Resin composition and products thereof

Abstract

The present invention discloses a resin composition comprising 10 parts by weight of a first prepolymer and 5 to 30 parts by weight of a vinyl-containing polyphenylene ether resin, wherein the first prepolymer is prepared by a prepolymerization reaction of a reaction mixture, wherein the reaction mixture comprises polyphenylmethane maleimide, a compound having a structure represented by formula (1), and a compound having a structure represented by formula (2), and the weight ratio of the polyphenylmethane maleimide, the compound having a structure represented by formula (1), and the compound having a structure represented by formula (2) is 100:10 to 30:15 to 45, and the resin composition does not comprise a second prepolymer, wherein the second prepolymer is prepared by a prepolymerization reaction of maleimide and bis(trifluoromethyl)diphenylamine. Products made from the aforementioned resin composition can improve at least one of the properties of chemical copper plating rate, storage modulus, and copper foil tensile strength. #imgabs0#

Description

Technical Field

[0001] The present invention relates to a resin composition, in particular to a resin composition which can be used to prepare a prepreg, a resin film, a laminate or a printed circuit board. Background Art

[0002] In recent years, with the development of electronic signal transmission methods towards 5G, as well as the high functionality and miniaturization of electronic equipment, communication devices, personal computers, etc., the requirements for circuit boards have become increasingly higher, and the circuit design has become increasingly complex. Correspondingly, the number of layers required for circuit boards has increased, and the number of holes in the same circuit board has also increased, and the aperture has also become smaller and smaller. The smaller the aperture, the greater the difficulty of chemical copper plating on the hole wall and the lower the chemical copper plating rate. Therefore, it is necessary to invent a material that can meet a high chemical copper plating rate (such as 100%) to improve the yield of the circuit board. In addition, in order to meet the higher requirements for the comprehensive performance of the substrate, it is also necessary to develop a material that has high tensile strength against the copper foil. Summary of the Invention

[0003] In view of the problems encountered in the prior art, in particular, the inability of existing materials to meet one or more of the above-mentioned technical problems, the main object of the present invention is to provide a resin composition that can overcome at least one of the above-mentioned technical problems, and an article made using the resin composition.

[0004] In order to achieve the above object, the present invention discloses a resin composition comprising 10 parts by weight of a first prepolymer and 5 to 30 parts by weight of a vinyl-containing polyphenylene ether resin, wherein:

[0005] The first prepolymer is prepared by prepolymerization of a reaction mixture, wherein the reaction mixture comprises polyphenylmethanemaleimide, a compound having a structure represented by formula (1), and a compound having a structure represented by formula (2), and the weight ratio of the polyphenylmethanemaleimide, the compound having a structure represented by formula (1), and the compound having a structure represented by formula (2) is 100:10-30:15-45.

[0006]

[0007]

[0008] as well as

[0009] The resin composition does not include a second prepolymer, and the second prepolymer is prepared by prepolymerization of maleimide and bis(trifluoromethyl)benzenediamine.

[0010] For example, in one embodiment, the vinyl-containing polyphenylene ether resin includes vinyl benzyl biphenyl polyphenylene ether resin, methacrylate-containing polyphenylene ether resin, vinyl benzyl bisphenol A polyphenylene ether resin, or a combination thereof.

[0011] For example, in one embodiment, the resin composition further comprises 5 to 35 parts by weight of a maleimide resin, and the maleimide resin comprises 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, a compound having a structure represented by formula (3), a compound having a structure represented by formula (4), or a combination thereof.

[0012]

[0013] Formula (3), wherein m is an integer from 1 to 10;

[0014]

[0015] Formula (4), wherein n is an integer from 1 to 5.

[0016] For example, in one embodiment, the resin composition further comprises 10 to 30 parts by weight of a polyolefin, and the polyolefin comprises a styrene-butadiene copolymer, an epoxy-containing polybutadiene, a styrene-butadiene-divinylbenzene terpolymer, or a combination thereof.

[0017] For example, in one embodiment, the resin composition further includes an inorganic filler, a hardening accelerator, a flame retardant, a polymerization inhibitor, a solvent, a silane coupling agent, a colorant, a toughening agent, or a combination thereof.

[0018] Another main object of the present invention is to provide a product made from the aforementioned resin composition, wherein the product includes a prepreg, a resin film, a laminate or a printed circuit board.

[0019] For example, in one embodiment, the aforementioned product has one, multiple, or all of the following characteristics:

[0020] The chemical copper plating rate is 100%;

[0021] A storage modulus greater than or equal to 7.2 GPa as measured by the method described in IPC-TM-650 2.4.24.4; and

[0022] The tensile force on the copper foil measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 0.62 kgf / cm. DETAILED DESCRIPTION

[0023] To facilitate understanding of the features and benefits of the present invention by those skilled in the art, the following provides a general description and definition of terms and expressions used in the specification and claims. Unless otherwise indicated, all technical and scientific terms used herein have the ordinary meanings as understood by those skilled in the art regarding the present invention. In the event of conflict, the definitions in this specification shall prevail.

[0024] As used herein, the terms "comprise," "include," "have," "contain," or any similar terms are open-ended transitional phrases that are intended to cover a non-exclusive inclusion. For example, a composition or article containing multiple elements is not limited to only those elements listed herein, but may also include other elements not expressly listed but generally inherent to the composition or article. In addition, unless expressly stated to the contrary, the term "or" refers to an inclusive "or" and not an exclusive "or." For example, any of the following situations satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist). In addition, in this document, the terms "comprising", "including", "having", and "containing" should be interpreted as having specifically disclosed and also covering closed conjunctions such as "consisting of", "consisting of", and "the remainder is", as well as conjunctions such as "substantially consisting of", "mainly consisting of", "mainly consisting of", "basically containing", "essentially consisting of", "basically consisting of", and "essentially containing".

[0025] In this article, all features or conditions such as numerical values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are only for simplicity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be considered to have covered and specifically disclose all possible sub-ranges and individual values ​​within the range (including integers and fractions), particularly integer values. For example, the range description of "1.0 to 8.0" or "between 1.0 and 8.0" should be considered to have specifically disclosed all sub-ranges such as 1.0 to 8.0, 1.0 to 7.0, 2.0 to 8.0, 2.0 to 6.0, 3.0 to 6.0, 4.0 to 8.0, 3.0 to 8.0, etc., and should be considered to cover endpoint values, particularly sub-ranges defined by integer values, and should be considered to have specifically disclosed individual values ​​such as 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, etc. Unless otherwise indicated, the above explanation method is applicable to all contents of the present invention in its entirety, regardless of whether the scope is extensive or not.

[0026] If an amount, concentration or other numerical value or parameter is expressed as a range, a preferred range, a better range or a series of upper and lower limits, it should be understood that all ranges consisting of any pair of the upper limit or preferred value or better value of the range and the lower limit or preferred value or better value of the range have been specifically disclosed herein, regardless of whether these ranges are disclosed separately. In addition, when a numerical range is mentioned herein, unless otherwise specified, the range is intended to include its endpoints and all integers and fractions within the range.

