Resin composition and application thereof

Abstract

A resin composition comprising: (A) an epoxy resin; (B) a maleimide-triazine resin; and (C) a first flame retardant having the structure of formula (I): # imgabs0 # wherein Ar is a C3 to C18 heteroaryl group or a C6 to C18 aryl group; r1 is hydrogen or a C1 to C18 alkyl group; and R2 and R3 are each independently hydrogen, a C1 to C18 alkyl group, a C3 to C18 heteroaryl group, or a C6 to C18 aryl group.

Description

Technical Field

[0001] The present invention relates to a resin composition, and more particularly to a resin composition comprising an epoxy resin, a maleimide-triazine resin, and a specific flame retardant. 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] Printed circuit boards are circuit substrates for electronic devices. They carry other electronic components and electrically connect these components to provide a stable circuit working environment. Common printed circuit board substrates are copper clad laminates (CCL), which are mainly composed of resin, reinforcement materials and copper foil. Common resins include epoxy resin, phenolic resin, polyamine formaldehyde, silicone and Teflon; commonly used reinforcement materials include glass fiber cloth, glass fiber mat, insulation paper, linen cloth, etc.

[0003] Generally speaking, a printed circuit board can be prepared by the following method. A reinforcing material such as a glass fabric is impregnated with a resin composition (such as an epoxy resin composition), and the glass fabric impregnated with the resin composition is hardened to a semi-hardened state (i.e., B-stage) to obtain a semi-cured sheet. Subsequently, a predetermined number of prepregs are stacked, and a metal foil is stacked on at least one outer side of the stacked prepregs to provide a stack, and then the stack is subjected to a hot pressing operation (i.e., C-stage) to obtain a metal foil laminate. The metal foil on the surface of the metal foil laminate is etched to form a specific circuit pattern. Then, a plurality of holes are drilled in the metal foil laminate, and conductive materials are plated in these holes to form via holes, thereby completing the preparation of the printed circuit board.

[0004] When using epoxy resin compositions to make printed circuit boards, various flame retardants, such as halogen-containing flame retardants or phosphorus-containing flame retardants, are usually added to the compositions in order to give electronic materials flame retardancy. However, the use of halogen-containing flame retardants has been restricted due to environmental issues. Commonly used phosphorus-containing flame retardants include phosphazene compounds (such as SPB-100 produced by Otsuka Chemical) or condensed phosphate esters (such as PX-200 produced by Dahachi Chemical), but those flame retardants have problems such as low melting points, low thermal decomposition temperatures, and excessively high high-temperature freedom. The resulting substrate has a large thermal expansion coefficient, and is prone to cracking of the inner layer during the manufacturing process of the printed circuit board, thereby reducing the process yield.

[0005] WO 2010 / 135398 discloses a phosphorus-containing flame retardant, which is a derivative of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). Each molecule of the derivative contains two DOPO groups (DiDOPO) and has good thermal stability and flame retardancy.

[0006] In addition, it is known that bismaleimide-triazine resin (BT resin) can be used as an alternative material for epoxy resin, or bismaleimide-triazine resin can be added to epoxy resin composition to improve the heat resistance of the obtained dielectric material. However, since the imide group in the molecular structure of bismaleimide-triazine resin has polarity, adding bismaleimide-triazine resin will make the resin composition have poor water absorption resistance. The above shortcomings cause the application of bismaleimide-triazine resin in epoxy resin system to be limited.

[0007] Therefore, there is an urgent need to develop a new resin composition in this field to solve the above problems. Summary of the invention

[0008] In view of the above technical problems, the present invention provides a resin composition, which is a combination of epoxy resin, maleimide-triazine resin, and a specific flame retardant. The electronic material obtained after curing the resin composition can have good thermal expansion coefficient, heat resistance, dimensional stability, warpage, flame retardancy, water absorption, drill needle abrasion, and tear strength.

[0009] Therefore, an object of the present invention is to provide a resin composition comprising:

[0010] (A) Epoxy resin;

[0011] (B) a maleimide-triazine resin; and

[0012] (C) a first flame retardant having the structure of the following formula (I):

[0013]

[0014] in,

[0015] Ar is C 3 To C 18 Heteroaryl or C 6 To C 18 Aryl;

[0016] R 1 is hydrogen or C 1 To C 18 Alkyl; and

[0017] R 2 and R3 Each is independently hydrogen, C 1 To C 18 Alkyl, C 3 To C 18 Heteroaryl, or C 6 To C 18 Aryl.

