyl cumene tertiary butyl peroxide, tertiary butyl cumene peroxide, di(isopropyl cumene) peroxide, di-tertiary butyl peroxide, α,α'-bis(tertiary butyl peroxy)diisopropylbenzene, dibenzoyl peroxide (BPO), 1,1-bis(tertiary butyl peroxy)-3,3,5-trimethylcyclohexane, n-butyl 4,4-di(tertiary butyl peroxy)valerate, 2,5-dimethyl-2,5-di(tertiary butyl peroxy)hexane, 2,5-dimethyl-2,5-di(tertiary butyl peroxy)-3-hexyne, and combinations thereof.

[0042] The crosslinking agent may be selected from the following group: a polyfunctional allylic compound, a polyfunctional acrylate, a polyfunctional acrylamide, a polyfunctional styrenic compound, and combinations thereof.

[0043] The elastomer may be selected from the group consisting of polybutadiene, styrene-butadiene copolymer, styrene-butadiene-divinylbenzene copolymer, polyisoprene, styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, functionalized modified derivatives thereof, and combinations thereof.

[0044] The filler can be selected from the following group: silica, alumina, magnesium oxide, magnesium hydroxide, calcium carbonate, talc, clay, aluminum nitride, boron nitride, aluminum hydroxide, aluminum silicon carbide, silicon carbide, sodium carbonate, titanium dioxide, zinc oxide, zirconium oxide, quartz, diamond, diamondoid, graphite, calcined kaolin, kaolin, mica, hydrotalcite, polytetrafluoroethylene powder, glass beads, ceramic whiskers, carbon nanotubes, nanoscale inorganic powders, and combinations thereof.

[0045] Another object of the present invention is to provide a prepreg, which is obtained by impregnating or coating a substrate with the above-mentioned resin composition and drying the impregnated or coated substrate.

[0046] Another object of the present invention is to provide a metal foil laminate obtained by laminating the above-mentioned prepreg and metal foil, or by coating the above-mentioned resin composition on metal foil and drying the coated metal foil.

[0047] Another object of the present invention is to provide a printed circuit board made from the above-mentioned metal foil laminate.

[0048] In order to make the above-mentioned objectives, technical features and advantages of the present invention more obvious and easy to understand, some specific implementation schemes are described in detail below. DETAILED DESCRIPTION

[0049] Some specific embodiments according to the present invention will be described in detail below; however, the present invention can also be practiced in a variety of different forms, and the protection scope of the present invention should not be interpreted as being limited to what is stated in the description.

[0050] Unless otherwise stated, the terms “a”, “an”, “the” and similar terms used in the specification and claims should be understood to include both the singular and the plural.

[0051] Unless otherwise stated, the content of a component in a solution, mixture, or composition described in this specification and claims is calculated based on the total weight excluding the solvent.

[0052] The resin composition of the present invention, by combining a compound (A) of a specific structure and a specific component (B) having an ethylenically unsaturated double bond, can make the electronic material obtained after the resin composition is cured have good glass transition temperature (Tg), thermal expansion coefficient (CTE), dielectric constant (Dk) value, dielectric loss factor (Df), anti-aging properties (expressed by Df change), heat resistance after moisture absorption, processing stability (expressed by filling and adhesion properties), adhesion to metal layers (high tear strength), and water absorption. The following provides a detailed description of the resin composition of the present invention and its related applications.

[0053] 1. Resin composition

[0054] The resin composition of the present invention comprises (A) a compound having a structure of formula (I) and (B) a component having an ethylenically unsaturated double bond as essential components, and may further comprise optional components as required.

[0055] 1.1. (A) Compounds having the structure of formula (I)

[0056] The compound (A) has a structure represented by the following formula (I) and has an unsaturated functional group, and thus can undergo a cross-linking reaction with the component (B) having an ethylenically unsaturated double bond described below to form a three-dimensional network structure.

[0057]

[0058] In formula (I), Z is a divalent organic group, and specific examples thereof include but are not limited to 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane (i.e., ), 4-methyl-1,3-phenylene (i.e., ), bisphenol A diphenyl ether group (ie,

[0059]

[0060] 4,4'-diphenylmethane (i.e. ), metaphenylene (i.e., ), methyl (ie, -CH2-), or (2,2,4-trimethyl)hexyl (ie, ), wherein k is an integer from 1 to 5.

[0061] The compound (A) of formula (I) has an unsaturated functional group (i.e., a double bond) that can be used for crosslinking reaction, so the crosslinking reaction can be promoted by existing thermal or peroxide catalytic mechanisms to achieve the purpose of thermosetting, and can also co-react with existing crosslinking agents having unsaturated functional groups. Examples of the crosslinking agent include, but are not limited to, vinyl-containing compounds, allyl-containing compounds, and unsaturated functional group-modified PPE (such as allyl-modified PPE).

[0062] The compound (A) having the structure of formula (I) is a terminal vinylated bismaleimide (BMI) derivative, which can be prepared by functionalizing a bismaleimide (BMI) compound. The compound of the structure of formula (I) can be prepared by the following method: First, as shown in the following reaction formula, a vinylbenzyl halide (VB) (e.g., vinylbenzyl chloride) is reacted with cyclopentadiene (CPD) to obtain cyclopentadiene substituted with 4-vinylbenzyl (VB-CPD).

[0063]

[0064] Then, VB-CPD is reacted with a bismaleimide compound to obtain a terminal vinylated bismaleimide derivative of the structure of formula (I). For specific examples of the preparation of the compound of the structure of formula (I), reference can be made to the synthesis examples provided in the Examples section.

[0065] In the resin composition of the present invention, the content of the compound (A) having the structure of formula (I) may be 1 wt % to 30 wt %, such as 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt %, 13 wt %, 14 wt %, 15 wt %, 16 wt %, 17 wt %, 18 wt %, 19 wt %, 20 wt %, 21 wt %, 22 wt %, 23 wt %, 24 wt %, 25 wt %, 26 wt %, 27 wt %, 28 wt %, 29 wt %, or 30 wt %, based on the total weight of the resin composition, but the present invention is not limited thereto.

[0066] 1.2. (B) Components having ethylenically unsaturated double bonds

[0067] 1.2.1. Schemes of Formula (II) and Formula (III)

[0068] The component (B) having an ethylenically unsaturated double bond is selected from the following group: a compound having a structure of formula (II), a compound having a structure of formula (III), and a combination thereof,

[0069]

[0070] wherein m is an integer from 1 to 100, n is an integer from 1 to 100, and A, R, X, and Y are as defined below.

[0071] [A]

[0072] A is independently -O-, -S-, or -N(R1)-, wherein R1 is a hydrogen atom, a C1 to C20 hydrocarbon group, a C1 to C20 halogenated hydrocarbon group, or a group formed by replacing a portion of the hydrocarbon group or halogenated hydrocarbon group with at least one selected from an oxygen atom and a sulfur atom.

[0073] The C1 to C20 hydrocarbon group may be a C1 to C20 chain hydrocarbon group, a C3 to C20 alicyclic hydrocarbon group, or a C6 to C20 aromatic hydrocarbon group. Examples of the C1 to C20 chain hydrocarbon group include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, and pentynyl; examples of the C3 to C20 alicyclic hydrocarbon group include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantane, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and norbornyl; and examples of the C6 to C20 aromatic hydrocarbon group include, but are not limited to, phenyl, benzyl, xylyl, naphthyl, anthracenyl, benzyl, phenethyl, phenylpropyl, and naphthylmethyl.

