Maleimide prepolymer resin composition

Abstract

The present invention provides a resin composition containing a maleimide prepolymer resin and articles thereof. The resin composition containing the maleimide prepolymer resin comprises: 100 parts by weight of a vinyl-containing polyphenylene ether resin; 35 to 45 parts by weight of bis(vinylphenyl)ethane; and 30 to 60 parts by weight of the maleimide prepolymer resin; wherein the maleimide prepolymer resin is a prepolymer obtained by a prepolymerization reaction of an aromatic maleimide resin and a long-chain maleimide resin. The articles of the resin composition containing the maleimide prepolymer resin can improve at least one property among the variation amount of glass transition temperature, the tensile force on copper foil, the thermal expansion rate, the thermal expansion coefficient, and the surface appearance.

Description

Technical Field

[0001] The present invention relates to a resin composition and a product thereof, in particular to a resin composition containing maleimide prepolymer resin and a product thereof, which can be used to prepare products such as resin films, prepregs, laminates or printed circuit boards. Background Art

[0002] Low dielectric resin materials are important basic materials in the electronics industry and are widely used in electronic products such as various servers, large base stations, and cloud devices.

[0003] In recent years, electronic technology is developing towards higher density, lower power consumption and higher performance. Therefore, there are higher requirements for low-dielectric resin materials. With the high integration of electronic components per unit area, the heat dissipated by electronic components during operation is increasing. Especially in extremely harsh environments such as high temperature and high humidity, the glass transition temperature of low-dielectric resin materials in the environment is required to be higher. Furthermore, in order to improve the interconnectivity and installation reliability of electronic components, the resin material needs to have a lower thermal expansion coefficient to ensure that the resin material has a higher dimensional stability, which is convenient for smooth positioning during the subsequent printed circuit board processing. At the same time, the resin material also needs to have sufficient adhesion to ensure that it can be tightly bonded to the metal circuit and will not fail due to the falling of the metal circuit. In this way, the demand for low-dielectric resin materials to be used in printed circuit boards can be met.

[0004] The low dielectric resin materials in the prior art utilize unsaturated polyphenylene ether resin to introduce maleimide resin and bis(vinylphenyl)ethane to solve the problems of low glass transition temperature, large thermal expansion coefficient and insufficient heat resistance. However, if aromatic maleimide resin is added to unsaturated polyphenylene ether resin and bis(vinylphenyl)ethane, the overreaction may cause the substrate to dry out, the copper foil tension is too low, and the heat resistance is insufficient. If long-chain maleimide resin is added instead, the heat resistance may be insufficient, and the heat expansion coefficient may be large, the thermal expansion rate may be large, and the heat resistance may be insufficient. Summary of the invention

[0005] With regard to the problems encountered in the prior art, the main purpose of the present invention is to provide a resin composition containing maleimide prepolymer resin (i.e., the maleimide prepolymer resin composition referred to in the name of the invention of this application) and its products, wherein an aromatic maleimide resin and a long-chain maleimide resin are first subjected to a prepolymerization reaction to form a maleimide prepolymer resin, and then appropriate weight portions are added to form the resin composition containing maleimide prepolymer resin and a vinyl polyphenylene ether resin and bis(vinylphenyl)ethane to solve at least one of the above-mentioned prior art problems.

[0006] Specifically, the article of the resin composition containing maleimide prepolymer resin provided by the present invention can improve at least one property of the glass transition temperature variation, the tensile strength against copper foil, the thermal expansion rate, the thermal expansion coefficient, and the surface appearance.

[0007] The resin composition containing maleimide prepolymer resin of the present invention comprises: 100 parts by weight of a vinyl-containing polyphenylene ether resin; 35 to 45 parts by weight of bis(vinylphenyl)ethane; and 30 to 60 parts by weight of maleimide prepolymer resin; wherein the maleimide prepolymer resin is a prepolymer obtained by a prepolymerization reaction of an aromatic maleimide resin and a long-chain maleimide resin, and the long-chain maleimide resin contains a structure represented by any one of formulas (1) to (4);

[0008] Formula (1)

[0009]

[0010] Formula (2)

[0011]

[0012] Formula (3)

[0013]

[0014] Formula (4)

[0015]

[0016] Wherein, in formulas (1) and (2), n is an integer from 1 to 10 respectively; in formula (3), m1 is an integer from 1 to 5, and m2 is an integer from 1 to 5; in formula (4), n is an integer from 1 to 3; and the weight ratio of the aromatic maleimide resin to the long-chain maleimide resin is 1:3 to 1:5.

[0017] The resin composition containing maleimide prepolymer resin of the present invention, wherein the vinyl-containing polyphenylene ether resin comprises a methacrylate polyphenylene ether resin, a vinylbenzyl biphenyl polyphenylene ether resin, a vinylbenzyl bisphenol A polyphenylene ether resin, a vinyl-extended polyphenylene ether resin, or a combination thereof.

[0018] The resin composition containing maleimide prepolymer resin of the present invention, wherein the aromatic maleimide resin comprises bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bisphenol A diphenyl ether bismaleimide, polystyrene methane maleimide, and 4,4'-diphenylmethane bismaleimide, or a combination thereof.