[0018] In some embodiments of the present invention, the weight ratio of the first flame retardant (C) to the maleimide-triazine resin (B) is 1:6 to 5:2.

[0019] In some embodiments of the present invention, the epoxy resin (A) is selected from the following groups: bisphenol epoxy resin, novolac epoxy resin, distyrene epoxy resin, epoxy resin containing a triazine skeleton, epoxy resin containing a fluorene skeleton, trisphenol methane epoxy resin, xylylene epoxy resin, biphenyl epoxy resin, biphenyl aralkyl epoxy resin, naphthalene epoxy resin, dicyclopentadiene (DCPD) epoxy resin, alicyclic epoxy resin, and combinations thereof.

[0020] In some embodiments of the present invention, the maleimide-triazine resin (B) is obtained by reacting a maleimide compound with a cyanate compound.

[0021] The maleimide compound is preferably a bismaleimide compound.

[0022] The cyanate compound is preferably a compound having two or more cyanate groups, and more preferably an aromatic compound having two or more cyanate groups directly bonded to an aromatic ring. The cyanate compounds can be used alone or in combination.

[0023] In some embodiments of the present invention, the first flame retardant (C) is selected from the following group:

[0024]

[0025]

[0026] and combinations thereof.

[0027] In some embodiments of the present invention, the resin composition further comprises a hardener selected from the following group: cyanate ester resin, benzoxazine resin, phenol novolac (PN), styrene maleic anhydride (SMA) resin, dicyandiamide (Dicy), diaminodiphenyl sulfone (DDS), amino triazinenovolac (ATN) resin, diaminodiphenylmethane, styrene-vinylphenol copolymer, and combinations thereof.

[0028] In some embodiments of the present invention, the resin composition further comprises a hardening accelerator selected from the following group: imidazole compounds, pyridine compounds, and combinations thereof.

[0029] In some embodiments of the present invention, the resin composition further comprises an elastomer 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.

[0030] In some embodiments of the present invention, the resin composition further comprises a filler 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 (PTFE) powder, glass beads, ceramic whiskers, carbon nanotubes, nanoscale inorganic powders, and combinations thereof.

[0031] 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.

[0032] 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.

[0033] Another object of the present invention is to provide a printed circuit board made from the above-mentioned metal foil laminate.

[0034] 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

[0035] 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.

[0036] Unless otherwise specified, 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.

[0037] Unless otherwise stated, when describing the content of a component in a solution, mixture, or composition in this specification and claims, it is calculated based on the total weight excluding the solvent.

[0038] Unless otherwise specified, the terms “first”, “second” and the like used in the specification and the claims are merely used to distinguish the described elements or components and have no special meanings and are not used to represent a sequence.

[0039] Unless otherwise specified, when "above", "below" and similar terms are used in this specification and claims to describe a numerical range, the defined endpoint values ​​are included. For example, "more than two" includes all values ​​greater than two.

[0040] The resin composition of the present invention uses epoxy resin (A), maleimide-triazine resin (B), and specific flame retardant (C) in combination, so that the electronic material obtained after curing the resin composition can have good thermal expansion coefficient, heat resistance, dimensional stability, warpage, flame retardancy, water absorption, drill needle wear, and tear strength. The following provides a detailed description of the resin composition of the present invention and its related applications.

[0041] 1. Resin composition

[0042] The resin composition of the present invention comprises (A) epoxy resin, (B) maleimide-triazine resin, and (C) a first flame retardant with a specific structure as essential components, and may further comprise optional components as required. Detailed descriptions of each component are as follows.

[0043] 1.1.(A) Epoxy resin

[0044] In the present invention, epoxy resin refers to a thermosetting resin having at least two epoxy functional groups in one molecule, such as a multifunctional epoxy resin, a phenolic epoxy resin or a combination thereof. Examples of multifunctional epoxy resins include, but are not limited to, difunctional epoxy resins, tetrafunctional epoxy resins, and octafunctional epoxy resins. There is no particular limitation on the type of epoxy resin, and a person skilled in the art of the present invention may select the epoxy resin as needed after reading the specification of the present invention. For example, a bromine-containing epoxy resin may be used to impart better flame retardancy to the thermosetting resin composition, and an epoxy resin that does not contain halogen (such as bromine) may also be used to meet the environmental protection requirements of halogen-free.