[0027] In this document, numerical values ​​should be understood to have the accuracy of the number of significant digits as long as the purpose of the invention can be achieved. For example, the number 40.0 should be understood to cover the range from 39.50 to 40.49.

[0028] In this document, where Markush groups or optional terms are used to describe features or embodiments of the present invention, those skilled in the art will appreciate that any combination of subgroups or individual members of the Markush group or optional list can also be used to describe the present invention. For example, if X is described as "selected from the group consisting of X1, X2, and X3," this fully describes the claim that X is X1 and the claim that X is X1 and / or X2 and / or X3. Furthermore, where Markush groups or optional terms are used to describe features or embodiments of the present invention, those skilled in the art will appreciate that any combination of subgroups or individual members of the Markush group or optional list can also be used to describe the present invention. Accordingly, for example, if X is described as "selected from the group consisting of X1, X2, and X3," and Y is described as "selected from the group consisting of Y1, Y2, and Y3," this fully describes the claim that X is X1, X2, or X3, and Y is Y1, Y2, or Y3.

[0029] Unless otherwise specified, in this disclosure, a compound refers to a chemical substance formed by two or more elements linked by chemical bonds, including, but not limited to, small molecule compounds and polymer compounds. The term "compound" as used herein is not limited to a single chemical substance but may also refer to chemical substances of the same type with the same composition or properties.

[0030] In this article, a prepolymer refers to a product that still contains reactive functional groups or has polymerization potential after a compound or mixture (monomer) undergoes a prepolymerization (partial polymerization) reaction. For example, the molecular weight or viscosity can be used to assist in confirming whether the reaction degree of the prepolymerization reaction meets the requirements. The prepolymerization method used in this article includes, but is not limited to, using solution heating to initiate the prepolymerization reaction, or using a hot melt reaction to initiate the prepolymerization reaction. For example, solution heating prepolymerization is to add raw materials to a solvent and mix and dissolve them to obtain a solution, and optionally add a catalyst or inhibitor to the solution. After all raw materials have dissolved in the solvent, the temperature is raised to react, thereby initiating the prepolymerization reaction. Hot melt reaction prepolymerization is to directly heat and melt the raw materials to initiate the prepolymerization reaction. The prepolymerized product (prepolymer) has a larger molecular weight than the unprepolymerized compound monomer or mixture monomer, and can be analyzed by gel permeation chromatography (GPC). The graph of the residence time (X-axis) and molecular weight (Y-axis) distribution results shows that the molecular weight distribution peak of the prepolymer is located at the front end (shorter residence time), while the molecular weight distribution peak of the monomer is located at the back end (longer residence time). Furthermore, the resulting prepolymer has a broader molecular weight distribution peak with multiple consecutive peaks, while the monomer has a narrower molecular weight distribution peak with only a single peak.

[0031] To those skilled in the art, a resin composition containing three compounds A, B, and C and an additive (comprising four components in total) and a resin composition containing a prepolymer formed by the three compounds A, B, and C and an additive (comprising two components in total) are different resin compositions, and the two are completely different in many aspects, such as the preparation method, the physical and chemical properties of the compounds themselves, and the properties of their products. For example, the former is formed by mixing A, B, C, and the additive to form a resin composition, while the latter requires first prepolymerizing the mixture including A, B, and C under appropriate conditions to form a prepolymer, and then mixing the prepolymer with the additive to prepare the resin composition. For example, to those skilled in the art, the two resin compositions have completely different compositions, and because the function of the prepolymer formed by the three compounds A, B, and C in the resin composition is completely different from the function of A, B, and C individually or collectively in the resin composition, the two resin compositions should be considered to be completely different chemical substances with completely different chemical positions. For example, to those skilled in the art, because the two resin compositions are completely different chemical substances, their products will not have the same properties. For example, in a resin composition comprising a prepolymer formed by three compounds A, B, and C and a crosslinking agent, since A, B, and C have partially reacted or converted to form the prepolymer during the prepolymerization reaction, when the resin composition is subsequently heated at a high temperature to form a semi-cured state, a partial crosslinking reaction occurs between the prepolymer and the crosslinking agent, rather than a partial crosslinking reaction between A, B, and C and the crosslinking agent individually. Therefore, the products formed from the two resin compositions will be completely different and have completely different properties.

[0032] Unless otherwise specified, "resin" is generally a customary name for a synthetic polymer. However, in the present invention, "resin" can be interpreted to include monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and polymers thereof, and is not limited thereto.

[0033] As used herein, a vinyl group refers to a compound structure containing an ethylenic carbon-carbon double bond (C=C) or a functional group derived therefrom. Examples of vinyl groups include, but are not limited to, functional groups such as vinyl, allyl, vinylbenzyl, and methacrylate groups. Unless otherwise specified, the position of these functional groups is not particularly limited and may, for example, be located at the end of a long chain structure. Thus, for example, a vinyl-containing polyphenylene ether resin refers to a polyphenylene ether resin containing functional groups such as vinyl, allyl, vinylbenzyl, and methacrylate groups, but is not limited thereto.

[0034] In this document, unless otherwise specified, specific examples of acrylate compounds written in the form of "(meth)" should be interpreted as including both cases containing a methyl group and not containing a methyl group. For example, cyclohexanedimethanol di(meth)acrylate should be interpreted as including cyclohexanedimethanol diacrylate and cyclohexanedimethanol dimethacrylate.

[0035] Unless otherwise specified, in the present invention, modified products (also referred to as modified products) include: products after modification of the reactive functional groups of each resin, products after prepolymerization of each resin with other resins, products after cross-linking of each resin with other resins, products after homopolymerization of each resin, products after copolymerization of each resin with other resins, and the like.

[0036] Unless otherwise specified, the alkyl and alkenyl groups described in the present invention include their various isomers. For example, propyl should be interpreted as including n-propyl and isopropyl.

[0037] As used herein, parts by weight represent parts by weight, which may be any weight unit, such as, but not limited to, kilograms, grams, pounds, etc. For example, 100 parts by weight of a prepolymer may represent 100 kilograms of prepolymer or 100 pounds of prepolymer.

[0038] The following detailed description is merely illustrative in nature and is not intended to limit the present invention and its uses. In addition, this document is not bound by any theory described in the foregoing prior art or summary of the invention or in the following detailed description or examples.

[0039] As mentioned above, the main object of the present invention is to provide a resin composition comprising 10 parts by weight of a first prepolymer and 5 to 30 parts by weight of a vinyl-containing polyphenylene ether resin, wherein:

[0040] The first prepolymer is prepared by prepolymerization of a reaction mixture, wherein the reaction mixture comprises polyphenylmethanemaleimide, a compound having a structure represented by formula (1), and a compound having a structure represented by formula (2), and the weight ratio of the polyphenylmethanemaleimide, the compound having a structure represented by formula (1), and the compound having a structure represented by formula (2) is 100:10-30:15-45.