[0019] In one embodiment, the resin composition of the present invention containing maleimide prepolymer resin further comprises a flame retardant, a crosslinking agent, an inorganic filler, a curing accelerator, a solvent, a polymerization inhibitor, a silane coupling agent, a coloring agent, a toughening agent, core-shell rubber or a combination thereof.

[0020] The article of the resin composition of the present invention containing maleimide prepolymer resin includes: a resin film, a prepreg, a laminate or a printed circuit board.

[0021] The article of the resin composition of the present invention containing maleimide prepolymer resin is measured according to the method described in IPC-TM-650 2.4.24.4, and the variation of its glass transition temperature is ≤ 3°C.

[0022] The article of the resin composition of the present invention containing maleimide prepolymer resin is measured according to the method described in IPC-TM-650 2.4.8, and its tensile strength against copper foil is ≥ 3.2 lb / in.

[0023] The article of the resin composition of the present invention containing maleimide prepolymer resin is measured according to the method described in IPC-TM-650 2.4.24.5, and its Z-axis thermal expansion rate is ≤ 2.5%.

[0024] The article of the resin composition of the present invention containing maleimide prepolymer resin is measured according to the method described in IPC-TM-650 2.4.24.5, and its Z-axis thermal expansion coefficient is ≤ 45 ppm / °C.

[0025] The article of the resin composition of the present invention containing maleimide prepolymer resin is tested by visual inspection of the appearance, and there is no dry plate and no texture phenomenon, and its appearance is normal. Description of the Drawings

[0026] Figure 1 For the appearance to be normal and there is no dry plate and texture exposure phenomenon, the test result is "OK".

[0027] Figure 2 There is a dry plate and texture exposure phenomenon, and the test result is "NG". Detailed Description of the Invention

[0028] To enable those with ordinary knowledge in the art to understand the features and effects of the present invention, the following generally describes and defines the terms and phrases mentioned in the specification and the claims. Unless otherwise specified, all technical and scientific terms used in the text have the ordinary meaning understood by those with ordinary knowledge in the art for the present invention. When there is a conflict, the definition in this specification shall prevail.

[0029] The theories or mechanisms described and disclosed herein, whether right or wrong, shall not in any way limit the scope of the present invention, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0030] As used herein, the expressions "a", "an", "one", or similar expressions are used to describe the components and technical features of the present invention. Such descriptions are merely for convenience of expression and to give a general meaning to the scope of the present invention. Therefore, such descriptions should be understood to include one or at least one, and the singular also includes the plural, unless clearly indicated otherwise.

[0031] As used herein, "or a combination thereof" means "or any one combination thereof", and "any one", "any kind", "any one" means "any one", "any kind", "any one".

[0032] As used herein, the terms "comprising", "including", "having", "containing" or any other similar terms are all open-ended transitional phrases, which are intended to cover non-exclusive inclusions. For example, a composition or article containing plural elements is not limited to only these elements listed herein, but may also contain other elements that are not explicitly listed but are usually inherent in the composition or article. In addition, unless otherwise clearly stated, the term "or" means an inclusive "or" rather than 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), A and B are both true (or exist). In addition, as used herein, the interpretations of the terms "comprising", "including", "having", "containing" should be regarded as having specifically disclosed and simultaneously covered the conjunctions such as "consisting of" and "substantially consisting of".

[0033] As used herein, if a feature or condition is defined in the form of a numerical range or a percentage range, it is only for the sake of brevity and convenience. Accordingly, the description of a numerical range or a percentage range should be regarded as having covered and specifically disclosed all possible sub-ranges and individual values within the range, especially integer values. For example, the range description of "1 to 8" should be regarded as having specifically disclosed all sub-ranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., especially the sub-ranges defined by all integer values, and should be regarded as having specifically disclosed the individual values such as 1, 2, 3, 4, 5, 6, 7, 8 within the range. Similarly, the range description of "between 1 and 8" should be regarded as having specifically disclosed all ranges such as 1 to 8, 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., and includes the endpoint values. Unless otherwise specified, the foregoing interpretation method applies to all contents of the present invention throughout the text, regardless of the scope.

[0034] If a quantity or other numerical value or parameter is expressed as a range, a preferred range, or a series of upper and lower limits, it should be understood that all ranges formed by any pair of the upper limits or preferred values of the said range and the lower limits or preferred values of the said range are specifically disclosed herein, whether or not such ranges are separately disclosed. In addition, when a numerical range is mentioned herein, unless otherwise specified, the said range shall include its endpoints and all integers and fractions within the range.

[0035] In this document, on the premise that the invention object can be achieved, a numerical value should be understood to have the precision of the significant digits of the said numerical value. For example, the number 40.0 should be understood to cover the range from 39.50 to 40.49.