[0045] Epoxy resins that can be used in the present invention include, but are not limited to, bisphenol epoxy resins, novolac epoxy resins, stilbene epoxy resins, epoxy resins containing triazine skeletons, epoxy resins containing fluorene skeletons, trisphenol methane epoxy resins, xylylene epoxy resins, biphenyl epoxy resins, biphenyl aralkyl epoxy resins, naphthalene epoxy resins, dicyclopentadiene (DCPD) epoxy resins, and alicyclic epoxy resins. Examples of bisphenol epoxy resins include, but are not limited to, bisphenol A epoxy resins, bisphenol F epoxy resins, and bisphenol S epoxy resins. Examples of novolac epoxy resins (e.g., linear novolac epoxy resins) include, but are not limited to, phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A novolac epoxy resins, and bisphenol F novolac epoxy resins. Examples of epoxy resins may include diglycidyl ether compounds of polycyclic aromatics such as polyfunctional phenols and anthracene.

[0046] The aforementioned epoxy resins can be used alone or in any combination, and those skilled in the art can prepare them according to actual needs. In some embodiments of the present invention, bisphenol A epoxy resin, novolac epoxy resin or a combination thereof is used.

[0047] In the resin composition of the present invention, the content of the epoxy resin may be 3 wt % to 15 wt %, such as 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt %, 13 wt %, 14 wt %, or 15 wt %, based on the total weight of the resin composition, or a range between any two of the above values, but the present invention is not limited thereto.

[0048] 1.2. (B) Maleimide-triazine resin

[0049] Maleimide-triazine resin has reactive functional groups and can undergo cross-linking reactions with other components containing unsaturated functional groups or epoxy groups.

[0050] The maleimide-triazine resin (B) can be prepared by reacting a maleimide compound with a cyanate compound. For example, the maleimide compound and the cyanate compound can be heated to a molten state under solvent-free conditions, and then fully mixed and polymerized to prepare the maleimide-triazine resin. Alternatively, the maleimide compound and the cyanate compound can be dissolved in a suitable organic solvent and polymerized to prepare the maleimide-triazine resin. Examples of the suitable organic solvent include, but are not limited to, methyl ethyl ketone, N-methyl pyrrolidone, dimethylformamide, dimethylacetamide, toluene, and xylene.

[0051] The type of the maleimide compound is not particularly limited, and can be any compound having one or more maleimide groups (i.e., ). According to the number of maleimide groups contained in one molecule, the maleimide compound can be divided into a monomaleimide compound having one maleimide group in one molecule and a polyfunctional maleimide compound having two or more maleimide groups in one molecule. In some embodiments of the present invention, the maleimide compound is preferably a polyfunctional maleimide compound, such as a bismaleimide compound having two maleimide groups in one molecule.

[0052] Examples of the monomaleimide compound include, but are not limited to, N-phenylmaleimide, N-hydrophenylmaleimide.

[0053] Bismaleimide compounds may have wherein Z can be selected from the following groups: methylene (-CH 2 -), 4,4'-diphenylmethane