[0041]

[0042]

[0043] as well as

[0044] The resin composition does not include a second prepolymer, and the second prepolymer is prepared by prepolymerization of maleimide and bis(trifluoromethyl)benzenediamine.

[0045] In the resin composition of the present invention, the first prepolymer is prepared by a prepolymerization reaction of a reaction mixture. For example, the prepolymerization reaction can be carried out by heating the components of the reaction mixture to 180° C. to 400° C. and melt mixing for 6 to 600 seconds, preferably heating to 200° C. to 250° C. and melt mixing for 60 to 200 seconds, to obtain the first prepolymer, i.e., a prepolymer formed by polyphenylmethanemaleimide, the compound having the structure represented by formula (1), and the compound having the structure represented by formula (2). For example, the temperature of the prepolymerization reaction can be 180° C., 200° C., 210° C., 220° C., 230° C., 240° C., 250° C., 300° C., or 400° C., but is not limited thereto. For example, the prepolymerization time may be 6 seconds, 20 seconds, 70 seconds, 80 seconds, 90 seconds, 100 seconds, 110 seconds, 120 seconds, 130 seconds, 140 seconds, 150 seconds, 160 seconds, 170 seconds, 180 seconds, 190 seconds, 300 seconds, 450 seconds or 600 seconds, but is not limited thereto.

[0046] In one embodiment, the method for producing the second prepolymer comprises heating and melting a maleimide resin until it becomes liquid, then adding bis(trifluoromethyl)biphenyl diamine, and continuing the reaction at 50 to 200°C for 1 to 6 hours. After the reaction is complete, a solvent is added and the mixture is dispersed by stirring to obtain the second prepolymer, which is a prepolymer of maleimide and bis(trifluoromethyl)biphenyl diamine. In another embodiment, the method for producing the second prepolymer comprises dissolving the maleimide resin in a solvent, then adding bis(trifluoromethyl)biphenyl diamine and stirring to dissolve it. After complete dissolution, the mixture is allowed to react at a high temperature (e.g., 50 to 150°C) for 2 to 8 hours to obtain the second prepolymer, which is a prepolymer of maleimide and bis(trifluoromethyl)biphenyl diamine.

[0047] In the present invention, the amount of the vinyl-containing polyphenylene ether resin added is 5 to 30 parts by weight relative to 10 parts by weight of the first prepolymer.

[0048] In the present invention, during the prepolymerization reaction of the reaction mixture to prepare the first prepolymer, the weight ratio of polyphenylmethanemaleimide, the compound having the structure represented by formula (1), and the compound having the structure represented by formula (2) is 100:10-30:15-45. For example, in one embodiment, compared to 100 parts by weight of polyphenylmethanemaleimide, the reaction mixture may include 10-30 parts by weight of the compound having the structure represented by formula (1). For example, in one embodiment, compared to 100 parts by weight of polyphenylmethanemaleimide, the reaction mixture may include 15-45 parts by weight of the compound having the structure represented by formula (2).

[0049] Unless otherwise specified, the polyphenylmethane maleimide mentioned in the embodiments of the present invention may be various commercially available polyphenylmethane maleimides, such as but not limited to BMI-2300 produced by Yamato Chemical Industry Co., Ltd.

[0050] Unless otherwise specified, the vinyl-containing polyphenylene ether resins mentioned in the various embodiments of the present invention may include various polyphenylene ether resins whose terminals are modified with vinyl groups, allyl groups, or (meth)acrylate groups, such as vinyl benzyl biphenyl polyphenylene ether resins, methacrylate-containing polyphenylene ether resins, vinyl benzyl bisphenol A polyphenylene ether resins, or combinations thereof, and are not limited thereto.

[0051] For example, in one embodiment, the aforementioned vinyl-containing polyphenylene ether resin may include various types of vinyl-containing polyphenylene ether resins known in the art. The vinyl-containing polyphenylene ether resins suitable for the present invention are not particularly limited and may be any one or more commercially available products, homemade products, or a combination thereof. Examples thereof may include, but are not limited to, polyphenylene ether resins containing vinyl, allyl, vinylbenzyl, or methacrylate. For example, in one embodiment, the aforementioned vinyl-containing polyphenylene ether resin includes a vinylbenzyl biphenyl polyphenylene ether resin, a methacrylate-containing polyphenylene ether resin (i.e., a methacryloyl-containing polyphenylene ether resin), an allyl-containing polyphenylene ether resin, a vinylbenzyl bisphenol A polyphenylene ether resin, or a combination thereof. For example, the vinyl-containing polyphenylene ether resin may be a vinyl benzyl biphenyl polyphenylene ether resin having a number average molecular weight of approximately 1200 (e.g., OPE-2st1200, available from Mitsubishi Gas Chemical Co., Ltd.), a vinyl benzyl biphenyl polyphenylene ether resin having a number average molecular weight of approximately 2200 (e.g., OPE-2st2200, available from Mitsubishi Gas Chemical Co., Ltd.), a methacrylate-containing polyphenylene ether resin having a number average molecular weight of approximately 1900 to 2300 (e.g., SA9000, available from Sabic Corporation), a vinyl benzyl bisphenol A polyphenylene ether resin having a number average molecular weight of approximately 2400 to 2800, or a combination thereof, but the present invention is not limited thereto.

[0052] In the present invention, the resin composition does not include a second prepolymer, which is prepared by prepolymerizing maleimide and bis(trifluoromethyl)benzenediamine. Adding a second prepolymer to the resin composition would degrade both the electroless copper plating rate and the copper foil tensile strength of the resin composition.

[0053] For example, the second prepolymer may be a prepolymer obtained by reacting polyphenylmethanemaleimide and 2,2'-bis(trifluoromethyl)-4,4'-biphenylenediamine, a prepolymer obtained by reacting 2,2'-bis-[4-(4-maleimidophenoxy)phenyl]propane and 2,2'-bis(trifluoromethyl)-4,4'-biphenylenediamine, or a prepolymer obtained by reacting 1,6-bismaleimido-(2,2,4-trimethyl)hexane and 2,2'-bis(trifluoromethyl)-4,4'-biphenylenediamine.

[0054] For example, in one embodiment, the resin composition of the present invention further includes 5 to 35 parts by weight of a maleimide resin, compared to 10 parts by weight of the first prepolymer.