[0036] In this document, in the case where a Markush group or alternative terms are used to describe the features or examples of the present invention, those with ordinary knowledge in the art should understand that all subgroups or any individual members within the Markush group or alternative 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", it also means that the claims that X is X1 and the claims that X is X1 and / or X2 and / or X3 have been fully described. Furthermore, for those using a Markush group or alternative terms to describe the features or examples of the present invention, those with ordinary knowledge in the art should understand that any combination of all subgroups or individual members within the Markush group or alternative 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", it means that the claims that X is X1 or X2 or X3 and Y is Y1 or Y2 or Y3 have been fully described.

[0037] In the present invention, unless otherwise specified, a compound refers to a chemical substance formed by the connection of two or more elements through chemical bonds, including small molecule compounds and high molecular compounds, and is not limited thereto. Compounds can include monomers, polymer forms, but are not limited thereto. In this document, a compound is not limited to a single chemical substance when being interpreted, but can also be interpreted as a class of chemical substances having the same composition or the same properties.

[0038] In the present invention, unless otherwise specified, a monomer refers to a molecule that can be covalently bonded to the same or other molecules to form a polymer.

[0039] In the present invention, unless otherwise specified, a polymer refers to a product formed by monomers through a polymerization reaction, which often includes many aggregates of macromolecules. Each macromolecule is composed of many simple structural units repeatedly connected by covalent bonds, and the monomer is the compound used to synthesize the polymer. Polymers can include homopolymers (also known as self-polymers), copolymers, prepolymers, etc., and are not limited thereto. A prepolymer is a chemical substance produced by a polymerization reaction with a monomer conversion rate between 10% and 90%. Polymers of course include oligomers, and are not limited thereto. An oligomer, also known as a low polymer, is a polymer composed of 2 to 20 repeating units, usually a polymer composed of 2 to 5 repeating units. For example, when interpreting a diene polymer, it includes diene homopolymers, diene copolymers, diene prepolymers, and of course also diene oligomers, etc.

[0040] In this article, a prepolymer refers to a product that still contains reactive functional groups or has polymerization potential after a prepolymerization (partial polymerization) reaction of a compound or mixture (monomer). For example, the degree of the prepolymerization reaction can be assisted in confirmation by the high or low molecular weight or viscosity. The prepolymerization methods used in this article, for example but not limited to, using solvent heating to initiate the prepolymerization reaction, or using a thermal melting reaction to initiate the prepolymerization reaction. For example, solvent heating prepolymerization is to add raw materials to a solvent for dissolution, and a catalyst or inhibitor can be selectively added as needed. After all raw materials are dissolved in the solvent, a heating reaction is carried out to initiate the prepolymerization reaction. Thermal melting reaction prepolymerization is to directly heat and melt the raw materials to initiate the prepolymerization reaction. The product after prepolymerization (prepolymer) has a larger molecular weight compared to the un-prepolymerized compound monomer or mixture monomer, and can be analyzed by a Gel Permeation Chromatograph (GPC). In the result graph of the retention time (X-axis) and molecular weight (Y-axis) distribution, the peak of the molecular weight distribution of the prepolymer is located at a relatively front position (shorter retention time), while the peak of the molecular weight distribution of the monomer is located at a relatively rear position (longer retention time). In addition, the obtained prepolymer has a wider molecular weight distribution peak with multiple peaks continuously connected, while in contrast, the monomer has a narrower molecular weight distribution peak that only includes a single peak.

[0041] For those with ordinary knowledge in the art, a resin composition containing three compounds A, B, and C and an additive (a total of four components), and a resin composition containing a prepolymer formed by three compounds A, B, and C and an additive (a total of two components) are different resin compositions, and they are completely different in many aspects such as preparation methods, physical and chemical properties of themselves, and properties of their products. For example, the former is to mix A, B, C, and the additive to form a resin composition, while the latter is to first carry out a prepolymerization reaction on the mixture including A, B, and C under appropriate conditions to form a prepolymer, and then mix the prepolymer with the additive to obtain a resin composition. For example, for those with ordinary knowledge in the art, the above two resin compositions have completely different compositions, and since the functions played by the prepolymer formed by the three compounds A, B, and C in the resin composition are completely different from the functions played by A, B, and C individually or jointly in the resin composition, the two resin compositions should be regarded as completely different chemical substances and have completely different chemical statuses. For example, for those with ordinary knowledge in the art, since the above two resin compositions are completely different chemical substances, their products will not have the same properties. For example, a resin composition including a prepolymer formed by three compounds A, B, and C and a crosslinking agent. Since A, B, and C have partially reacted or transformed during the prepolymerization reaction to form a prepolymer, when the resin composition is heated at a high temperature to form a semi-cured state later, a partial crosslinking reaction occurs between the prepolymer and the crosslinking agent, rather than a partial crosslinking reaction between A, B, and C individually and the crosslinking agent. Therefore, the products formed by the two resin compositions will also be completely different and have completely different properties.

[0042] In the present invention, unless otherwise specified, "resin" generally can be a conventional name for a synthetic polymer. However, in the present invention, when interpreting "resin", it can include monomers, their polymers, a collection of monomers, a combination of their polymers, or a combination of monomers and their polymers, etc., and is not limited thereto. A collection of monomers is a group formed by multiple monomers. For example, in the present invention, when interpreting "maleimide resin", it includes maleimide monomers, maleimide polymers, a combination of maleimide monomers, a combination of maleimide polymers, or a combination of maleimide monomers and maleimide polymers. Resins can include compounds and mixtures. Compounds include monomers or polymers. Mixtures include two or more compounds. Mixtures can also include copolymers or other additives, etc., and are not limited thereto. For example, resins can include a collection of monomers. A collection of monomers is a group formed by multiple monomers.