[0055] Metaphenylene Bisphenol A diphenyl ether 3,3'-Dimethyl-5,5'-diethyl-4,4'-diphenylmethane 4-Methyl-1,3-phenylene and (2,2,4-trimethyl)-1,6-hexylene Specific examples of the bismaleimide compounds include, but are not limited to, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 1,3-bismaleimidobenzene, 1,4-bismaleimidobenzene, 2,4-bismaleimidotoluene, 4,4'-bismaleimidodiphenylmethane, 4,4'-bismaleimidodiphenyl ether, 3,3'-bismaleimidodiphenyl sulfone, 4,4'-bismaleimidodiphenyl sulfone, and 4,4'-bismaleimidodiphenyl ether. 1,3-bis(maleimidomethyl)cyclohexane, 1,3-bis(maleimidomethyl)benzene, 1,1-bis(4-maleimidophenyl)cyclohexane, 1,3-bis(dichloromaleimido)benzene, 4,4'-biscitraconimidodiphenylmethane, 3,5-bis(4-maleimidophenyl)pyridine, 2,6-bismaleimidopyridine, 1,3-bis(maleimidomethyl)cyclohexane, 1,3-bis(maleimidomethyl)benzene, 1,1-bis(4-maleimidophenyl)cyclohexane, 1,3-bis(dichloromaleimido)benzene, 4,4'-biscitraconimidodiphenylmethane e), 2,2-bis(4-maleimidophenyl)propane, 1-phenyl-1,1-bis(4-maleimidophenyl)ethane, α,α-bis(4-maleimidophenyl)toluene, 3,5-bismaleimido-1,2,4-triazole, N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bismaleimide, N,N'-4,4'-diphenylmethane bismaleimide, N,N'-4,4'-diphenyl ether bismaleimide, N,N'-4,4'-diphenyl sulfone bismaleimide, N,N'-4,4'-dicyclohexylmethane bismaleimide, N,N'-α,α'-4,4'-dimethylenecyclohexane bismaleimide, N,N'-m-xylene bismaleimide, N,N'-4,4'-diphenylcyclohexane bismaleimide, and N,N'-methylenebis(3-chloro-p-phenylene)bismaleimide.

[0056] When preparing the maleimide-triazine resin (B), the maleimide compounds mentioned above may be used alone or in any combination, and may be used in the form of monomers, oligomers, and polymers.

[0057] The type of the cyanate compound is not particularly limited, as long as it has a cyanate group (i.e., -OC≡N) in the molecule. In some embodiments of the present invention, the cyanate compound is preferably a compound having two or more cyanate groups, and more preferably an aromatic compound having two or more cyanate groups directly bonded to an aromatic ring.

[0058] Cyanate compounds can be obtained by replacing the hydroxyl group of a compound containing a hydroxyl group with a cyanate group. Examples of the compounds containing a hydroxyl group include, but are not limited to, bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolac resin, cresol novolac resin, dicyclopentadiene novolac resin, tetramethyl bisphenol F, bisphenol A novolac resin, brominated bisphenol A, brominated phenol novolac resin, trifunctional phenol, quadrifunctional phenol, naphthyl phenol, biphenyl phenol, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, dicyclopentadiene aralkyl resin, alicyclic phenol, and phenol containing phosphorus. Therefore, examples of cyanate compounds include, but are not limited to, compounds obtained by replacing the hydroxyl group of the above-mentioned compounds with a cyanate group.

[0059] When preparing the maleimide-triazine resin (B), the aforementioned cyanate compounds may be used alone or in any combination, and may be used in the form of a monomer, an oligomer, or a polymer.

[0060] In some embodiments of the present invention, the maleimide-triazine resin (B) is a bismaleimide-triazine resin, which can be prepared by reacting a bismaleimide compound with a cyanate compound, or can be obtained commercially. Commercially available maleimide-triazine resins include products with the model numbers Nanozine 520 and Nanozine 600 available from Nanokor, and products with the model numbers BT-2100, BT-2170, BT-2160L, BT-2160, and BT-2164 available from Mitsubishi Gas Chemical. In the resin composition of the present invention, the aforementioned maleimide-triazine resins can be used alone or in any combination, and those skilled in the art can prepare them according to actual needs. In some embodiments of the present invention, Nanozine 520, BT-2100, or a combination thereof is used.

[0061] In the resin composition of the present invention, the content of the maleimide-triazine resin may be 5 wt % to 30 wt %, such as 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.

[0062] 1.3.(C) First flame retardant

[0063] Generally speaking, flame retardants can improve the flame retardancy of the electronic materials produced. Herein, the first flame retardant is a compound having a specific structure of the following formula (I):

[0064]