[0055] For example, in the present invention, unless otherwise specified, the aforementioned maleimide resin to be added as needed should be interpreted to include maleimide monomers, maleimide polymers, combinations of maleimide monomers, combinations of maleimide polymers, and combinations of maleimide monomers and maleimide polymers. For example, the maleimide resin refers to a compound, monomer, mixture, or polymer (including oligomers) having one or more maleimide functional groups in the molecule. Unless otherwise specified, the aforementioned maleimide resin to be added as needed can be any one or more maleimide resins suitable for use in the production of prepregs, resin films, laminates, or printed circuit boards. Specific examples include, but are not limited to, 4,4'-diphenylmethane bismaleimide, phenylmethane maleimide oligomer (or polyphenylmethane maleimide), bismaleimide toluene, diethyl bismaleimide toluene, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide (or 2,2'-bis-[4-(4-maleimidophenoxy)phenyl]propane), 3,3'-dimethyl-5, 5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,3-dimethylphenylmaleimide, 2,6-dimethylphenylmaleimide, N-phenylmaleimide, maleimide resins containing biphenyl structures, maleimide resins containing aliphatic long-chain structures, or combinations thereof. Furthermore, unless otherwise specified, the maleimide resins described herein also encompass prepolymers of the aforementioned compounds, such as, but not limited to, prepolymers of diallyl compounds and maleimide compounds, prepolymers of polyfunctional amines (including diamines) and maleimide compounds, or prepolymers of acidic phenol compounds and maleimide compounds.

[0056] For example, the maleimide resin may be a maleimide resin produced by Yamato Chemical Co., Ltd. under the trade names BMI-TMH, BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000, BMI-4000H, BMI-5000, BMI-5100, BMI-7000, and BMI-7000H, or a maleimide resin produced by KI Chemical Co., Ltd. under the trade names BMI-70 and BMI-80, or a maleimide resin produced by Nippon Kayaku Co., Ltd. under the trade names MIR-3000, or a maleimide resin produced by Evonik Chemical Co., Ltd. under the trade names Compimide MDAB, Compimide TDAB, and Compimide DE-TDAB.

[0057] For example, the maleimide resin containing an aliphatic long chain structure may be a maleimide resin produced by a designer company under the trade names BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-3000J, BMI-3000G, BMI-3000GE, BMI-5000, and BMI-6000. For example, the maleimide resin containing an aliphatic long chain structure may be a maleimide resin having an aliphatic long chain structure of 40 to 720 carbon atoms.

[0058] For example, in one embodiment, the maleimide resin used in the present invention includes 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, a compound having a structure represented by formula (3), a compound having a structure represented by formula (4), or a combination thereof.

[0059]

[0060] Formula (3), wherein m is an integer from 1 to 10;

[0061]

[0062] Formula (4), wherein n is an integer from 1 to 5.

[0063] For example, in one embodiment, the resin composition of the present invention further comprises 10 to 30 parts by weight of a polyolefin relative to 10 parts by weight of the first prepolymer. For example, in one embodiment, the resin composition of the present invention further comprises 5 to 35 parts by weight of a maleimide resin and 10 to 30 parts by weight of a polyolefin relative to 10 parts by weight of the first prepolymer.

[0064] For example, in the present invention, unless otherwise specified, examples of the aforementioned optionally added polyolefins include, but are not limited to, styrene-butadiene-divinylbenzene terpolymers, styrene-butadiene-maleic anhydride terpolymers, vinyl-polybutadiene-urethane oligomers, styrene-butadiene copolymers, hydrogenated styrene-butadiene copolymers (or styrene-ethylene-butylene-styrene block polymers), styrene-isoprene copolymers, hydrogenated styrene-isoprene copolymers, hydrogenated styrene-butadiene-divinylbenzene terpolymers, polybutadiene (i.e., butadiene homopolymers), maleic anhydride-butadiene copolymers, methyl styrene copolymers, or combinations thereof. Preferably, the polyolefin is a styrene-butadiene copolymer, a hydrogenated styrene-butadiene copolymer, polybutadiene, a styrene-butadiene-maleic anhydride terpolymer, or a maleic anhydride-butadiene copolymer. For example, the polybutadiene may include hydrogenated polybutadiene without reactive functional groups. The polybutadiene may include polybutadiene with reactive functional groups, polybutadiene containing hydroxyl groups, polybutadiene containing phenolic hydroxyl groups (having a polybutadiene structure and phenolic hydroxyl groups), polybutadiene containing carboxyl groups, polybutadiene containing acid anhydride groups, polybutadiene containing epoxy groups, polybutadiene containing isocyanate groups, polybutadiene containing urethane groups, hydrogenated polybutadiene with terminal hydroxyl groups vinylized (no longer containing hydroxyl groups), or combinations thereof. For example, the polybutadiene may include polybutadiene containing epoxy groups.

[0065] In addition, the resin composition may further include an inorganic filler, a hardening accelerator, a flame retardant, a polymerization inhibitor, a solvent, a silane coupling agent, a colorant, a toughening agent, or a combination thereof as needed, but is not limited thereto.

[0066] For example, the inorganic filler can be any one or more inorganic fillers suitable for use in the production of prepregs, resin films, laminates, or printed circuit boards. Specific examples include, but are not limited to, silica (molten, non-molten, porous, or hollow), aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite (AlOOH), calcined talc, talc, silicon nitride, or calcined kaolin. Furthermore, the inorganic filler can be spherical, fibrous, plate-like, granular, flake-like, or needle-like, and may optionally be pretreated with a silane coupling agent.

[0067] For example, the hardening accelerator (including the hardening initiator) may include a catalyst such as a Lewis base or a Lewis acid. The Lewis base may include one or more of imidazole, boron trifluoride amine complex, ethyltriphenylphosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP), and 4-dimethylaminopyridine (DMAP). The Lewis acid may include a metal salt compound, such as a metal salt compound of manganese, iron, cobalt, nickel, copper, or zinc, or a metal catalyst such as zinc octoate or cobalt octoate. The hardening accelerator also includes a hardening initiator, such as a peroxide that can generate free radicals. The hardening initiator includes but is not limited to: diisopropyl benzene peroxide, t-butyl peroxybenzoate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne (25B) and bis(t-butylperoxyisopropyl)benzene or a combination thereof.

[0068] For example, the flame retardant may be any one or more flame retardants suitable for use in the production of prepregs, resin films, laminates, or printed circuit boards, such as, but not limited to, phosphorus-containing flame retardants, preferably including: ammonium polyphosphate, hydroquinone bis-(diphenylphosphate), bisphenol A bis-(diphenylphosphate), tri(2-carboxyethyl)phosphine (TCEP), tris(chloroisopropyl)phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), resorcinol bis(dixylenyl phosphate), tris ...2-carboxyethyl)phosphine (TCEP), tris(2-carboxyethyl)phosphine (TCEP), tris(2-carboxyethyl)phosphine (TCEP), tris(2-carboxyethyl)phosphine (TCEP), tris(2-carboxyethyl)phosphine (TCEP), tris(2-carboxyethyl)phosphine (TCEP), tris(2-carboxyethyl)phosphine (TCEP), tri phosphate), RDXP, such as commercial products such as PX-200, PX-201, and PX-202, phosphazene compounds (such as commercial products such as SPB-100, SPH-100, and SPV-100), melamine polyphosphate, DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and its derivatives or resins, DPPO (diphenylphosphine oxide) and its derivatives or resins, melamine cyanurate, tri-hydroxy ethyl isocyanurate, aluminum phosphinate (such as products such as OP-930 and OP-935), or combinations thereof.