[0043] In the present invention, for example, when interpreting "vinyl-containing", it includes vinyl, vinylene, allyl, (meth)acrylate group, or a combination thereof.

[0044] In the present invention, unless otherwise specified, in the specific examples of acrylate compounds written in the form of "(meth)", when interpreted, it should be understood to include both cases of containing methyl and not containing methyl. For example, cyclohexanedimethanol di(meth)acrylate should be interpreted to include cyclohexanedimethanol diacrylate and cyclohexanedimethanol dimethacrylate.

[0045] It should be understood that the features disclosed in each embodiment herein can be arbitrarily combined to form the technical solutions of this application, as long as there is no contradiction in the combination of these features.

[0046] In this text, unless otherwise specified, parts by weight represent parts by weight, which can be any weight unit, such as but not limited to weight units such as kilograms, grams, pounds, etc. For example, 100 parts by weight of maleimide resin means it can be 100 kilograms of maleimide resin or 100 pounds of maleimide resin.

[0047] The following specific embodiments are essentially illustrative only and are not intended to limit the present invention and its uses. In addition, this text is not limited by any theory described in the foregoing prior art or the summary of the invention or the following specific embodiments or examples.

[0048] In one embodiment, the resin composition of the present invention containing maleimide prepolymer resin comprises: 100 parts by weight of vinyl-containing polyphenylene ether resin; 35 to 45 parts by weight of bis(vinylphenyl)ethane; and 30 to 60 parts by weight of maleimide prepolymer resin; wherein the maleimide prepolymer resin is a prepolymer obtained by prepolymerization of aromatic maleimide resin and long-chain maleimide resin, and the long-chain maleimide resin contains a structure shown in any one of formulas (1) to (4);

[0049] Formula (1)

[0050]

[0051] Formula (2)

[0052]

[0053] Formula (3)

[0054]

[0055] Formula (4)

[0056]

[0057] Wherein, in Formula (1) and Formula (2), n is an integer from 1 to 10; in Formula (3), m1 is an integer from 1 to 5 and m2 is an integer from 1 to 5; in Formula (4), n is an integer from 1 to 3; and the weight ratio of the aromatic maleimide resin to the long-chain maleimide resin is from 1:3 to 1:5.

[0058] In one embodiment, the reaction conditions (i.e., the prepolymerization reaction) of the prepolymer of the present invention refer to adding 10 parts by weight of the aromatic maleimide resin and 30 to 50 parts by weight of the long-chain maleimide resin into an appropriate amount of solvent, stirring evenly at room temperature to dissolve the aromatic maleimide resin and the long-chain maleimide resin in the solvent to obtain a solution, heating the solution to 100°C to 150°C and reacting for 30 minutes to 90 minutes to obtain the maleimide prepolymer resin of the present invention, and the solid content of the solution is between 50% and 70%. A curing initiator (such as, but not limited to, peroxide) in an amount of 0.1 to 0.5 parts by weight can be added during the reaction process as needed. One of the features of the present invention lies in controlling the reaction conversion rate of the aromatic maleimide resin and the long-chain maleimide resin under appropriate conditions, enabling partial reaction between the components, while the product still retains residual vinyl groups (i.e., unreacted vinyl groups). For example, after the prepolymerization reaction, the reaction conversion rate of the maleimide prepolymer resin of the present invention can be between 10% and 90%.

[0059] In one embodiment, the vinyl group-containing polyphenylene ether resin includes a methacrylate polyphenylene ether resin, a vinylbenzyl biphenyl polyphenylene ether resin, a vinylbenzyl bisphenol A polyphenylene ether resin, a vinyl-extended polyphenylene ether resin, or a combination thereof.

[0060] For example, in one embodiment, the vinyl group-containing polyphenylene ether resin can include various vinyl group-containing polyphenylene ether resins known in the art. The vinyl group-containing polyphenylene ether resin suitable for the present invention is not particularly limited and can be any one or more commercially available products, self-made products, or a combination thereof. In some embodiments, any one or more of the following vinyl group-containing polyphenylene ether resins can be used: vinylbenzyl biphenyl polyphenylene ether resin (such as OPE-2st, available from Mitsubishi Gas Chemical Company), methacrylate polyphenylene ether resin (such as SA9000, available from Sabic Company), vinylbenzyl bisphenol A polyphenylene ether resin, vinyl-extended polyphenylene ether resin, or a combination thereof. The vinyl-extended polyphenylene ether resin can include various polyphenylene ether resins in the US patent application with publication number 2016 / 0185904A1, the entire content of which is incorporated herein by reference.

[0061] In one embodiment, the aromatic maleimide resin includes bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bisphenol A diphenyl ether bismaleimide, polyphenylmethane maleimide, and 4,4'-diphenylmethane bismaleimide, or a combination thereof.