[0065] In formula (I), Ar can be C 3 To C 18 Heteroaryl or C 6 To C 18 Aryl; R 1 Can be hydrogen or C 1 To C 18 Alkyl; and R 2 and R 3 can be independently hydrogen, C 1 To C 18 Alkyl, C 3 To C 18 Heteroaryl, or C 6 To C 18 Aryl. The above C 3 To C 18 The heteroaryl group refers to an aromatic ring or condensed ring structure having 3 to 18 carbon atoms and having one or more heteroatoms (such as oxygen, nitrogen and sulfur) in one or more aromatic rings or condensed rings. 6 To C 18 The aryl group refers to an aromatic monocyclic, polycyclic or condensed ring structure having 6 to 18 carbon atoms. 3 To C 18 Examples of heteroaryl groups include, but are not limited to, pyridyl, furyl, and imidazolyl; C 6 To C 18 Examples of aryl groups include, but are not limited to, phenyl, naphthyl, and anthracenyl; and C 1 To C 18 Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. In addition, Ar of the first flame retardant is preferably phenyl, naphthyl, or anthracene, more preferably phenyl or naphthyl, and particularly preferably phenyl. When the first flame retardant meets the above conditions, the electronic material made from the resin composition may have better properties, including better thermal expansion, heat resistance, dimensional stability, warpage, water absorption, and tear strength.

[0066] Examples of the first flame retardant (C) include, but are not limited to, at least one selected from the following group:

[0067]

[0068] and

[0069] In some embodiments of the present invention, the first flame retardant (C) is a flame retardant having a structure of formula (I-1), a flame retardant having a structure of formula (I-2), or a combination thereof.

[0070] Compared with other DOPO-based flame retardants, the first flame retardant (C) used in the present invention comprises a bridging group of an ethylenic group substituted with an aryl group. Without being limited by theory, it is believed that the first flame retardant (C) has better rigidity due to the shorter chain of the bridging group; and the aromatic substituent on the ethylenic group causes a greater steric hindrance effect, thereby giving the first flame retardant (C) good chemical stability and low volatility, so that the electronic material prepared from the resin composition of the present invention can have better flame retardant properties.

[0071] In addition, the present inventors have found that the first flame retardant (C) and the maleimide-triazine resin (B) unexpectedly can play a special synergistic role, which can improve the problem of poor water absorption caused by adding bismaleimide-triazine resin to the epoxy resin system, and at the same time provide good laminate properties.

[0072] The weight ratio of the first flame retardant (C) to the maleimide-triazine resin (B) is preferably 1:6 to 5:2, such as 1:6, 2:11, 1:5, 2:9, 1:4, 2:7, 1:3, 2:5, 1:2, 2:3, 1:1, 3:2, 2:1, or 5:2, or a range between any two of the above values. When the weight ratio of the first flame retardant (C) to the maleimide-triazine resin (B) is within the above range, the electronic material prepared by the resin composition of the present invention can have better drill wear and water absorption.

[0073] 1.3. Selection of ingredients

[0074] In addition to the above-mentioned components, the resin composition of the present invention may further include other optional components to specifically improve the physicochemical properties of the electronic material made from the resin composition, or to improve the processability of the resin composition during the manufacturing process. The optional components of the resin composition of the present invention may be any additives available in the art, such as hardeners, hardening accelerators, elastomers, fillers, dispersants, toughening agents, viscosity modifiers, other flame retardants other than the first flame retardant (C), plasticizers, coupling agents, etc. The use of such additives is something that can be carried out and completed as needed by those skilled in the art of the present invention according to their common knowledge after observing the disclosure of this specification, and it is not the technical focus of the present invention, so it will not be described in detail here. The following examples of hardeners, hardening accelerators, elastomers, and fillers are given for illustration.

[0075] 1.3.1. Hardener

[0076] The resin composition of the present invention may further include a hardener. The hardener may be any existing hardener applicable to epoxy resins, such as hydroxyl-containing compounds, amine-containing compounds, anhydride compounds, and active ester compounds. Examples of hardeners include, but are not limited to, cyanate resins, benzoxazine resins, phenolic resins (PN), novolac resins, styrene maleic anhydride resins (SMA), dicyandiamide (Dicy), diaminodiphenyl sulfone (DDS), aminotriazine phenolic resins (ATN), diaminodiphenylmethane, and styrene-vinylphenol copolymers. The aforementioned hardeners may be used alone or in any combination. In some embodiments of the present invention, novolac resins, benzoxazine resins, or combinations thereof are used.

[0077] Based on the total weight of the resin composition, the content of the hardener may be 0 wt % to 15 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 %, or 15 wt %, or a range between any two of the above values, but the present invention is not limited thereto.