[0069] For example, the flame retardant may be a DPPO compound (e.g., a bis-DPPO compound, such as commercially available products such as PQ-60), a DOPO compound (e.g., a bis-DOPO compound), a DOPO resin (e.g., DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN), or a DOPO-bonded epoxy resin. DOPO-PN is a DOPO phenol novolac compound, and DOPO-BPN may be a bisphenol novolac compound such as DOPO-BPAN (DOPO-bisphenol A novolac), DOPO-BPFN (DOPO-bisphenol F novolac), or DOPO-BPSN (DOPO-bisphenol S novolac).

[0070] For example, the polymerization inhibitor may include, but is not limited to, 1,1-diphenyl-2-trinitrophenylhydrazine, methacrylonitrile, 2,2,6,6-tetramethyl-1-oxy-piperidine, dithioesters, nitroxide-stabilized free radicals, triphenylmethyl free radicals, metal ion free radicals, sulfhydryl free radicals, hydroquinone, p-methoxyphenol, p-benzoquinone, phenothiazine, β-phenylnaphthylamine, p-tert-butylcatechol, methylene blue, 4,4'-butylenebis(6-tert-butyl-3-methylphenol), and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), or combinations thereof. For example, the nitroxide-stabilized free radical may include, but is not limited to, nitroxide free radicals derived from cyclic hydroxylamines, such as 2,2,6,6-substituted-1-piperidinyloxy free radicals or 2,2,5,5-substituted-1-pyrrolidinyloxy free radicals. The substituent is preferably an alkyl group with 4 or fewer carbon atoms, such as a methyl group or an ethyl group. Specific nitrogen oxide free radical compounds are not limited, and examples include but are not limited to 2,2,6,6-tetramethyl-1-piperidinyloxy free radical, 2,2,6,6-tetraethyl-1-piperidinyloxy free radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy free radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy free radical, 1,1,3,3-tetramethyl-2-isoindolinyloxy free radical, N,N-di-tert-butylamineoxy free radical, etc. Stable free radicals such as galvinoxyl free radical can also be used to replace the nitrogen oxide free radical. The polymerization inhibitor suitable for the resin composition of the present invention can also be a product derived from the hydrogen atom or atomic group in the polymerization inhibitor being replaced by other atoms or atomic groups. For example, the hydrogen atom in the polymerization inhibitor is replaced by an atomic group such as an amino group, a hydroxyl group, or a ketocarbonyl group.

[0071] For example, the above-mentioned solvent is not particularly limited and can be any solvent suitable for dissolving the resin composition of the present invention, including but not limited to: methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide, propylene glycol methyl ether and the like solvents or mixed solvents thereof.

[0072] For example, the silane coupling agent may include a silane compound (such as, but not limited to, a siloxane compound), which can be further classified into amino silane compounds, epoxide silane compounds, vinyl silane compounds, acrylate silane compounds, methacrylate silane compounds, hydroxy silane compounds, isocyanate silane compounds, methacryloxy silane compounds, and acryloxy silane compounds based on the type of functional group.

[0073] For example, the coloring agent may include but is not limited to dye or pigment.

[0074] In the present invention, the addition of a toughening agent primarily improves the toughness of the resin composition. For example, such toughening agents may include, but are not limited to, carboxyl-terminated butadiene acrylonitrile rubber (CTBN), core-shell rubber, and other compounds, or combinations thereof.

[0075] The resin compositions of the aforementioned embodiments can be made into various products, such as components suitable for use in various electronic products, including but not limited to prepregs, resin films, laminates, or printed circuit boards.

[0076] For example, the resin composition of the present invention can be made into a prepreg (or prepreg).

[0077] For example, the semi-cured sheet (or prepreg) described in the present invention has a reinforcing material and a layered material arranged on the reinforcing material, and the layered material is formed by heating the aforementioned resin composition to a semi-cured state (B-stage) at a high temperature. The baking temperature for making the semi-cured sheet is, for example, between 60°C and 130°C. The reinforcing material can be a fiber material or a non-fibrous material, and the form of the reinforcing material can be any one of a woven fabric and a non-woven fabric, and the woven fabric preferably includes glass fiber cloth. The type of glass fiber cloth is not particularly limited, and can be commercially available glass fiber cloth that can be used for various printed circuit boards, such as E-type glass fiber cloth, D-type glass fiber cloth, S-type glass fiber cloth, T-type glass fiber cloth, L-type glass fiber cloth or Q-type glass fiber cloth, wherein the types of fibers include yarn and roving, etc., and the form can include open fiber or non-open fiber. The aforementioned non-woven fabric preferably includes liquid crystal resin non-woven fabric, such as polyester non-woven fabric, polyurethane non-woven fabric, etc., but is not limited thereto. The aforementioned fabric may also include, but is not limited to, a liquid crystal resin fabric, such as a polyester fabric or a polyurethane fabric. This reinforcing material can increase the mechanical strength of the prepreg. In a preferred embodiment, the reinforcing material may also be optionally pre-treated with a silane coupling agent. The prepreg is subsequently heated and cured (C-stage), forming an insulating layer.

[0078] For example, the resin compositions can be uniformly mixed to form a varnish, which is then placed in an impregnation tank. A glass fiber cloth is then immersed in the tank to adhere the resin composition to the glass fiber cloth. The varnish is then heated and baked at an appropriate temperature until it reaches a semi-cured state, thereby obtaining a prepreg.

[0079] For example, the resin composition of the present invention can be made into a resin film.

[0080] For example, in one embodiment, the resin film of the present invention is formed by baking the resin composition to a semi-cured state (B-stage). For example, the resin composition can be selectively coated on a liquid crystal resin film, a polyethylene terephthalate film (PET film), or a polyimide film. For another example, the resin composition of each embodiment of the present invention can be coated on a copper foil to ensure uniform adhesion of the resin composition. The resin film is then baked at a temperature of 60°C to 130°C for 5 to 15 minutes until the semi-cured state is formed, thereby obtaining a copper foil-clad resin film.

[0081] For example, the resin composition of the present invention can be made into a laminate.

[0082] For example, in one embodiment, the laminate described herein includes at least two metal foils and an insulating layer disposed between the metal foils. The insulating layer can be formed by curing the aforementioned resin composition under high temperature and high pressure conditions (C-stage), wherein a suitable curing temperature can be between 180°C and 270°C, preferably between 200°C and 250°C, and a curing time can be between 60 and 150 minutes, preferably between 90 and 120 minutes. The insulating layer can be formed by curing the aforementioned prepreg or resin film (C-stage). The metal foil can include copper, aluminum, nickel, platinum, silver, gold, or alloys thereof. For example, the metal foil can be copper foil. In one embodiment, the laminate is a copper clad laminate (CCL).