[0062] In one embodiment, the resin composition containing a maleimide prepolymer resin of the present invention may further include a flame retardant, a crosslinking agent, an inorganic filler, a curing accelerator, a solvent, a polymerization inhibitor, a silane coupling agent, a dye, a toughening agent, a core-shell rubber, or a combination thereof.

[0063] For example, in one embodiment, compared with 100 parts by weight of the vinyl-containing polyphenylene ether resin, the content of any one of the foregoing components may be 0.01 part by weight to 300 parts by weight, such as but not limited to 0.01 part by weight to 3 parts by weight, 30 parts by weight to 80 parts by weight, or 50 parts by weight to 300 parts by weight.

[0064] Unless otherwise specified, the flame retardant applicable to the present invention can be any one or more flame retardants applicable to the production of resin films, prepregs, laminates or printed circuit boards. For example, but not limited to, phosphorus-containing flame retardants, preferably including: ammonium polyphosphate, hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenylphosphate), tri(2-carboxyethyl)phosphine (TCEP), tris(2-chloroisopropyl) phosphate, trimethyl phosphate (TMP), dimethyl methylphosphonate (DMMP), resorcinol bis(dixylenylphosphate) (RDXP, such as commercially available products like PX-200, PX-201, PX-202, etc.), phosphazene (such as commercially available products like SPB-100, SPH-100, SPV-100, etc.), melamine polyphosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and its derivatives (such as bis-DOPO compounds) or resins, diphenylphosphine oxide (DPPO) and its derivatives (such as bis-DPPO compounds) or resins, melamine cyanurate, tri-hydroxyethylisocyanurate, aluminum hypophosphite salts (such as products like OP-930, OP-935, etc.) or combinations thereof. Unless otherwise specified, the dosage of the above flame retardants is not particularly limited.

[0065] For example, the flame retardant may be a DPPO compound (such as a bis-DPPO compound), a DOPO compound (such as a bis-DOPO compound), a DOPO resin (such as DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN), a DOPO-bonded epoxy resin, etc., where DOPO-PN is a DOPO phenol novolac resin, and DOPO-BPN may be a bisphenol novolac resin such as DOPO-BPAN (DOPO-bisphenol Anovolac), DOPO-BPFN (DOPO-bisphenol F novolac), or DOPO-BPSN (DOPO-bisphenol S novolac). Without specific indication, the dosage of the above flame retardants is not particularly limited.

[0066] For example, in one embodiment, the crosslinking agent suitable for the present invention may be various crosslinking agents known in the art for resin compositions, including but not limited to triallyl isocyanurate, polyolefins, or combinations thereof. For example, compared with 100 parts by weight of the vinyl-containing polyphenylene ether resin, in the resin composition of the present invention, the dosage of the above crosslinking agent is not particularly limited, and preferably may be 5 parts by weight to 15 parts by weight.

[0067] Without specific indication, the dosage of the curing accelerator used in the present invention can be adjusted as needed. For example, compared with 100 parts by weight of the vinyl-containing polyphenylene ether resin, in the resin composition of the present invention, the dosage of the above curing accelerator is not particularly limited. For example, it may be 0.01 parts by weight to 0.5 parts by weight, or for example, 0.1 parts by weight to 1 part by weight.

[0068] For example, the above-mentioned hardening accelerators (including hardening initiators) may include catalysts such as Lewis bases or Lewis acids. Among them, the Lewis bases may include imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP), 4-dimethylaminopyridine (DMAP), or combinations thereof. The Lewis acids may include metal salt compounds, such as metal salt compounds of manganese, iron, cobalt, nickel, copper, zinc, etc., such as zinc octoate, cobalt octoate and other metal catalysts. The hardening accelerator also includes a hardening initiator, for example, a peroxide that can generate free radicals. The hardening initiator includes but is not limited to: diisopropylbenzene peroxide, tert-butyl peroxybenzoate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B), bis(tert-butylperoxyisopropyl)benzene, or combinations thereof.

[0069] The polymerization inhibitor applicable to the present invention has the effect of inhibiting the polymerization reaction. Without special indication, its specific examples are not particularly limited and may include various molecular type polymerization inhibitors, stable free radical type polymerization inhibitors known in the art, or combinations thereof. For example, the molecular type polymerization inhibitors applicable to the present invention include but are not limited to phenolic compounds, quinone compounds, aromatic amine compounds, aromatic nitro compounds, sulfur-containing compounds, variable valence metal chlorides, or combinations thereof. More specifically, the molecular type polymerization inhibitors applicable to the present invention include but are not limited to phenol, hydroquinone, 4-tert-butylcatechol, benzoquinone, chloroquinone, 1,4-naphthoquinone, trimethylquinone, aniline, nitrobenzene, Na2S, FeCl3, CuCl2, or combinations thereof. For example, the stable free radical type polymerization inhibitors applicable to the present invention include but are not limited to 1,1-diphenyl-2-trinitrophenylhydrazine (DPPH), triphenylmethyl radical, or combinations thereof.