[0074] The C1 to C20 halogenated hydrocarbon group refers to a group formed by replacing some or all of the hydrogen atoms in the aforementioned C1 to C20 hydrocarbon group with halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0075] The groups formed by replacing a part of the hydrocarbon group or halogenated hydrocarbon group with at least one selected from oxygen atoms and sulfur atoms include but are not limited to groups formed by replacing with -O-, -S-, =O, -S(O)-, or -S(O)2-.

[0076] [R]

[0077] R is an unsubstituted or substituted divalent nitrogen-containing heteroaromatic ring, and each R may be the same as or different from each other.

[0078] Examples of the divalent nitrogen-containing heteroaromatic ring include, but are not limited to, a pyrrole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, a phthalazine ring, a quinazoline ring, a naphthyridine ring, a carbazole ring, an acridine ring, and a phenazine ring, and the nitrogen-containing heteroaromatic ring is preferably a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, or a triazine ring.

[0079] The term "substituted" means that the divalent nitrogen-containing heteroaromatic ring may be substituted by one or more of the following groups: a halogen atom, a nitro group, a cyano group, an amine group (including a primary amine group, a secondary amine group, and a tertiary amine group), a C1 to C20 hydrocarbon group, a C1 to C20 halogenated hydrocarbon group, and a group formed by replacing a portion of the hydrocarbon group or the halogenated hydrocarbon group with at least one selected from an oxygen atom and a sulfur atom, wherein examples of the group formed by replacing a portion of the C1 to C20 hydrocarbon group, the C1 to C20 halogenated hydrocarbon group, and a portion of the hydrocarbon group or the halogenated hydrocarbon group with at least one selected from an oxygen atom and a sulfur atom include, but are not limited to, those described above for A in formula (II) and formula (III).

[0080] [X]

[0081] X is Furthermore, X in formula (II) and formula (III) may be the same as or different from each other.

[0082] At In the above, p is an integer of 0 to 5, and when p is 2 or more, each Ar1 may be the same as or different from each other.

[0083] R2 and R3 are each independently a direct bond or a C1 to C4 alkylene group. Examples of the C1 to C4 alkylene group include, but are not limited to, a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, and a sub-butylene group.

[0084] Ar1 and Ar2 are each independently an unsubstituted or substituted divalent aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include, but are not limited to, phenyl, naphthyl, anthracene, and biphenyl. The substituted group refers to one or more of the following groups: an allyl group, a halogen atom, a nitro group, a cyano group, an amine group (including a primary amine group, a secondary amine group, and a tertiary amine group), a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a C1 to C20 hydrocarbon group, a C1 to C20 halogenated hydrocarbon group, a C1 to C20 alkoxy group, and a C1 to C20 alkylthio group, wherein examples of the C1 to C20 hydrocarbon group and the C1 to C20 halogenated hydrocarbon group include, but are not limited to, those described above for A in formula (II) and formula (III).

[0085] L is a direct bond, -O-, -S-, -N(R4)-, -C(O)-O-, -C(O)-NH-, -S(O)-, -S(O)2-, -P(O)-, a C1 to C20 alkylene group, a C1 to C20 halogenated alkylene group, a divalent cardo structure, or an unsubstituted or substituted divalent C5 to C30 alicyclic hydrocarbon group.

[0086] In -N(R4)-, R4 is a hydrogen atom, a C1 to C20 hydrocarbon group, or a C1 to C20 halogenated hydrocarbon group. Examples of the C1 to C20 hydrocarbon group and the C1 to C20 halogenated hydrocarbon group include, but are not limited to, those described above with respect to A in formula (II) and formula (III).

[0087] Examples of the C1 to C20 alkylene group include, but are not limited to, methylene, ethylene, n-propylene, isopropylene, n-butylene, sub-butylene, neopentylene, 4-methyl-pentane-2,2-diyl, nonane-1,9-diyl, and decane-1,1-diyl.

[0088] Examples of the C1 to C20 halogenated alkylene groups include, but are not limited to, groups formed by replacing some or all of the hydrogen atoms in the aforementioned C1 to C20 alkylene groups with halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0089] The cardo structure refers to a side chain ring structure suspended on the main chain of the molecule, examples of which include but are not limited to and

[0090] The C5 to C30 alicyclic hydrocarbon group may be a C5 to C15 monocyclic alicyclic hydrocarbon group, a C5 to C15 monocyclic fluorinated alicyclic hydrocarbon group, a C7 to C30 polycyclic alicyclic hydrocarbon group, or a C7 to C30 polycyclic fluorinated alicyclic hydrocarbon group. Examples of C5 to C15 monocyclic alicyclic hydrocarbon groups include, but are not limited to, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and cyclododecyl. Examples of C7 to C30 polycyclic alicyclic hydrocarbon groups include, but are not limited to, norbornyl, adamantyl, tricyclo[2.2.1.02,6]heptyl, and camphenyl. Examples of the C5 to C15 monocyclic fluorinated alicyclic hydrocarbon groups and the C7 to C30 polycyclic fluorinated alicyclic hydrocarbon groups include, but are not limited to, groups in which some or all of the hydrogen atoms of the aforementioned C5 to C15 monocyclic alicyclic hydrocarbon groups and the C7 to C30 polycyclic alicyclic hydrocarbon groups are substituted with fluorine atoms.

[0091] The C5 to C30 alicyclic hydrocarbon group may be substituted, which means that it may be substituted by one or more of the following groups: a halogen atom, a nitro group, a cyano group, an amine group (including a primary amine group, a secondary amine group, and a tertiary amine group), a C1 to C20 hydrocarbon group, a C1 to C20 halogenated hydrocarbon group, and a group formed by replacing a portion of the hydrocarbon group or the halogenated hydrocarbon group with at least one selected from an oxygen atom and a sulfur atom, wherein examples of the C1 to C20 hydrocarbon group, the C1 to C20 halogenated hydrocarbon group, and a group formed by replacing a portion of the hydrocarbon group or the halogenated hydrocarbon group with at least one selected from an oxygen atom and a sulfur atom include those described above for A in formula (II) and formula (III).

[0092] In some embodiments of the present invention, L is C1 to C10 alkylene, C1 to C10 halogenated alkylene, or an unsubstituted or substituted divalent C5 to C30 alicyclic hydrocarbon group, wherein R5 and R6 are each independently a fluorine atom, or a C1 to C20 chain hydrocarbon group, R7 and R8 are each independently a direct bond, an unsubstituted or substituted chain hydrocarbon group, or an unsubstituted or substituted alicyclic hydrocarbon group, and j is an integer from 0 to 4.

[0093] [Y]

[0094] Y is a group containing an ethylenic unsaturated double bond, and each Y may be the same as or different from each other. The group containing an ethylenic unsaturated double bond is preferably a C3 to C50 group containing an ethylenic unsaturated double bond, and specific examples thereof include but are not limited to 2-isopropenylphenyl, 3-isopropenylphenyl, 4-isopropenylphenyl, 2-allylphenyl, 3-allylphenyl, 4-allylphenyl, 2-methoxy-4-allylphenyl, 4-(1-propenyl)-2-methoxyphenyl, 4-vinylbenzyl, 3-vinylbenzyl, 2-vinylbenzyl, allyl, acrylic, methacrylic, and methallyl.

[0095] 1.2.2. Schemes of Formula (IIa) and Formula (IIIa)

[0096] In some embodiments of the present invention, the component (B) having an ethylenically unsaturated double bond comprises at least two different Xs. Specifically, the component (B) having an ethylenically unsaturated double bond is selected from the following group: a compound having a structure of formula (IIa), a compound having a structure of formula (IIIa), and a combination thereof,

[0097]

[0098]

[0099] wherein R, A and Y in formula (IIa) and (IIIa) have the same definitions as R, A and Y in formula (II) and (III), respectively; X1 and X2 each independently have the same definition as X in formula (II) and (III), and X1 and X2 are different from each other; X' is X1 or X2; n1 and n2 each independently are integers from 0 to 50, and the sum of n1 and n2 is less than 100; and m1 and m2 each independently are integers from 0 to 50, but m1 and m2 are not 0 at the same time.