[0078] 1.3.2. Hardening accelerator

[0079] The resin composition of the present invention may further include a hardening accelerator. The hardening accelerator can promote the reaction of epoxy functional groups and reduce the curing reaction temperature of the resin composition. The hardening accelerator can be any substance that can promote the ring opening of epoxy functional groups and reduce the curing reaction temperature, and its examples include tertiary amines, quaternary amines, imidazole compounds, and pyridine compounds, and the aforementioned hardening accelerators can be used alone or in combination. In some embodiments of the present invention, the hardening accelerator is an imidazole compound, a pyridine compound, or a combination thereof. Examples of imidazole compounds include, but are not limited to, 2-methylimidazole (2-methyl-imidazole, 2MI), 2-ethyl-4-methylimidazole (2-ethyl-4-methyl-imidazole, 2E4MZ), and 2-phenylimidazole (2-phenyl-imidazole, 2PI). Examples of pyridine compounds include, but are not limited to, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,6-diaminopyridine, 4-dimethylaminopyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, and 2-amino-3-nitropyridine. In some embodiments of the present invention, 2-phenylimidazole, 2-ethyl-4-methylimidazole, or a combination thereof is used.

[0080] Based on the total weight of the resin composition, the content of the hardening accelerator may be 0.01 wt % to 0.60 wt %, for example, 0.01 wt %, 0.05 wt %, 0.10 wt %, 0.15 wt %, 0.20 wt %, 0.25 wt %, 0.30 wt %, 0.35 wt %, 0.40 wt %, 0.45 wt %, 0.50 wt %, 0.55 wt %, or 0.60 wt %, or a range between any two of the above values, but the present invention is not limited thereto.

[0081] 1.3.3. Elastomer

[0082] The resin composition of the present invention may further include an elastomer to improve the toughness of the electronic material. 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 some embodiments of the present invention, styrene-butadiene copolymers are used.

[0083] 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.

[0084] 1.3.4. Filling

[0085] The resin composition of the present invention may further include fillers to improve the dimensional stability of the electronic material. Examples of fillers include, but are not limited to, organic or inorganic fillers selected from the following groups: 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 some embodiments of the present invention, a silica filler is used.

[0086] Based on the total weight of the resin composition, the filler content may be 40 wt % to 50 wt %, for example, 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.

[0087] 1.4. Preparation of resin composition

[0088] The resin composition of the present invention can be made into a varnish-like form by uniformly mixing the components of the resin composition, including epoxy resin (A), maleimide-triazine resin (B), first flame retardant (C), and other selected components, with a stirrer and dissolving or dispersing them in a solvent. 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 and N,N-dimethylacetyl is used as the solvent.

[0089] 2. Prepreg

[0090] 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, 2116 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.

[0091] 3. Metal foil laminates and printed circuit boards

[0092] The present invention also provides a metal foil laminate, which can be obtained by laminating the above-mentioned prepreg and metal foil. For example, a plurality of layers of the above-mentioned prepreg can be laminated as a dielectric layer, and then a metal foil (such as copper foil) is laminated on at least one outer surface of the dielectric layer as a metal layer to provide a laminate, and then the laminate is subjected to a heat pressing operation to obtain a 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 a metal foil laminate.

[0093] The outer metal foil of the metal foil laminate may be further patterned to form a printed circuit board.

[0094] 4. Examples

[0095] 4.1. Measurement method description

[0096] The present invention is further illustrated by the following specific embodiments, wherein the measuring instruments and methods used are as follows:

[0097] [Coefficient of thermal expansion (z-CTE) test]

[0098] 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); perform a thermomechanical analysis on the test sample in the expansion / compression mode under the above conditions; 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 %.

[0099] [Heat resistance (T288) test]

[0100] Six prepreg sheets were laminated with copper foil to prepare a copper foil laminate of 6.5 mm in length and 6.5 mm in width as the test sample. According to the IPC-TM-650 2.4.24.1 specification, a thermal mechanical analyzer (TMA) was used to test at 288°C and the time for the copper foil laminate to explode was recorded. The longer the time for the explosion, the higher the heat resistance of the copper foil laminate. If the test time exceeds 60 minutes and there is still no explosion, it is marked as “>60”, which means that the T288 heat resistance test can exceed 60 minutes without explosion.