[0070] The main function of adding a solvent to the present invention is to dissolve each component in the resin composition, change the solid content of the resin composition, and adjust the viscosity of the resin composition. For example, the solvent may include, but is not limited to, solvents such as methanol, ethanol, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone (also known as butanone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, propylene glycol methyl ether, anisole, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, or a mixed solvent thereof. The amount of the foregoing solvent is not particularly limited, and the addition amount of the solvent can be adjusted according to the viscosity required by the resin composition.

[0071] Unless otherwise specified, the inorganic filler applicable to the present invention may be any one or more inorganic fillers applicable to the production of resin films, prepregs, laminates, or printed circuit boards. Specific examples include, but are not limited to: silica (fused, non-fused, porous, or hollow), alumina, aluminum hydroxide, magnesia, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, barium titanate, lead titanate, strontium titanate, calcium titanate, magnesium titanate, barium zirconate, lead zirconate, magnesium zirconate, lead zirconate titanate, zinc molybdate, calcium molybdate, magnesium molybdate, ammonium molybdate, zinc molybdate-modified talc, zinc oxide, zirconia, mica, boehmite (AlOOH), calcined talc, talc, silicon nitride, or calcined kaolin. In addition, the inorganic filler may be spherical, fibrous, plate-like, granular, flaky, or whisker-like, and may be selectively pretreated with a silane coupling agent as needed.

[0072] Unless otherwise specified, the silane coupling agent applicable to the present invention may include silane compounds (silane, such as, but not limited to, siloxane compounds), and can be further classified into amino silane compounds, epoxide silane compounds, vinyl silane compounds, ester group silane compounds, hydroxyl silane compounds, isocyanate group silane compounds, methacryloxy silane compounds, and acryloxy silane compounds according to the type of functional group. The amount of the foregoing silane coupling agent is not particularly limited, and the addition amount of the silane coupling agent can be adjusted according to the dispersibility of the inorganic filler in the resin composition.

[0073] Unless otherwise specified, the colorant applicable to the present invention may include, but is not limited to, dyes or pigments.

[0074] The main function of adding a toughening agent in the present invention is to improve the toughness of the resin composition. Unless otherwise specified, the toughening agent applicable to the present invention may include, but is not limited to, carboxyl-terminated butadieneacrylonitrile rubber (CTBN) and other rubbers.

[0075] In one embodiment, the article of the resin composition containing the maleimide prepolymer resin of the present invention includes: a resin film, a prepreg, a laminate, or a printed circuit board.

[0076] For example, the resin composition described in the present invention can be made into a resin film.

[0077] For example, in one embodiment, the resin film of the present invention is formed by baking and heating the resin composition to a semi-cured state. 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, and then heated and baked at an appropriate heating temperature to a semi-cured state to form a resin film. Another example is that the resin compositions of various embodiments of the present invention can be respectively coated on a copper foil to make the resin composition evenly adhere, and then heated and baked at an appropriate temperature to a semi-cured state to obtain a resin film. Here, the resin film coated on the copper foil can also be called a copper foil with adhesive.

[0078] For example, the resin composition described in the present invention can be made into a prepreg.

[0079] For example, in one embodiment, the prepreg of the present invention has a reinforcing material and a layer disposed on the reinforcing material, and the layer 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 prepreg is, for example, between 130°C and 150°C. The reinforcing material can be a fiber material or a non-fiber material, and the form of the reinforcing material can be any one of woven fabric and non-woven fabric, and the woven fabric preferably includes a glass fiber cloth. The type of the glass fiber cloth is not particularly limited and can be a 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 yarns and rovings, etc., and the forms can include fibrillated or non-fibrillated. The aforementioned non-woven fabric preferably includes a liquid crystal resin non-woven fabric, such as a polyester non-woven fabric, a polyurethane non-woven fabric, etc., and is not limited thereto. The aforementioned woven fabric can also include a liquid crystal resin woven fabric, such as a polyester woven fabric or a polyurethane woven fabric, etc., and is not limited thereto. This reinforcing material can increase the mechanical strength of the prepreg. In a preferred embodiment, the reinforcing material can also be selectively pretreated via a silane coupling agent. After the prepreg is subsequently heated for curing (C-stage), an insulating layer is formed.

[0080] For example, in one embodiment, the resin compositions can be uniformly mixed respectively to form a varnish, the varnish is placed in an impregnation tank, and then the glass fiber cloth is immersed in the impregnation tank so that the resin composition adheres to the glass fiber cloth, and then it is heated and baked at an appropriate temperature to the semi-cured state to obtain the prepreg.

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

[0082] For example, in one embodiment, the laminate of the present invention includes at least two metal foils and at least one insulating layer, the insulating layer is disposed between the two metal foils, and the insulating layer can be cured from the aforementioned resin composition under high temperature and high pressure (C-stage). The applicable curing temperature is, for example, between 190°C and 210°C, preferably between 195°C and 205°C, the curing time is 120 minutes to 180 minutes, preferably 150 minutes to 160 minutes, and the applicable pressure is between 400 psi and 600 psi, preferably 500 psi. The aforementioned insulating layer can be obtained by curing the aforementioned prepreg or resin film. The material of the aforementioned metal foil can be copper, aluminum, nickel, platinum, silver, gold or their alloys, such as copper foil. In a preferred embodiment, the laminate is a copper foil substrate (also known as a copper clad laminate).