[0100] 1.2.3. Synthesis of component (B)

[0101] There is no particular limitation on the synthesis method of the component (B) having an ethylenically unsaturated double bond. Based on the disclosure of the present specification, a person skilled in the art can prepare the component (B) having an ethylenically unsaturated double bond using an existing chemical synthesis method. For example, the component (B) having an ethylenically unsaturated double bond having a structure of formula (II) or formula (III) can be synthesized by the following synthesis method: in an organic solvent, in the presence of an alkali metal or an alkali metal compound, a monomer comprising an R portion, a monomer comprising an X portion, and a monomer comprising a Y portion are reacted together, or a monomer comprising an R portion is first reacted with a monomer comprising an X portion, and then further reacted with a monomer comprising a Y portion, to form a component (B) in which the X portion and the Y portion, the X portion and the R portion, and the Y portion and the R portion are connected by a portion A, wherein the portion A can be derived from a monomer comprising an X portion or a monomer comprising a Y portion.

[0102] Examples of monomers comprising an R moiety include, but are not limited to, 4,6-dichloropyrimidine, 4,6-dibromopyrimidine, 2,4-dichloropyrimidine, 2,5-dichloropyrimidine, 2,5-dibromopyrimidine, 5-bromo-2-chloropyrimidine, 5-bromo-2-fluoropyrimidine, 5-bromo-2-iodopyrimidine, 2-chloro-5-fluoropyrimidine, 2-chloro-5-iodopyrimidine, 2-phenyl-4,6-dichloropyrimidine, 2-methylthio-4,6-dichloropyrimidine, 2-methylsulfonyl-4,6-dichloropyrimidine, 5-methyl-4,6-dichloropyrimidine, 2-amino-4,6-dichloropyrimidine, 5-amino-4,6-dichloropyrimidine, 2,5-diamino-4,6-dichloropyrimidine, 4-amino-2,6-dichloropyrimidine, 5-methoxy-4,6- Pyrimidine compounds such as dichloropyrimidine, 5-methoxy-2,4-dichloropyrimidine, 2-methyl-4,6-dichloropyrimidine, 6-methyl-2,4-dichloropyrimidine, 5-methyl-2,4-dichloropyrimidine, 5-nitro-2,4-dichloropyrimidine, 4-amino-2-chloro-5-fluoropyrimidine, 2-methyl-5-amino-4,6-dichloropyrimidine, and 5-bromo-4-chloro-2-methylthiopyrimidine; pyridazine compounds such as 3,6-dichloropyridazine, 3,5-dichloropyridazine, and 4-methyl-3,6-dichloropyridazine; pyrazine compounds such as 2,3-dichloropyrazine, 2,6-dichloropyrazine, 2,5-dibromopyrazine, 2,6-dibromopyrazine, 2-amino-3,5-dibromopyrazine, and 5,6-dicyano-2,3-dichloropyrazine. The aforementioned monomers containing R moieties may be used alone or in any combination.

[0103] Examples of the monomer compound containing the X portion include, but are not limited to, dihydroxyphenyl compounds such as hydroquinone, resorcinol, catechol, and phenylhydroquinone; 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-allylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 4,4'-(1,3-dimethylbutylene)bisphenol, 1,1-bis(4-hydroxyphenyl)-nonane, bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, Bisphenol compounds such as 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 4,4'-cyclododecylidenebisphenol, and 4,4'-decylidenebisphenol; and diol compounds such as PRIPLAST 1901, 1838, 3186, 3192, 3197, and 3199 (manufactured by Croda Japan Co., Ltd.). The aforementioned monomers containing the X moiety may be used alone or in any combination.

[0104] Examples of the monomers containing the Y portion include, but are not limited to, monophenol compounds such as 4-isopropenylphenol, 3-isopropenylphenol, 2-isopropenylphenol, 4-vinylphenol, 2-allylphenol, 3-allylphenol, and 4-allylphenol; aliphatic halides such as allyl chloride, 4-(chloromethyl)styrene, 3-(chloromethyl)styrene, and 2-(chloromethyl)styrene; acid halides such as acryloyl chloride and methacryloyl chloride; acid anhydrides such as acrylic anhydride and methacrylic anhydride; unsaturated alcohols such as (4-vinylphenyl)methanol, (3-vinylphenyl)methanol, and (2-vinylphenyl)methanol. The aforementioned monomers containing the Y portion can be used alone or in any combination.

[0105] Examples of the organic solvent include, but are not limited to, tetrahydrofuran (THF), dioxane, cyclopentyl methyl ether, anisole, phenethyl ether, diphenyl ether, dialkoxybenzene, trialkoxybenzene, N,N-dimethylacetamide (DMAc), N,N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, cyclopentane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, diphenyl sulfone, benzophenone, 2-heptanone, cyclohexanone, methyl ethyl ketone, dichloromethane, chloroform, chlorobenzene, benzene, toluene, and xylene. The aforementioned solvents can be used alone or in any combination.

[0106] Examples of the alkali metal or alkali metal compound include, but are not limited to, lithium, sodium, potassium, sodium hydride, potassium hydride, lithium hydride, lithium carbonate, sodium carbonate, potassium carbonate, lithium bicarbonate, sodium bicarbonate, and potassium bicarbonate. The aforementioned alkali metal or alkali metal compound can be used alone or in any combination.

[0107] The weight average molecular weight (Mw) of the synthesized component (B) having ethylenically unsaturated double bonds is preferably 1000 to 500,000, but the present invention is not limited thereto. The weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) and compared and converted with a standard product, and its unit is "g / mol (g / mol)".

[0108] For specific examples of the method for synthesizing the component (B) having an ethylenically unsaturated double bond, reference can be made to the synthesis examples provided below.

[0109] 1.2.4. Content of ingredient (B)

[0110] In the resin composition of the present invention, the content of the component (B) having an ethylenically unsaturated double bond may be 15 wt % to 40 wt %, for example, 15 wt %, 16 wt %, 17 wt %, 18 wt %, 19 wt %, 20 wt %, 21 wt %, 22 wt %, 23 wt %, 24 wt %, 25 wt %, 26 wt %, 27 wt %, 28 wt %, 29 wt %, 30 wt %, 31 wt %, 32 wt %, 33 wt %, 34 wt %, 35 wt %, 36 wt %, 37 wt %, 38 wt %, 39 wt %, or 40 wt %, based on the total weight of the resin composition, but the present invention is not limited thereto.

[0111] In the resin composition of the present invention, the weight ratio of the compound (A) having the structure of formula (I) to the component (B) having an ethylenically unsaturated double bond is preferably 1:9 to 1:1, for example 1:9, 1:8.5, 1:8, 1:7.5, 1:7, 1:6.5, 1:6, 1:5.5, 1:5, 1:4.5, 1:4, 1:3.5, 1:3, 1:2.5, 1:2, 1:1.5, or 1:1, or a range between any two of the above values. The weight ratio of the component (A) to the component (B) of the resin composition of the present invention can achieve better effects of the invention within the above range.

[0112] 1.3. Selection of ingredients

[0113] Without violating the technical principle of the present invention, the resin composition of the present invention may further include optional components as needed, such as catalysts, crosslinking agents, elastomers, fillers and additives available in the art as exemplified below, to adaptably improve the processability of the resin composition during the manufacturing process, or improve the physical and chemical properties of the electronic material made of the resin composition. Examples of additives available in the art include, but are not limited to, dispersants, toughening agents, viscosity modifiers, flame retardants, plasticizers, and coupling agents.