[0083] In addition, the aforementioned laminate can be further processed through a circuit manufacturing process to form a circuit board, such as a printed circuit board.

[0084] One method of manufacturing the printed circuit board of the present invention can be to use a double-sided copper foil substrate with a thickness of 28 mils and 0.5 ounces of HVLP (hyper very low profile) copper foil (such as product EM-891, available from Taiwan Optoelectronic Materials Co., Ltd.), drill holes and then perform electroplating to form electrical conductivity between the upper copper foil and the bottom copper foil. The upper copper foil and the bottom copper foil are then etched to form the inner layer circuit. The inner layer circuit is then subjected to a browning and roughening treatment to form a concave-convex structure on the surface to increase the roughness. Then, the copper foil, the aforementioned prepreg, the aforementioned inner layer circuit, the aforementioned prepreg, and the copper foil are stacked in sequence, and then a vacuum lamination device is used to heat at a temperature of 190°C to 245°C for 90 to 240 minutes to cure the insulating layer material of the prepreg. Then, various circuit board manufacturing processes known in the art, such as blackening, drilling, and copper plating, are performed on the copper foil on the outermost surface to obtain a printed circuit board.

[0085] In one embodiment, the resin composition provided by the present invention can improve at least one of the following properties: electroless copper plating rate, storage modulus, copper foil tensile strength, and winding appearance test.

[0086] For example, in one embodiment, the aforementioned product has one, multiple, or all of the following characteristics:

[0087] The chemical copper plating rate is 100%;

[0088] A storage modulus, as measured according to the method described in IPC-TM-650 2.4.24.4, is greater than or equal to 7.2 GPa, e.g., between 7.2 GPa and 8.9 GPa, or between 8.3 GPa and 8.9 GPa, for example, a storage modulus of 7.2 GPa, 7.8 GPa, 8.0 GPa, 8.3 GPa, 8.4 GPa, 8.5 GPa, 8.6 GPa, 8.7 GPa, 8.8 GPa, or 8.9 GPa;

[0089] The copper foil tensile force measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 0.62 kgf / cm, for example, between 0.62 kgf / cm and 1.20 kgf / cm, and for example, between 0.82 kgf / cm and 1.20 kgf / cm, for example, the copper foil tensile force is 0.62 kgf / cm, 0.75 kgf / cm, 0.77 kgf / cm, 0.79 kgf / cm, 0.80 kgf / cm, 0.82 kgf / cm, 0.86 kgf / cm, 0.87 kgf / cm, 0.89 kgf / cm, 0.95 kgf / cm, 1.12 kgf / cm, or 1.20 kgf / cm; and

[0090] Can pass the winding appearance test (for example, when the resin film is wound on a 6-inch tube, the surface has cracks less than 5 mm or no cracks, and when it is wound on a 3-inch tube, the surface has cracks greater than or equal to 5 mm; or when the resin film is wound on a 6-inch tube and a 3-inch tube, the surface has no cracks or cracks less than 5 mm).

[0091] The resin compositions of the examples and comparative examples of the present invention were prepared using various raw materials from the following sources in the amounts shown in Tables 1 to 4, and were further prepared into various test samples.

[0092] The chemical raw materials used in the resin compositions of the embodiments of the present invention and the comparative examples and the chemical raw materials used in the prepolymer preparation examples are as follows:

[0093] SA9000: polyphenylene ether resin containing methacrylate, purchased from Sabic.

[0094] OPE-2st 1200: vinylbenzyl biphenyl polyphenylene ether resin, purchased from Mitsubishi Gas Chemical.

[0095] OPE-2st 2200: vinylbenzyl biphenyl polyphenylene ether resin, purchased from Mitsubishi Gas Chemical.

[0096] Ricon 100: styrene-butadiene copolymer, available from Cray Valley.

[0097] JP-100: epoxy-containing polybutadiene, purchased from Japan Soda.

[0098] Ricon 257: styrene-butadiene-divinylbenzene terpolymer, available from Cray Valley.

[0099] BMI-70: 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, purchased from KI Chemicals.

[0100] BMI-3000: a compound having the structure shown in formula (3), purchased from the designer's molecular company.

[0101]

[0102] Formula (3), wherein m is an integer from 1 to 10;

[0103] MIR-3000: a compound having the structure shown in formula (4), purchased from Nippon Kayaku Co., Ltd.

[0104]

[0105] Formula (4), wherein n is an integer from 1 to 5.

[0106] BMI-2300: polyphenylmethanemaleimide, purchased from Yamato Chemical.

[0107] X1: A compound having the structure represented by formula (1), purchased from Shikoku Chemicals.

[0108] X2: a compound having the structure represented by formula (2), purchased from Printec.

[0109] 25B: 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, purchased from NOF Corporation.

[0110] SC-2500-SMJ: spherical silica surface-treated with a methacrylate-based silane coupling agent, purchased from Admatechs.

[0111] MEK: butanone, commercially available.

[0112] TFMB: 2,2′-bis(trifluoromethyl)-4,4′-benzenediamine, purchased from Sigma-Aldrich.

[0113] BMI-80: 2,2'-bis-[4-(4-maleimidephenoxy)phenyl]propane, purchased from KI Chemicals.

[0114] BMI-TMH: 1,6-bismaleimido-(2,2,4-trimethyl)hexane, purchased from Yamato Chemical.

[0115] DAIP: diallyl isophthalate, purchased from Hengqiao Industry.

[0116] DABPA: diallyl bisphenol A, purchased from Yamato Chemical.

[0117] In the table, Y represents the total weight of the dosage codes A, B, C, and D, and Z represents the total weight of the dosage codes A, B, C, D, and E.

[0118] Preparation Example 1

[0119] 100 parts by weight of maleimide resin BMI-2300, 10 parts by weight of X1, and 15 parts by weight of X2 were heated to 230° C. on a hot plate and melt-mixed for 90 seconds, and then cooled to room temperature (about 25° C.) to obtain prepolymer 1.

[0120] Preparation Example 2

[0121] 100 parts by weight of maleimide resin BMI-2300, 10 parts by weight of X1, and 45 parts by weight of X2 were heated to 230° C. on a hot plate and melt-mixed for 90 seconds, and then cooled to room temperature (about 25° C.) to obtain prepolymer 2.

[0122] Preparation Example 3

[0123] 100 parts by weight of maleimide resin BMI-2300, 30 parts by weight of X1, and 15 parts by weight of X2 were heated to 220° C. on a hot plate and melt-mixed for 95 seconds, and then cooled to room temperature (about 25° C.) to obtain prepolymer 3.