[0083] For example, in one embodiment, the aforementioned laminate can be further processed into a printed circuit board via circuit processing.

[0084] For example, in one embodiment, one way to fabricate 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 ounce HVLP (hyper very low profile) copper foil (such as product EM-891, available from Taiguang Electronic Materials Co., Ltd.). After drilling, electroplating is performed to form electrical conduction between the upper copper foil and the lower copper foil. Then, the upper copper foil and the lower copper foil are etched to form the inner layer circuit. Next, the inner layer circuit is subjected to brownification and roughening treatment to form an uneven structure on the surface to increase 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 210 °C for 120 minutes to 180 minutes to cure the insulating layer material of the prepreg. Next, various circuit board manufacturing processes known in the art such as blackening treatment, drilling, and copper plating are performed on the copper foil on the outermost surface to obtain a printed circuit board.

[0085] In one embodiment, for the product of the resin composition containing maleimide prepolymer resin of the present invention, measured according to the method described in IPC-TM-650 2.4.24.4, the glass transition temperature variation is ≤ 3 °C, for example, between 0 °C and 3 °C.

[0086] In one embodiment, for the product of the resin composition containing maleimide prepolymer resin of the present invention, measured according to the method described in IPC-TM-650 2.4.8, the tensile strength against copper foil is ≥ 3.2 lb / in, for example, between 3.2 lb / in and 3.5 lb / in.

[0087] In one embodiment, for the product of the resin composition containing maleimide prepolymer resin of the present invention, measured according to the method described in IPC-TM-650 2.4.24.5, the Z-axis thermal expansion rate is ≤ 2.5%, for example, between 2.3% and 2.5%.

[0088] In one embodiment, for the product of the resin composition containing maleimide prepolymer resin of the present invention, measured according to the method described in IPC-TM-650 2.4.24.5, the Z-axis thermal expansion coefficient is ≤ 45 ppm / °C, for example, between 35 ppm / °C and 45 ppm / °C.

[0089] In one embodiment, for the product of the resin composition containing maleimide prepolymer resin of the present invention, through visual inspection of the appearance, there is no dry plate and no texture phenomenon, and its appearance is normal.

[0090] The chemical raw materials used in the preparation examples of the maleimide prepolymer resin, the examples and comparative examples of the resin composition containing maleimide prepolymer resin and their products of the present invention are as follows:

[0091] SA9000: Polymethacrylate polyphenylene ether resin, purchased from Sabic.

[0092] OPE-2st-1200: Vinylbenzyl biphenyl polyphenylene ether resin with a weight average molecular weight (Mw) of 1200, purchased from Mitsubishi Gas Chemical.

[0093] OPE-2st-2200: Vinylbenzyl biphenyl polyphenylene ether resin with a weight average molecular weight (Mw) of 2200, purchased from Mitsubishi Gas Chemical.

[0094] BVPE: Bis(vinylphenyl)ethane, purchased from Linchuan Chemical Industry.

[0095] BMI-70: Bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, purchased from K.I Chemical.

[0096] BMI-80: Bisphenol A diphenyl ether bismaleimide, purchased from K.I Chemical.

[0097] BMI-2300: Polyphenylmethane maleimide, purchased from Daido Kasei Co., Ltd.

[0098] BMI-1000: 4,4'-Diphenylmethane bismaleimide, purchased from Daido Kasei Co., Ltd.

[0099] BMI-3000: Maleimide resin of the structure of formula (1), purchased from Designer Molecules, Inc.

[0100] BMI-1700: Maleimide resin of the structure of formula (2), purchased from Designer Molecules, Inc.

[0101] BMI-2500: Maleimide resin of the structure of formula (3), purchased from Designer Molecules, Inc.

[0102] BMI-1500: Maleimide resin of the structure of formula (4), purchased from Designer Molecules, Inc.

[0103] TAIC: Triallyl isocyanurate, commercially available.

[0104] SC-2050SVJ: Spherical silica, purchased from Admatechs Co., Ltd.

[0105] 25B: 2,5-Dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, purchased from NOF Corporation.

[0106] Mixed solvent 1: A mixed solvent of toluene and methyl ethyl ketone (MEK), where the weight ratio of toluene to methyl ethyl ketone is 4:1, prepared by self-formulation.

[0107] Mixed solvent 2: A mixed solvent of anisole and methyl ethyl ketone (MEK), where the weight ratio of anisole to methyl ethyl ketone is 4:1, prepared by self-formulation.