[0114] [catalyst]

[0115] In some embodiments of the present invention, the resin composition further comprises a catalyst. A catalyst refers to a component that can promote a crosslinking reaction. Examples of catalysts include, but are not limited to, organic peroxides. Examples of organic peroxides include, but are not limited to, diisopropyl peroxide, tertiary butyl peroxybenzoate, di-tertiary amyl peroxide, isopropyl isopropyl tertiary butyl peroxide, tertiary butyl isopropyl peroxide, di(isopropyl isopropyl) peroxide, di-tertiary butyl peroxide, α,α'-bis(tertiary butyl peroxy) diisopropylbenzene, dibenzoyl peroxide, 1,1-bis(tertiary butyl peroxy)-3,3,5-trimethylcyclohexane, 4,4-di(tertiary butyl peroxy) valerate n-butyl ester, 2,5-dimethyl-2,5-di(tertiary butyl peroxy) hexane, and 2,5-dimethyl-2,5-di(tertiary butyl peroxy)-3-hexyne. Each of the aforementioned organic peroxides may be used alone or in any combination. In the following examples, α,α′-bis(tertiary butylperoxy)diisopropylbenzene (Perbutyl P) was used.

[0116] Based on the total weight of the resin composition, the content of the catalyst may be 0.1 wt % to 1 wt %, for example 0.1 wt %, 0.2 wt %, 0.3 wt %, 0.4 wt %, 0.5 wt %, 0.6 wt %, 0.7 wt %, 0.8 wt %, 0.9 wt %, or 1 wt %, or a range between any two of the above values, but the present invention is not limited thereto.

[0117] [Crosslinking agent]

[0118] In some embodiments of the present invention, the resin composition further comprises a crosslinking agent. The crosslinking agent refers to a component having an unsaturated group and capable of undergoing a crosslinking reaction with the compound (A) having the structure of formula (I) or the component (B) having an ethylenically unsaturated double bond to form a three-dimensional network structure, wherein the unsaturated group refers to a group that can initiate an addition polymerization reaction by light or heat in the presence of a polymerization initiator. Examples of unsaturated groups include, but are not limited to, vinyl, vinyl benzyl, allyl, acrylic, and methacrylic.

[0119] The crosslinking agent can be divided into a monofunctional crosslinking agent having only one unsaturated group and a polyfunctional crosslinking agent having at least two unsaturated groups according to the number of unsaturated groups contained, and a polyfunctional crosslinking agent is preferably used. Examples of the polyfunctional crosslinking agent include, but are not limited to, polyfunctional allyl compounds, polyfunctional acrylates, polyfunctional acrylamides, and polyfunctional styrene compounds. Each crosslinking agent can be used alone or in any combination.

[0120] The polyfunctional allyl compound refers to a compound containing at least two allyl groups. Examples of the polyfunctional allyl compound include, but are not limited to, diallyl phthalate, diallyl isophthalate, triallyl trimellitate, triallyl mesate, 1,1'-(1,4-butyl)bis(3,5-diallyl-1,3,5-triazine-2,4,6-trione) (hereinafter referred to as "Di-L-DAIC"), triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), and prepolymers of the aforementioned compounds. In the examples attached below, TAIC or Di-L-DAIC is used.

[0121] The multifunctional acrylate refers to a compound containing at least two acrylate groups. Examples of the multifunctional acrylate include, but are not limited to, trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butanedioldi(meth)acrylate, 1,4-butanediol di(meth)acrylate, cyclohexane dimethanol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and prepolymers containing the foregoing compounds.

[0122] The polyfunctional styrene compound refers to a compound having at least two alkenyl groups connected to an aromatic ring. Examples of the polyfunctional styrene compound include, but are not limited to, 1,3-divinylbenzene, 1,4-divinylbenzene, trivinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,2-bis(p-vinylphenyl)ethane, 1,2-bis(m-vinylphenyl)ethane, 1-(p-vinylphenyl)-2-(m-vinylphenyl)ethane, 1,4-bis(p-vinylphenylethyl)benzene ...m-vinylphenylethyl)benzene, 1,4-bis(p-vinylphenylethyl)benzene, 1,4-bis(m-vinylphenylethyl)benzene, 1,4-bis(m-vinylphenylethyl)ben benzene), 1,4-bis(m-vinylphenylethyl)benzene, 1,3-bis(p-vinylphenylethyl)benzene, 1,3-bis(m-vinylphenylethyl)benzene, 1-(p-vinylphenylethyl)-4-(m-vinylphenylethyl)benzene, 1-(p-vinylphenylethyl)-3-(m-vinylphenylethyl)benzene, and prepolymers containing the foregoing compounds.

[0123] Based on the total weight of the resin composition, the content of the cross-linking agent may be 0 wt % to 20 wt %, for example, 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt %, 13 wt %, 14 wt %, 15 wt %, 16 wt %, 17 wt %, 18 wt %, 19 wt %, or 20 wt %, or a range formed by any two of the above values, but the present invention is not limited thereto.

[0124] [Elastomer]

[0125] In some embodiments of the present invention, the resin composition further comprises an elastomer. In the present invention, the resin composition may further comprise an elastomer to improve the toughness of the electronic material produced. Examples of elastomers include, but are not limited to, polybutadiene, styrene-butadiene copolymers, styrene-butadiene-divinylbenzene copolymers, polyisoprene, styrene-isoprene copolymers, acrylonitrile-butadiene copolymers, acrylonitrile-butadiene-styrene copolymers, and the aforementioned functionalized modified derivatives, wherein examples of functionalized modified derivatives include, but are not limited to, maleic anhydride modified polybutadiene and maleic anhydride modified polybutadiene-styrene copolymers. The aforementioned elastomers may be used alone or in any combination. In the attached examples, styrene-butadiene-divinylbenzene copolymers are used.

[0126] Based on the total weight of the resin composition, the elastomer content may be 0 wt % to 10 wt %, for example, 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, or 10 wt %, or a range between any two of the above values, but the present invention is not limited thereto.

[0127] [filler]

[0128] In some embodiments of the present invention, the resin composition further comprises a filler. Examples of fillers include, but are not limited to, silica (including solid silica and hollow silica), alumina, magnesium oxide, magnesium hydroxide, calcium carbonate, talc, clay, aluminum nitride, boron nitride, aluminum hydroxide, aluminum silicon carbide, silicon carbide, sodium carbonate, titanium dioxide, zinc oxide, zirconium oxide, quartz, diamond, diamondoid, graphite, calcined kaolin, kaolin, mica, hydrotalcite, polytetrafluoroethylene (PTFE) powder, glass beads, ceramic whiskers, carbon nanotubes, and nanoscale inorganic powders. Each filler can be used alone or in any combination. In the attached examples, silica is used.

[0129] Based on the total weight of the resin composition, the filler content may be 30 wt % to 50 wt %, for example, 30 wt %, 31 wt %, 32 wt %, 33 wt %, 34 wt %, 35 wt %, 36 wt %, 37 wt %, 38 wt %, 39 wt %, 40 wt %, 41 wt %, 42 wt %, 43 wt %, 44 wt %, 45 wt %, 46 wt %, 47 wt %, 48 wt %, 49 wt %, or 50 wt %, or a range between any two of the above values, but the present invention is not limited thereto.