[0101] [Dimensional stability test]

[0102] The copper foil laminate used for evaluation was cut into 12-inch × 11-inch samples and then drilled. The copper foil on both sides was then removed by etching to prepare a non-cladding board with holes for testing. According to IPC-TM-650 2.4.39 specification, the sample was baked in an oven at 105°C for 4 hours and then baked at 150°C for 2 hours. The dimensional change rate of the sample in the longitudinal direction was measured in ppm / °C.

[0103] [Warp test]

[0104] According to IPC TM-650-2.4.22, the copper foil laminate was etched on one side, the warping of the copper foil laminate was observed, and the warping rate was calculated.

[0105] [Flammability test]

[0106] Using the UL94V: vertical burning test method, the copper foil laminate is fixed in a vertical position and burned with a Bunsen burner to compare its self-ignition and combustion-supporting characteristics. The ranking of flame retardancy is: V0>V1>V2.

[0107] [Water absorption test]

[0108] Measure the weight of the copper foil laminate sample (W1). Then, place the copper foil laminate in a container and perform a pressure cooker test (PCT) at 121°C, 100% relative humidity (RH), 1.2 atmospheres, and 2 hours to measure the weight of the sample after moisture absorption (W2). Calculate the water absorption of the copper foil laminate according to the following formula.

[0109] Water absorption = [(W2-W1) / W1] × 100%

[0110] [Drill wear test]

[0111] A 0.3mm diameter drill was used to drill holes in the copper foil laminate, and the wear of the drill head was observed after drilling 2000 times. Since the cutting edge (CE) of the drill will continuously contact and wear the copper foil laminate during the drilling process, wear will occur at the cutting corner (CC) of the cutting edge CE, so in this test, the cutting corner CC is measured to obtain the wear rate.

[0112] [Tear strength test]

[0113] Tear strength refers to the adhesion of metal foil to prepreg laminated by heat pressing. It is expressed by the amount of force required to tear a 1 / 8 inch wide copper foil (0.5 ounce) vertically from the board surface. The unit of tear strength is pound force / inch (lbf / in).

[0114] 4.2. List of raw material information used in Examples and Comparative Examples:

[0115]

[0116]

[0117]

[0118] 4.3. Preparation of resin composition

[0119] According to the components and amounts shown in Tables 1 and 2, the components were mixed at room temperature using a stirrer, and methyl ethyl ketone and cyclohexanone (both purchased from Genxiang Industrial 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 E12 and Comparative Examples CE1 to CE6.

[0120] Table 1

[0121]

[0122]

[0123] Table 2

[0124]

[0125] 4.4. Preparation and quality measurement of metal foil laminates

[0126] The obtained resin composition was used to prepare metal foil laminates of Examples E1 to E12 and Comparative Examples CE1 to CE6. First, glass fiber cloth (model: 2116, thickness: 0.08 mm) was impregnated with the resin composition of Examples E1 to E12 and Comparative Examples CE1 to CE6 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 15 minutes to obtain a semi-cured sheet in a semi-cured state (B-stage) (the resin content of the semi-cured sheet was 55%). After that, several sheets of the semi-cured sheets were laminated, and a 0.5 ounce copper foil was laminated on the outermost layers of each of the two 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 3°C / min, and hot pressing and curing at this temperature with a total pressure of 15 kg / cm2 (initial pressure of 8 kg / cm2) for 180 minutes.

[0127] The various properties of the metal foil laminates of Examples E1 to E12 and Comparative Examples CE1 to CE6, including thermal expansion coefficient, heat resistance, dimensional stability, warpage, flame retardancy, water absorption, drill needle abrasion, and tear strength, were measured according to the measurement methods described above, and the results are recorded in Tables 3 and 4.

[0128] Table 3

[0129]

[0130] Table 4

[0131]

[0132] As shown in Tables 3 and 4, the metal foil laminated board made from the resin composition of the present invention has excellent thermal expansion coefficient, heat resistance, dimensional stability, warpage, flame retardancy, water absorption, drill needle abrasion, and tear strength. In contrast, the comparative example shows that if the resin composition does not simultaneously contain the epoxy resin (A), the maleimide-triazine resin (B), and the first flame retardant (C) having the structure of formula (I), the metal foil laminated board produced cannot simultaneously have the above excellent properties.