[0124] Preparation Example 4

[0125] 100 parts by weight of maleimide resin BMI-2300, 30 parts by weight of X1, and 45 parts by weight of X2 were heated to 210° C. on a hot plate and melt-mixed for 115 seconds, and then cooled to room temperature (about 25° C.) to obtain prepolymer 4.

[0126] Preparation Example 5

[0127] 100 parts by weight of maleimide resin BMI-2300 were added to a reaction vessel containing 150 parts by weight of dimethylacetamide and stirred until the maleimide resin dissolved. 15 parts by weight of 2,2'-bis(trifluoromethyl)-4,4'-diphenylenediamine (TFMB) was then added and stirred until dissolved. After complete dissolution, the mixture was stirred at 90°C for 3 hours to obtain Prepolymer 5, which is not a prepolymer within the scope of the present invention.

[0128] Preparation Example 6

[0129] 100 parts by weight of maleimide resin BMI-80 and 20 parts by weight of diallyl isophthalate (DAIP) were added to a reaction vessel containing 150 parts by weight of dimethylacetamide and 40 parts by weight of butanone. The mixture was stirred until the maleimide resin and diallyl isophthalate were dissolved. 7.5 parts by weight of 2,2'-bis(trifluoromethyl)-4,4'-benzenediamine (TFMB) was then added and stirred until dissolved. After complete dissolution, the mixture was stirred at 90°C for 3 hours to obtain Prepolymer 6, which is not a prepolymer within the scope of the present invention.

[0130] Preparation Example 7

[0131] 100 parts by weight of maleimide resin BMI-TMH and 10 parts by weight of diallyl isophthalate (DAIP) were added to a reaction vessel containing 150 parts by weight of dimethylacetamide and 40 parts by weight of butanone. The mixture was stirred until the maleimide resin and diallyl isophthalate were dissolved. 30 parts by weight of 2,2'-bis(trifluoromethyl)-4,4'-benzenediamine (TFMB) was then added and stirred until dissolved. After complete dissolution, the mixture was stirred at 90°C for 3 hours to obtain Prepolymer 7, which is not a prepolymer within the scope of the present invention.

[0132] The compositions of the resin compositions of the Examples and Comparative Examples (all in parts by weight) and their properties are shown in the following table:

[0133] [Table 1] Composition of the resin composition of the embodiment (unit: weight parts) and characteristic test

[0134]

[0135] [Table 2] Composition of the resin composition of the embodiment (unit: weight parts) and characteristic test

[0136]

[0137] [Table 3] Composition (unit: weight parts) and characteristic tests of comparative resin compositions

[0138]

[0139]

[0140] [Table 4] Composition (unit: weight parts) and characteristic tests of comparative resin compositions

[0141]

[0142]

[0143] The aforementioned characteristics are prepared by referring to the following method to prepare the object to be tested (sample), and then the characteristics are analyzed according to specific conditions.

[0144] 1. Copper-clad resin film 1: Resin compositions of Examples E1-E13 and Comparative Examples C1-C10 (parts by weight) were selected and added to a stirring tank and mixed uniformly to form a varnish. The varnish was then applied to copper foil (trade name MT18Ex, containing an 18-micron carrier copper foil and a 3-micron thin copper foil, purchased from Mitsui Metals) to ensure uniform adhesion of the resin composition. The varnish was then baked at 80°C for 10 minutes to obtain a copper-clad resin film 1. The copper-clad resin film 1 comprised a resin film layer, a thin copper layer, and a carrier copper foil layer. The resin film layer had a thickness of 32.5 microns.

[0145] 2. Copper-clad resin film 2: Prepare a copper-clad resin film 1, remove the 18-micron carrier copper foil, and then thicken the 3-micron thin copper to 18-micron by electroplating to obtain copper-clad resin film 2.

[0146] 3. Copper-Containing Substrate (Formed by Laminating Two Copper-Clad Resin Films 2): Prepare two copper-clad resin films 2 prepared by the aforementioned method, stack them together, with the two resin film layers adjacent to each other and the outer sides being copper foil layers. Press and cure them in a nitrogen-filled, high-temperature press at a pressing pressure of 2000 psi and a pressing temperature of 230°C for 2.5 hours to form a copper-containing substrate (formed by laminating two copper-clad resin films 2).

[0147] 4. Copper-free substrate (formed by pressing two copper-clad resin films 2 together): Etch and remove the copper foil on both sides of the above copper-containing substrate (formed by pressing two copper-clad resin films 2 together) to obtain a copper-free substrate (formed by pressing two copper-clad resin films 2 together).

[0148] 5. Resin film 1: Prepare a copper-clad resin film 1 prepared by the above method, remove 18 microns of the carrier copper foil, and then remove 3 microns of thin copper by etching to obtain a resin film 1, wherein the thickness of the resin film 1 is 32.5 microns.

[0149] 6. Resin Film 2: The resin compositions of Examples E1-E13 and Comparative Examples C1-C10 (parts by weight) were added to a stirring tank and mixed uniformly to form a varnish. The varnish was then applied to a polyethylene terephthalate film (PET film, 50 μm thick) to ensure uniform adhesion of the resin composition. The varnish was then baked at 80°C for 10 minutes to form a PET-coated resin film. The PET-coated resin film comprised a resin film layer and a PET layer, wherein the resin film layer had a thickness of 32.5 μm.

[0150] For the aforementioned samples to be tested, the test methods and their characteristic analysis items are described as follows:

[0151] Ratio of electroless copper plating

[0152] The above-mentioned resin film 2 is selected and cut into a sample with a length of 10 cm and a width of 10 cm. On the resin film layer, chemical copper plating with a target thickness of 5 microns is performed to obtain a copper layer. Then, a grid with a length of 10 mm and a width of 10 mm is drawn on the surface of the copper layer, for a total of 100 grids. The appearance of each grid is observed with the naked eye. If a white area greater than or equal to 1 mm * 1 mm appears in any area of ​​any grid, it means that the copper plating of the grid is uneven and it is judged as FAIL; on the contrary, if no white area appears or a white area less than 1 mm * 1 mm appears, it is judged as PASS. Definition of chemical copper plating rate = (number of PASS / 100 grids) * 100%. As far as this field is concerned, the higher the chemical copper plating rate, the better. Generally speaking, a difference in chemical copper plating rate greater than 10% indicates a significant difference (significant technical difficulty).

[0153] storage modulus

[0154] The copper-free substrate described above (made of two copper-clad resin films 2 laminated together) was selected as the test sample. The storage modulus of the test sample was measured using dynamic mechanical analysis (DMA) according to the method described in IPC-TM-650 2.4.24.4. The measurement temperature range was 25°C to 300°C, with a temperature rise rate of 2°C / minute. The storage modulus (in GPa) at 50°C was recorded. The higher the storage modulus value, the better the substrate's support (without deformation under pressure). Generally speaking, a storage modulus difference greater than 0.1 GPa is considered significant (significant technical difficulty).