[0130] 1.4. Preparation of resin composition

[0131] Regarding the preparation of the resin composition of the present invention, the components of the resin composition, including the compound (A) having the structure of formula (I), the component (B) having an ethylenically unsaturated double bond, and other selected components, can be uniformly mixed with a stirrer and dissolved or dispersed in a solvent to form a varnish-like form for subsequent processing. The solvent can be any inert solvent that can dissolve or disperse the components of the resin composition but does not react with these components. Examples of the inert solvent include but are not limited to toluene, γ-butyrolactone, methyl ethyl ketone, cyclohexanone, butanone, acetone, xylene, methyl isobutyl ketone, N,N-dimethylformamide (N,N-dimethyl formamide, DMF), N,N-dimethylacetamide (N,N-dimethyl acetamide, DMAc), and N-methylpyrolidone (N-methyl-pyrolidone, NMP), and the aforementioned solvents can be used alone or in combination. There is no particular limitation on the amount of the solvent, as long as the components of the resin composition can be uniformly dissolved or dispersed therein. In some embodiments of the present invention, a mixture of methyl ethyl ketone (MEK) and toluene is used as the solvent.

[0132] 2. Prepreg

[0133] The present invention also provides a prepreg made from the above resin composition, wherein the prepreg is made by impregnating a substrate with the above resin composition or coating the above resin composition on a substrate, and drying the impregnated or coated substrate. Common substrates include, but are not limited to, paper, cloth or felt made from materials selected from the following groups: paper fiber, glass fiber, quartz fiber, organic polymer fiber, carbon fiber, and combinations thereof. Examples of organic polymer fibers include, but are not limited to, high-modulus polypropylene (HMPP) fiber, polyamide fiber, ultra-high molecular weight polyethylene (UHMWPE) fiber, and liquid crystal polymer (LCP) fiber, and the cloth made from the above group of materials can be a woven fabric or a non-woven fabric. In some embodiments of the present invention, 1078 reinforced glass fiber cloth is used as a reinforcing material, and is heated and dried at 175°C for 2 to 15 minutes (B-stage) to obtain a prepreg in a semi-cured state.

[0134] 3. Metal foil laminates and printed circuit boards

[0135] The present invention also provides a metal foil laminate, which is obtained by laminating the above-mentioned prepreg and metal foil. Specifically, the metal foil laminate of the present invention comprises a dielectric layer and a metal layer, wherein the dielectric layer is provided by the above-mentioned prepreg, wherein the above-mentioned prepreg can be stacked in multiple layers as the dielectric layer, and a metal foil (such as copper foil, as the metal layer) is stacked on at least one outer surface of the dielectric layer formed by stacking the prepreg to provide a stack, and the stack is subjected to a hot pressing operation to obtain the metal foil laminate. Alternatively, the above-mentioned resin composition can be directly coated on a metal foil and the coated metal foil can be dried to obtain the metal foil laminate.

[0136] In addition, a printed circuit board can be manufactured by further patterning the outer metal foil of the metal foil laminate.

[0137] 4. Examples

[0138] 4.1. Measurement method description

[0139] The present invention is further illustrated by the following specific embodiments, wherein the measuring instruments and methods used are as follows:

[0140] [Tear strength test]

[0141] Tear strength refers to the adhesion of the metal foil as a conductive layer to the dielectric layer. The strength of the adhesion is expressed by the amount of force required to tear a 1 / 8 inch wide copper foil vertically from the board surface. The unit of tear strength is pound force / inch (lbf / in).

[0142] [Glass transition temperature (Tg) test]

[0143] The copper foil of the copper foil laminate is removed by etching to obtain a non-clad board. The glass transition temperature (Tg) of the non-clad board is measured. Specifically, a dynamic mechanical analyzer (DMA) with the model "Q800" manufactured by TA Instruments is used to determine the Tg of the non-clad board. The test conditions are as follows: a bending module is used with a frequency of 10 Hz and a heating rate of 5°C / min, and dynamic viscoelasticity measurements are performed during the process of heating from room temperature to 280°C. Tg is the temperature at which tanδ reaches a maximum value in the obtained viscoelasticity curve.

[0144] [Coefficient of thermal expansion (z-CTE) test]

[0145] The thermal expansion coefficient (z-CTE) of the fully cured resin composition in the Z-axis direction (thickness direction) is measured using a thermomechanical analyzer (TMA). The test method is as follows: prepare a 5 mm × 5 mm × 1.5 mm fully cured resin composition as a test sample, set the starting temperature to 30°C, the ending temperature to 330°C, the heating rate to 10°C / min, and the load to 0.05 Newton (N). Under the above conditions, perform a thermomechanical analysis on the test sample in the expansion / compression mode, measure the thermal expansion per 1°C in the temperature range of 30°C to 330°C and take the average value. The unit of z-CTE is %.

[0146] [Dielectric property test (dielectric constant Dk0 and dielectric loss factor Df0 in dry state)]

[0147] The copper foil laminate was etched to remove the copper foil on both sides to obtain a non-cladding board as a test piece, and its resin content (RC) was 70%. The test piece was placed in a 105°C dryer for 2 hours to remove moisture from the test piece. Then, the test piece was taken out of the dryer, placed in a desiccator and the temperature was returned to 25°C. The dielectric constant and dielectric loss factor of the test piece were measured by the cavity resonator perturbation method. Specifically, a network analyzer (ZNA67 manufactured by Rohde & Schwarz Co., Ltd.) was used to measure the dielectric constant (Dk0) and dielectric loss factor (Df0) of the test piece in a dry state at 10GHz.

[0148] [Thermal oxidation aging test (change in dielectric loss factor after high temperature treatment ΔDf1)]

[0149] The copper foil laminate was etched to remove the copper foil on both sides to obtain a non-cladding board (RC is 70%) as a test piece. The test piece was placed in a dryer at 105°C for 2 hours to remove moisture from the test piece. Then, the test piece was taken out of the dryer, placed in a desiccator and the temperature was returned to 25°C. The dielectric loss factor (Df0) of the test piece in a dry state at 10 GHz was measured in the same way as the dielectric property test.

[0150] Afterwards, the dried test piece was placed in an oven at 125° C. for 30 days, and the dielectric loss factor (Df1) of the test piece at 10 GHz after high temperature treatment was measured using the same method as the dielectric property test.

[0151] The dielectric loss factor change ΔDf1 is calculated according to the following formula and evaluated according to the following criteria. The smaller the change, the better the thermal oxidation aging resistance of the test piece.

[0152] ΔDf1=Df1-Df0

[0153] ◎: Change 0.0025 or less

[0154] ○: Change is greater than 0.0025 and less than 0.0030

[0155] △: Change is greater than 0.0030 and less than 0.0045

[0156] ╳: Change is greater than 0.0045

[0157] [Anti-wet heat aging test (change in dielectric loss factor ΔDf2 after high temperature and high humidity treatment)]

[0158] The copper foil laminate was etched to remove the copper foil on both sides to obtain a non-cladding board (RC is 70%) as a test piece. The test piece was placed in a 105°C dryer and dried for 2 hours to remove moisture from the test piece. Then, the test piece was taken out of the dryer, placed in a desiccator and the temperature was returned to 25°C. The dielectric loss factor (Df0) of the test piece in a dry state at 10 GHz was measured in the same way as the dielectric property test.

[0159] After that, the dried test piece was placed in an environment of 85°C and 85% relative humidity (RH) for 30 days, and the dielectric loss factor (Df2) of the test piece after high temperature and high humidity treatment at 10GHz was measured by the same method as the dielectric property test. The change in dielectric loss factor ΔDf2 was calculated according to the following formula, and evaluated according to the following benchmarks. The smaller the change, the better the resistance of the test piece to moisture and heat aging.