[0133] Specifically, Comparative Example CE1 shows that when epoxy resin (A) is not used, the drill needle wear and tear strength of the obtained metal foil laminate are not good. Comparative Example CE2 shows that when maleimide-triazine resin (B) is not used, the thermal expansion coefficient, heat resistance, dimensional stability, warpage, and tear strength of the obtained metal foil laminate are not good. Comparative Example CE3 shows that when no flame retardant is used, the obtained metal foil laminate has many poor properties, especially the water absorption rate is very poor, which is speculated to be due to the presence of polar maleimide-triazine resin in the epoxy resin system. Comparative Examples CE4 to CE6 show that if the first flame retardant (C) is replaced by a common flame retardant in the art, the obtained metal foil laminate cannot have the above-mentioned excellent properties at the same time.

[0134] 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 familiar with the present technology without violating the technical principle of the present invention are within the scope of the present invention.

Claims

1. A resin composition, It is characterized in that Include: (A) Epoxy resin; (B) a maleimide-triazine resin; and (C) a first flame retardant having the structure of the following formula (I): in, Ar is C 3 To C 18 Heteroaryl or C 6 To C 18 Aryl; R 1 is hydrogen or C 1 To C 18 Alkyl; and R 2 and R 3 Each is independently hydrogen, C 1 To C 18 Alkyl, C 3 To C 18 Heteroaryl, or C 6 To C 18 Aryl.

2. The resin composition according to claim 1, It is characterized in that The weight ratio of the first flame retardant (C) to the maleimide-triazine resin (B) is 1:6 to 5:

2.

3. The resin composition according to claim 1, It is characterized in that The epoxy resin (A) is selected from the following groups: bisphenol epoxy resin, novolac epoxy resin, distyrene epoxy resin, epoxy resin containing triazine skeleton, epoxy resin containing fluorene skeleton, trisphenol methane epoxy resin, stubble-based epoxy resin, biphenyl epoxy resin, biphenyl aralkyl epoxy resin, naphthalene epoxy resin, dicyclopentadiene epoxy resin, alicyclic epoxy resin, and combinations thereof.

4. The resin composition according to claim 1, It is characterized in that The maleimide-triazine resin (B) is obtained by reacting a maleimide compound with a cyanate compound.

5. The resin composition according to claim 4, It is characterized in that The maleimide compound is a bismaleimide compound.

6. The resin composition according to claim 4, It is characterized in that The cyanate compound is a compound having two or more cyanate groups.

7. The resin composition according to claim 6, It is characterized in that The cyanate compound is an aromatic compound having two or more cyanate groups directly bonded to an aromatic ring.

8. The resin composition according to claim 1, It is characterized in that The first flame retardant (C) is selected from the following group: and combinations thereof.

9. The resin composition according to any one of claims 1 to 8, It is characterized in that The invention also comprises a hardener selected from the group consisting of cyanate resins, benzoxazine resins, phenolic resins, styrene maleic anhydride resins, dicyandiamide, diaminodiphenyl sulfone, aminotriazaphenolic resins, diaminodiphenylmethane, styrene-vinylphenol copolymers, and combinations thereof.

10. The resin composition according to any one of claims 1 to 8, It is characterized in that The invention also comprises a hardening accelerator selected from the group consisting of an imidazole compound, a pyridine compound, and a combination thereof.

11. The resin composition according to any one of claims 1 to 8, It is characterized in that The present invention also comprises an elastomer 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.

12. The resin composition according to any one of claims 1 to 8, It is characterized in that The invention also comprises a filler 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, diamond-like, graphite, calcined kaolin, kaolin, mica, hydrotalcite, polytetrafluoroethylene (PTFE) powder, glass beads, ceramic whiskers, carbon nanotubes, nanoscale inorganic powders, and combinations thereof.

13. A prepreg, It is 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 12, and drying the impregnated or coated substrate.

14. A metal foil laminate, It is characterized in that The prepreg according to claim 13 is prepared by laminating a metal foil, or by coating the resin composition according to any one of claims 1 to 12 on a metal foil and drying the coated metal foil.

15. A printed circuit board, It is characterized in that It is produced from the metal foil laminate according to claim 14.

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