[0155] Copper foil peeling strength (P / S)

[0156] The aforementioned copper-containing substrate (composed of two copper-clad resin films laminated together) was cut into rectangular samples with a width of 24 mm and a length greater than 60 mm. The surface copper foil was then etched, leaving only a strip of copper foil with a width of 3.18 mm and a length greater than 60 mm. Using a universal tensile strength tester, measurements were performed at room temperature (approximately 25°C) in accordance with the method described in IPC-TM-650 2.4.8. The force required to pull the copper foil away from the insulating surface of the substrate was measured, expressed in kgf / cm. In this field, a higher tensile force is preferred. Generally speaking, a difference in copper foil tensile force greater than 0.03 kgf / cm is considered significant (significant technical difficulty).

[0157] Rolling appearance

[0158] The resin film 1 was cut into samples with a width of 600 mm and a length of 100 m, and rolled into 6-inch tubes and 3-inch tubes in sequence. The following characteristics were defined:

[0159] X: When the resin film 1 is rolled up through a 6-inch tube and a 3-inch tube, cracks greater than or equal to 5 mm appear on the surface;

[0160] △: When the resin film 1 is rolled up on a 6-inch tube, cracks less than 5 mm or no cracks appear on the surface, and when it is rolled up on a 3-inch tube, cracks greater than or equal to 5 mm appear on the surface.

[0161] O: When the resin film 1 was rolled up into a 6-inch tube and a 3-inch tube, no cracks or cracks smaller than 5 mm appeared on the surface.

[0162] According to the above test results, the following phenomena can be observed.

[0163] Compared to Example E1, which uses a first prepolymer formed from polyphenylmethane maleimide, a compound having a structure represented by Formula (1), and a compound having a structure represented by Formula (2), Comparative Examples C1, C2, C9, and C10, which use a second prepolymer formed from maleimide and bis(trifluoromethyl)diphenylamine, fail to meet the requirements in terms of chemical copper plating rate and copper foil tensile strength.

[0164] Compared with Example E1, Comparative Examples C3, C5, and C6 do not use the first prepolymer of the present invention. Comparative Example C3 uses a vinyl-containing polyphenylene ether resin and externally adds polyphenylmethane maleimide, a compound having a structure represented by Formula (1), and a compound having a structure represented by Formula (2). Comparative Example C5 only uses a vinyl-containing polyphenylene ether resin. Comparative Example C6 uses a vinyl-containing polyphenylene ether resin and externally adds a hardening accelerator. The products cannot be formed or at least one of the properties such as storage modulus and copper foil tensile strength cannot meet the requirements.

[0165] Compared with Example E1, Comparative Example C4 does not use vinyl-containing polyphenylene ether resin and cannot meet the required tensile strength of the copper foil.

[0166] Compared to Example E1, Comparative Examples C7 and C8 do not use the first prepolymer of the present invention. Comparative Example C7 uses a vinyl-containing polyphenylene ether resin and externally adds a maleimide resin, and Comparative Example C8 uses a vinyl-containing polyphenylene ether resin and externally adds a polyolefin and a maleimide resin. At least one of the properties such as storage modulus and copper foil tensile strength cannot meet the requirements.

[0167] In general, the resin composition of the present invention can simultaneously achieve the following effects: an electroless copper plating rate of 100%, a storage modulus greater than or equal to 7.2 GPa, and a tensile strength on copper foil greater than or equal to 0.62 kgf / cm.

[0168] The above embodiments are merely illustrative and are not intended to limit the embodiments of the subject application or their applications or uses. As used herein, the term "exemplary" means "serving as an example, instance, or illustration." Any exemplary embodiment herein is not necessarily to be construed as preferred or advantageous over other embodiments.

[0169] Furthermore, although at least one exemplary embodiment or comparative example has been presented in the foregoing embodiments, it should be understood that the present invention is susceptible to numerous variations. It should also be understood that the embodiments described herein are not intended to limit the scope, use, or configuration of the claimed subject matter in any way. On the contrary, the foregoing embodiments will provide those skilled in the art with a simple guide to implementing one or more of the described embodiments. Furthermore, various changes may be made to the function and arrangement of components without departing from the scope defined by the claims, and the claims encompass known equivalents and all foreseeable equivalents at the time of filing of this patent application.

Claims

1. A resin composition, characterized in that The invention comprises 10 parts by weight of a first prepolymer and 5 to 30 parts by weight of a vinyl-containing polyphenylene ether resin, wherein: The first prepolymer is prepared by prepolymerization of a reaction mixture, wherein the reaction mixture comprises polyphenylmethanemaleimide, a compound having a structure represented by formula (1), and a compound having a structure represented by formula (2), and the weight ratio of the polyphenylmethanemaleimide, the compound having a structure represented by formula (1), and the compound having a structure represented by formula (2) is 100:10-30:15-45. as well as The resin composition does not include a second prepolymer, and the second prepolymer is prepared by prepolymerization of maleimide and bis(trifluoromethyl)benzenediamine.

2. The resin composition according to claim 1, wherein The vinyl-containing polyphenylene ether resin includes a vinyl-containing benzyl biphenyl polyphenylene ether resin, a methacrylate-containing polyphenylene ether resin, a vinyl-containing benzyl bisphenol A polyphenylene ether resin, or a combination thereof.

3. The resin composition according to claim 1, wherein The resin composition further comprises 5 to 35 parts by weight of a maleimide resin, and the maleimide resin comprises 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, a compound having a structure represented by formula (3), a compound having a structure represented by formula (4), or a combination thereof. Formula (3), wherein m is an integer from 1 to 10; Formula (4), wherein n is an integer from 1 to 5.

4. The resin composition according to claim 1, characterized in that The resin composition further includes 10 to 30 parts by weight of a polyolefin, and the polyolefin includes a styrene-butadiene copolymer, an epoxy-containing polybutadiene, a styrene-butadiene-divinylbenzene terpolymer, or a combination thereof.

5. The resin composition according to claim 1, wherein The resin composition further includes an inorganic filler, a hardening accelerator, a flame retardant, a polymerization inhibitor, a solvent, a silane coupling agent, a colorant, a toughening agent, or a combination thereof.

6. A product made from the resin composition according to claim 1, characterized in that: The product includes a prepreg, a resin film, a laminate or a printed circuit board.

7. The product according to claim 6, characterized in that The chemical copper plating rate of the product is 100%.

8. The product according to claim 6, characterized in that The storage modulus of the product measured according to the method described in IPC-TM-6502.4.24.4 is greater than or equal to 7.2 GPa.

9. The product according to claim 6, characterized in that The copper foil tensile force of the product measured according to the method described in IPC-TM-6502.4.8 is greater than or equal to 0.62 kgf / cm.

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