[0160] ΔDf2=Df2-Df0

[0161] ◎: Change 0.0025 or less

[0162] ○: Change is greater than 0.0025 and less than 0.0030

[0163] △: Change is greater than 0.0030 and less than 0.0045

[0164] ╳: Change is greater than 0.0045

[0165] [Heat resistance test after moisture absorption]

[0166] The heat resistance after moisture absorption is tested according to the JIS C5012 method, and the heat resistance of solder floating after 120 hours in an environment of 60°C and 60% relative humidity (RH) is evaluated. Specifically, the metal foil laminate is floated in a solder bath at 288°C for 60 seconds, and then the metal foil laminate is observed visually and under an optical microscope (5x to 1000x magnification can be used to assist observation) to see if there are any measlings or swellings on the metal foil laminate after the float test. If no measlings or swellings are observed, it means that the heat resistance after moisture absorption test has been passed, and it is recorded as "○"; if measlings or swellings are observed, it means that the heat resistance after moisture absorption test has been failed, and it is recorded as "╳".

[0167] [Glue filling test]

[0168] A glass fiber epoxy substrate having 588 plated through holes formed by plate plating was prepared, the substrate having a plate thickness of 1.8 mm and a plated through hole diameter of 0.9 mm. A NE-glass fiber cloth of model 1078 was impregnated or coated with a resin composition and dried at 175°C for 2 to 5 minutes (B-stage) to obtain a semi-cured sheet (resin content of 70% and thickness of 0.88 mm). Then, two semi-cured sheets were stacked on one side of the glass fiber epoxy substrate having through holes, and then heated to 200°C to 220°C at a heating rate of 2°C / min to 4°C / min, and hot-pressed and cured at this temperature for 120 minutes at a full pressure of 18 kg / cm2 (initial pressure of 8 kg / cm2), thereby preparing an evaluation sample. The sample was placed under an optical microscope with a magnification of 100 times, and the cross-section of the 588 filled through holes was observed. The evaluation criteria are as follows: if all through holes are completely filled or only a few through holes are not completely filled (the number of unfilled through holes is less than 118), it means that the filling is good and is recorded as "○"; and if the resin composition flows out from the bottom of the through hole or there are multiple unfilled through holes (the number of unfilled through holes is greater than 118), it means that the filling is poor and is recorded as "╳".

[0169] [Adhesion test]

[0170] The resin composition is impregnated or coated on NE-glass fiber cloth of model 1078, and dried at 175°C for 2 to 5 minutes (B-stage) to obtain a semi-cured prepreg, and multiple prepregs are stacked. Visually observe the stacking of the prepregs. If no colloid peeling or sticking behavior is found, it means that the prepreg is not sticky and has good processing stability, and is recorded as "○"; if colloid peeling or sticking behavior is found, it means that it will stick and has poor processing stability, and is recorded as "╳".

[0171] [Water absorption test]

[0172] Water absorption test is performed according to IPC-TM650 2.6.2.1. The prepreg is cut into 2 inch x 2 inch samples and weighed after drying (accurately weighed to 0.1 mg). After that, the sample is immersed in a constant temperature distilled water bath at 23±1.1℃ for 24 hours, and the sample after water absorption is weighed (accurately weighed to 0.1 mg). The difference between the weight after water absorption and the weight after drying relative to the weight after drying is the percentage of the water absorption.

[0173] 4.2. Preparation of compounds

[0174] 4.2.1. Preparation of compounds having the structure of formula (I)

[0175] [Preparation of terminal modifier VB-CPD]

[0176] 17.5 g of sodium hydride was washed with hexane to remove mineral oil. The washed sodium hydride was then suspended in 350 ml of hexane in a 1000 ml round bottom flask. The flask was filled with an inert atmosphere and cooled to 5°C.

[0177] 44.0 g of fresh-cracked cyclopentadiene (CPD) were added in portions under vigorous stirring. After the addition of CPD was completed, the temperature was raised to 60° C. with reflux system, and then 100 g of 4-vinylbenzyl chloride (VB) were added in portions.

[0178] 150 g of deionized water was added and stirred vigorously for 30 minutes to obtain a biphasic mixture. The organic phase of the biphasic mixture was then washed several times with 10 wt % HCl aqueous solution and deionized water.

[0179] The organic phase was separated and dried over sodium sulfate, and the solvent was removed by rotary distillation to obtain 4-vinylbenzyl substituted cyclopentadiene (VB-CPD) as shown below.

[0180]

[0181] [Synthesis Example A1: Synthesis of Compound S1B]

[0182] 7.80 g of VB-CPD and 10.0 g of 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (i.e., the compound of the following formula S1A) were mixed and dissolved in 20.0 g of dichloromethane solvent. The resulting homogeneous solution was reacted at room temperature for 30 minutes, and then the dichloromethane solvent was removed by rotary evaporation at 50° C. to obtain the following compound of formula S1B having the structure of formula (I).

[0183]

[0184] [Synthesis Example A2: Synthesis of S2B Compound]

[0185] 10.0 g of VB-CPD and 10.0 g of the compound of formula S2A were mixed and dissolved in 20.0 g of dichloromethane solvent. The resulting homogeneous solution was reacted at room temperature for 30 minutes, and then the dichloromethane solvent was removed by rotary evaporation at 50° C. to obtain the compound of formula S2B having the structure of formula (I). In formulas S2A and S2B, k is an integer from 1 to 5.

[0186]

[0187] 4.2.2. Preparation of components having ethylenically unsaturated double bonds

[0188] [Synthesis Example B1: Synthesis of Polymer 1]

[0189] Under an inert atmosphere, 29 g of 2,2-bis(4-hydroxy-3-methylphenyl)propane, 18.9 g of 2-phenyl-4,6-dichloropyrimidine, and 21.2 g of potassium carbonate were added to a 500 ml round-bottom flask, and 46.7 g of N-methyl-2-pyrrolidone solvent was added, followed by stirring at 100°C for 6 hours. After the reaction was completed, the product was cooled to 10°C, and a mixture of 12.7 g of 3-(chloromethyl)styrene and 4-(chloromethyl)styrene was slowly titrated at 10°C, then the temperature was raised to 100°C and reacted at 100°C for 4 hours. Then, 61 g of N-methyl-2-pyrrolidone solvent was added and stirred for 30 minutes. After that, methanol was added for repeated washing and filtration, and the solvent was removed by rotary distillation to obtain a polymer 1 shown in the following formula (II-1). In formula (II-1), n ​​is an integer from 1 to 5.

[0190]

[0191] [Synthesis Example B2: Synthesis of Polymer 2]

[0192] Under an inert atmosphere, 41 g of 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 20 g of 2-phenyl-4,6-dichloropyrimidine, and 22.4 g of potassium carbonate were added to a 500 ml round-bottom flask, and 51 g of N-methyl-2-pyrrolidone solvent was added, followed by stirring at 100°C for 6 hours. After the reaction was completed, the product was cooled to 10°C, and a mixture of 10.4 g of 3-(chloromethyl)styrene and 4-(chloromethyl)styrene was slowly titrated at 10°C, then the temperature was raised to 100°C and reacted at 100°C for 4 hours. Then, 67 g of N-methyl-2-pyrrolidone solvent was added and stirred for 30 minutes. After that, methanol was added for repeated washing and filtration, and the solvent was removed by rotary distillation to obtain polymer 2 shown in the following formula (II-2). In formula (II-2), n is an integer from 1 to 5.

[0193]

[0194] [Synthesis Example B3: Synthesis of Polymer 3]

[0195] Under an inert atmosphere, 49.2 g of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 43.3 g of 2-phenyl-4,6-dichloropyrimidine, and 48.5 g of potassium carbonate were added to a 500 ml round-bottom flask, and 236 g of N-methyl-2-pyrrolidone solvent was added, followed by stirring at 100°C for 6 hours. After the reaction was completed, the product was cooled to 10°C, and a mixture of 22.6 g of 3-(chloromethyl)styrene and 4-(chloromethyl)styrene was slowly titrated at 10°C, then the temperature was raised to 100°C and reacted at 100°C for 4 hours. Then, 72 g of N-methyl-2-pyrrolidone solvent was added and stirred for 30 minutes. After that, methanol was added for repeated washing and filtration, and the solvent was removed by rotary distillation to obtain polymer 3 shown in the following formula (II-3). In formula (II-3), n is an integer from 1 to 5.

[0196]

[0197] [Synthesis Example B4: Synthesis of Polymer 4]

[0198] Under an inert atmosphere, 99.6 g of 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 41.7 g of 2-phenyl-4,6-dichloropyrimidine, and 55 g of potassium carbonate were added to a 500 ml round-bottom flask, and 89.6 g of N-methyl-2-pyrrolidone solvent was added, followed by stirring at 140°C for 6 hours. After the reaction was completed, the product was cooled to 10°C, and 8.5 g of methacryloyl chloride was slowly titrated at 10°C, then the temperature was raised to 70°C and reacted at 70°C for 4 hours. Then, 515 g of N-methyl-2-pyrrolidone solvent was added and stirred for 30 minutes. After that, methanol was added for repeated washing and filtration, and the solvent was removed by rotary distillation to obtain polymer 4 shown in the following formula (II-4). In formula (II-4), n is an integer from 1 to 5.

[0199]

[0200] [Synthesis Example B5: Synthesis of Polymer 5]

[0201] Under an inert atmosphere, 72.0 g of 2,2-bis(4-hydroxy-3-methylphenyl)propane, 71.2 g of 2-phenyl-4,6-dichloropyrimidine, and 50.3 g of potassium carbonate were added to a 1000 ml round-bottom flask, and 89.6 g of N-methyl-2-pyrrolidone solvent was added, followed by stirring at 105°C for 7 hours. After the reaction was completed, the product was cooled to 10°C, and 11.2 g of (3-vinylphenyl)methanol and (4-vinylphenyl)methanol were slowly titrated at 10°C, then the temperature was raised to 105°C and reacted at 105°C for 5 hours. Then, 511 g of N-methyl-2-pyrrolidone solvent was added and stirred for 35 minutes. Afterwards, methanol was added for repeated washing and filtration, and the solvent was removed by rotary distillation to obtain a polymer 5 shown in the following formula (III-1). In formula (III-1), m is an integer from 1 to 5.

[0202]

[0203] [Synthesis Example B6: Synthesis of Polymer 6]

[0204] Under an inert atmosphere, 44.9 g of 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 82.6 g of 2-phenyl-4,6-dichloropyrimidine, and 59.2 g of potassium carbonate were added to a 1000 ml round-bottom flask, followed by 45.1 g of 2,2-bis(4-hydroxy-3-allylphenyl)propane and 96.5 g of N-methyl-2-pyrrolidone solvent, followed by stirring at 140° C. for 4 hours. After the reaction was completed, the product was cooled to 10° C., and 11.2 g of (3-vinylphenyl)methanol and (4-vinylphenyl)methanol were slowly titrated at 10° C., then the temperature was raised to 70° C. and reacted at 70° C. for 4 hours. Then, 515 g of N-methyl-2-pyrrolidone solvent was added and stirred for 30 minutes. Then, methanol was added for repeated washing and filtration, and the solvent was removed by rotary distillation to obtain a polymer 6 represented by the following formula (IIIa-1). In formula (IIIa-1), m1 is an integer of 1 to 5, and m2 is an integer of 1 to 5.

[0205]

[0206] 4.3. Preparation of resin composition

[0207] 4.3.1. List of raw materials used in the examples and comparative examples:

[0208]

[0209]

[0210] 4.3.2. Preparation method

[0211] According to the components and proportions shown in Tables 1-1, 1-2, and 2, the components were mixed at room temperature using a stirrer, and methyl ethyl ketone (purchased from Genxiang Industrial Co., Ltd.) and toluene (purchased from Sichuan Qing Chemical Co., Ltd.) were added. The resulting mixture was then stirred at room temperature for 60 to 120 minutes to obtain the resin compositions of Examples E1 to E16 and Comparative Examples CE1 to CE10.

[0212] Table 1-1

[0213]

[0214]

[0215] Table 1-2

[0216]

[0217] Table 2

[0218]

[0219] 4.4. Preparation and quality measurement of metal foil laminates

[0220] The obtained resin composition was used to prepare metal foil laminates of Examples E1 to E16 and Comparative Examples CE1 to CE10. First, glass fiber cloth (model: 1078, thickness: 0.043 mm) was impregnated with the resin composition of Examples E1 to E16 and Comparative Examples CE1 to CE10 respectively through a roll coater, and the thickness of the glass fiber cloth was controlled to a suitable degree. Then, the impregnated glass fiber was placed in a dryer at 175°C and heated and dried for 2 to 5 minutes to obtain a semi-cured sheet in a semi-cured state (B-stage) (the resin content of the semi-cured sheet was 70%). After that, several sheets of the semi-cured sheets were laminated, and a 0.5 ounce copper foil was laminated on the outermost layers on both sides, and then placed in a hot press for high-temperature hot pressing and curing. The hot pressing conditions are: heating to 200°C to 220°C at a heating rate of 2°C / min to 4°C / min, and hot pressing and curing at this temperature with a total pressure of 18 kg / cm2 (initial pressure of 8 kg / cm2) for 120 minutes.

[0221] Various properties of the metal foil laminates of Examples E1 to E16 and Comparative Examples CE1 to CE10 were measured according to the measurement methods described above, including glass transition temperature (Tg), coefficient of thermal expansion (z-CTE), dielectric properties, anti-aging characteristics, heat resistance after moisture absorption, processing stability (including filling and adhesion properties), tear strength, and water absorption, and the results are recorded in Tables 3-1, 3-2, and 4.

[0222] Table 3-1

[0223]

[0224] Table 3-2

[0225]

[0226] Table 4

[0227]

[0228]

[0229] As shown in Table 3-1, Table 3-2, and Table 4, the metal foil laminate made from the resin composition of the present invention has excellent tear strength, glass transition temperature (Tg), thermal expansion coefficient (z-CTE), dielectric properties, anti-aging properties, heat resistance after moisture absorption, processing stability (filling and adhesion properties), and water absorption. In contrast, the comparative example shows that if the resin composition does not simultaneously contain the compound (A) having the structure of formula (I) and the component (B) having an ethylenically unsaturated double bond, the metal foil laminate produced cannot simultaneously have the above excellent properties.

[0230] In particular, the comparison between Examples E1, E5 and E9 and Comparative Examples CE1 and CE3, and the comparison between Examples E4, E8 and E12 and Comparative Examples CE2 and CE4 show that, when the same content of the compound (A) having the structure of formula (I) is used, the combination of the component (B) having an ethylenically unsaturated double bond of the present invention can provide a better effect than the combination of the polyphenylene ether having an unsaturated functional group. Comparative Examples CE5 to CE7 and Comparative Examples CE8 and CE9 respectively show that the effect of the present invention cannot be achieved by using only the compound (A) having the structure of formula (I) or only the component (B) having an ethylenically unsaturated double bond. Comparative Example CE10 shows that if both the compound (A) having the structure of formula (I) and the component (B) having an ethylenically unsaturated double bond are not used, not only the effect of the present invention cannot be achieved, but also the properties of the obtained metal foil laminate are the worst.

[0231] The above embodiments are only used to illustrate the principle and efficacy of the present invention and to describe the technical features of the present invention, and are not intended to limit the scope of protection of the present invention. Any changes or arrangements that can be easily completed by a person skilled in the art without violating the technical principle of the present invention are within the scope of the present invention.

Claims

1. A resin composition, characterized in that: Include (A) a compound having the structure of formula (I); and (B) a component having an ethylenically unsaturated double bond selected from the following group: A compound having a structure of formula (II), a compound having a structure of formula (III), and a combination thereof, in, Z is a divalent organic group; A is independently -O-, -S-, or -N(R1)-, wherein R1 is a hydrogen atom, a C1 to C20 hydrocarbon group, a C1 to C20 halogenated hydrocarbon group, or a group formed by substituting a portion of the hydrocarbon group or halogenated hydrocarbon group with at least one selected from an oxygen atom and a sulfur atom; R is an unsubstituted or substituted divalent nitrogen-containing heteroaromatic ring, and each R may be the same as or different from each other; X is and each X may be the same as or different from each other, wherein R2 and R3 are each independently a direct bond or a C1 to C4 alkylene group, Ar1 and Ar2 are each independently an unsubstituted or substituted divalent aromatic hydrocarbon group, L is a direct bond, -O-, -S-, -N(R4)-, -C(O)-O-, -C(O)-NH-, -S(O)-, -S(O)2-, -P(O)-, a C1 to C20 alkylene group, a C1 to C20 halogenated alkylene group, a divalent cardo structure, or an unsubstituted or substituted divalent C5 to C30 alicyclic hydrocarbon group, R4 is a hydrogen atom, a C1 to C20 hydrocarbon group, or a C1 to C20 halogenated hydrocarbon group, p is an integer from 0 to 5, and when p is 2 or more, each Ar1 may be the same as or different from each other; Y is a group containing an ethylenically unsaturated double bond, and each Y may be the same as or different from each other; m is an integer from 1 to 100; and n is an integer from 1 to 100.

2. The resin composition according to claim 1, wherein The component (B) having an ethylenically unsaturated double bond is selected from the following group: a compound having a structure of formula (IIa), a compound having a structure of formula (IIIa), and a combination thereof, in, R, A and Y in formula (IIa) and (IIIa) have the same definitions as R, A and Y in formula (II) and (III), respectively; X1 and X2 each independently have the same definition as X in formula (II) and (III), and X1 and X2 are different from each other; X' is X1 or X2; n1 and n2 are each independently an integer from 0 to 50, and the sum of n1 and n2 is less than 100; and m1 and m2 are each independently an integer of 0 to 50, but m1 and m2 are not 0 at the same time.

3. The resin composition according to claim 1 or 2, characterized in that In formula (I), Z is -CH2-, or Here, k is an integer from 1 to 5.

4. The resin composition according to claim 1 or 2, characterized in that In formula (II), (III), (IIa), and (IIIa), R is independently an unsubstituted or substituted divalent nitrogen-containing heteroaromatic ring, and the nitrogen-containing heteroaromatic ring is a pyrrole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, a phthalazine ring, a quinazoline ring, a naphthyridine ring, a carbazole ring, an acridine ring, or a phenazine ring.

5. The resin composition according to claim 4, wherein In formula (II), (III), (IIa), and (IIIa), R is independently an unsubstituted or substituted divalent nitrogen-containing heteroaromatic ring, and the nitrogen-containing heteroaromatic ring is a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, or a triazine ring.

6. The resin composition according to claim 1 or 2, characterized in that Ar1 and Ar2 are each independently an unsubstituted or substituted divalent aromatic hydrocarbon group, and the aromatic hydrocarbon group is a phenyl group, a naphthyl group, an anthracenyl group, or a biphenyl group, and each Ar1 group may be the same as or different from each other.

7. The resin composition according to claim 1 or 2, characterized in that L is C1 to C10 alkylene, C1 to C10 halogenated alkylene, or an unsubstituted or substituted divalent C5 to C30 alicyclic hydrocarbon group, in, R5 and R6 are each independently a fluorine atom or a C1 to C20 chain hydrocarbon group; R7 and R8 are each independently a direct bond, an unsubstituted or substituted chain hydrocarbon group, or an unsubstituted or substituted alicyclic hydrocarbon group; and j is an integer from 0 to 4.

8. The resin composition according to claim 1 or 2, characterized in that Y in formula (II), (III), (IIa) and (IIIa) is independently 2-isopropenylphenyl, 3-isopropenylphenyl, 4-isopropenylphenyl, 2-allylphenyl, 3-allylphenyl, 4-allylphenyl, 2-methoxy-4-allylphenyl, 4-(1-propenyl)-2-methoxyphenyl, 4-vinylbenzyl, 3-vinylbenzyl, 2-vinylbenzyl, allyl, acrylic, methacrylic, or methallyl.

9. The resin composition according to claim 1 or 2, wherein: The weight ratio of the compound (A) having the structure of formula (I) to the component (B) having an ethylenically unsaturated double bond is 1:9 to 1:

1.

10. The resin composition according to claim 1 or 2, characterized in that The composition further comprises an additive selected from the following groups: a catalyst, a cross-linking agent, an elastomer, a filler, a dispersant, a toughening agent, a viscosity modifier, a flame retardant, a plasticizer, a coupling agent, and a combination thereof.

11. The resin composition according to claim 10, wherein The catalyst is selected from the following group: diisopropyl peroxide, tertiary butyl peroxybenzoate, di-tertiary amyl peroxide, isopropyl isopropyl benzene tertiary butyl peroxide, tertiary butyl isopropyl benzene peroxide, di(isopropyl isopropyl benzene) peroxide, di-tertiary butyl peroxide, α,α'-bis(tertiary butyl peroxy) diisopropyl benzene, dibenzoyl peroxide, 1,1-bis(tertiary butyl peroxy)-3,3,5-trimethylcyclohexane, 4,4-di(tertiary butyl peroxy) valerate, 2,5-dimethyl-2,5-di(tertiary butyl peroxy) hexane, 2,5-dimethyl-2,5-di(tertiary butyl peroxy)-3-hexyne, and combinations thereof.

12. The resin composition according to claim 10, wherein The crosslinking agent is selected from the following group: multifunctional allyl compounds, multifunctional acrylates, multifunctional acrylamides, multifunctional styrene compounds, and combinations thereof.

13. The resin composition according to claim 10, wherein The elastomer is selected from the following group: polybutadiene, styrene-butadiene copolymer, styrene-butadiene-divinylbenzene copolymer, polyisoprene, styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, functionalized modified derivatives thereof, and combinations thereof.

14. The resin composition according to claim 10, wherein The filler is selected from the following group: silicon dioxide, aluminum oxide, magnesium oxide, magnesium hydroxide, calcium carbonate, talc, clay, aluminum nitride, boron nitride, aluminum hydroxide, aluminum silicon carbide, silicon carbide, sodium carbonate, titanium dioxide, zinc oxide, zirconium oxide, quartz, diamond, diamondoid, graphite, calcined kaolin, kaolin, mica, hydrotalcite, polytetrafluoroethylene powder, glass beads, ceramic whiskers, carbon nanotubes, nanoscale inorganic powders, and combinations thereof.

15. A prepreg, characterized in that: The method is prepared by impregnating or coating a substrate with the resin composition according to any one of claims 1 to 14, and drying the impregnated or coated substrate.

16. A metal foil laminate, characterized in that: The prepreg according to claim 15 is prepared by laminating a metal foil, or by coating a metal foil with the resin composition according to any one of claims 1 to 14 and drying the coated metal foil.

17. A printed circuit board, characterized in that: It is produced from the metal foil laminate according to claim 16.

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