[0108] The preparation examples of maleimide prepolymer resins numbered 1 to 14 of the present invention are shown in Table 1 as follows:

[0109] Table 1 Preparation examples of maleimide prepolymer resins numbered 1 to 14 of the present invention

[0110]

[0111]

[0112] Taking the maleimide prepolymer resin numbered 1 as an example, the weight ratio of BMI-70 to BMI-3000 is 1:5, and the preparation method is as follows: After dissolving 10 grams of BMI-70 in 40 grams of methyl ethyl ketone, 150 grams of toluene is added and stirred continuously, then 50 grams of BMI-3000 and 0.3 grams of 25B are added, and the reaction is carried out at 130 °C for 60 minutes to obtain the maleimide prepolymer resin numbered 1, with a solid content of 60%. The conversion rate of the maleimide prepolymer resin numbered 1 is between 10% and 90%. For the preparation methods of the maleimide prepolymer resins numbered 2 to 14, please also refer to Table 1. Among them, the maleimide prepolymer resins numbered 1 to 10 are used in the examples for preparing resin compositions and their products containing maleimide prepolymer resins, while the maleimide prepolymer resins numbered 1, 11 to 14 are used in the comparative examples of the present invention. The conversion rates of the maleimide prepolymer resins numbered 2 to 10 are also between 10% and 90%.

[0113] The components (by weight) of Examples E1 to E16 of the resin composition containing maleimide prepolymer resin of the present invention are shown in Table 2 as follows:

[0114] Table 2 Components (by weight) of Examples E1 to E16 of the resin composition containing maleimide prepolymer resin of the present invention

[0115]

[0116]

[0117] Taking Example E1 of the resin composition containing maleimide prepolymer resin as an example, its components are as follows: 42 parts by weight of the maleimide prepolymer resin numbered 1 in Table 1, 100 parts by weight of the vinyl-containing polyphenylene ether resin (which contains 20 parts by weight of SA9000, 65 parts by weight of OPE-2st-2200, and 15 parts by weight of OPE-2st-1200), 40 parts by weight of bis(vinylphenyl)ethane (BVPE), 8 parts by weight of crosslinking agent (TAIC), 70 parts by weight of inorganic filler (SC-2050SVJ), 0.02 parts by weight of curing accelerator (25B), and 150 parts by weight of mixed solvent 1 (the weight ratio of toluene to methyl ethyl ketone is 4:1). The composition components of the remaining Examples E2 to E16 have been clearly and distinctly disclosed in Table 2. Furthermore, Examples E1 to E16 were prepared using the maleimide prepolymer resins numbered 1 to 10 in Table 1.

[0118] The components (parts by weight) of Comparative Examples C1 to C14 of the present invention are shown in Table 3 as follows:

[0119] Table 3 Components (parts by weight) of Comparative Examples C1 to C14 of the present invention

[0120]

[0121] Taking Comparative Example C1 as an example, the components of its resin composition are as follows: 42 parts by weight of maleimide resin (containing 7 parts by weight of BMI-70 and 35 parts by weight of BMI-3000), 100 parts by weight of the vinyl-containing polyphenylene ether resin (containing 20 parts by weight of SA9000, 65 parts by weight of OPE-2st-2200, and 15 parts by weight of OPE-2st-1200), 40 parts by weight of bis(vinylphenyl)ethane (BVPE), 8 parts by weight of crosslinking agent (TAIC), 70 parts by weight of inorganic filler (SC-2050SVJ), 0.02 parts by weight of curing accelerator (25B), and 150 parts by weight of mixed solvent 1 (the weight ratio of toluene to methyl ethyl ketone is 4:1). The composition components of the remaining Examples C2 to C14 have been clearly and distinctly disclosed in Table 3.

[0122] The preparation methods of the products of the resin compositions containing maleimide prepolymer resin of the present invention, the product examples or comparative example products are as described below:

[0123] 1. Prepreg:

[0124] In the resin compositions of Examples E1 to E16 (listed in Table 2) containing maleimide prepolymer resin or the resin compositions of Comparative Examples C1 to C14 (listed in Table 3), after uniformly mixing the respective chemical reagents in the resin composition to form a varnish, the varnish was placed in an impregnation tank, and then a glass fiber cloth (for example, an L-glass fiber fabric with a specification of 1078, purchased from Asahi Corporation) was immersed in the above impregnation tank so that the resin composition adhered to the glass fiber cloth, and it was heated to a semi-cured state (B-Stage) at 130 °C to 150 °C to obtain a semi-cured sheet with a resin content of approximately 70%.

[0125] 2. Copper-clad laminate composed of six semi-cured sheets:

[0126] Prepare 2 sheets of 0.5-ounce HVLP (hyper very low profile) copper foil and six of the above semi-cured sheets, stack them in the order of copper foil, six semi-cured sheets, and copper foil, and laminate them under vacuum at a lamination pressure of 400 psi to 600 psi and a temperature of 190 °C to 210 °C for 120 minutes to 180 minutes to obtain a copper-clad laminate (composed of six semi-cured sheets laminated). The six mutually laminated semi-cured sheets are cured to form an insulating layer between the two copper foils, and the resin content of the insulating layer is approximately 70%.

[0127] 3. Copper-clad laminate composed of eight semi-cured sheets:

[0128] Prepare 2 sheets of 0.5-ounce thick HVLP (hyper very low profile) copper foil and eight of the above semi-cured sheets, stack them in the order of copper foil, eight semi-cured sheets, and copper foil, and laminate them under vacuum at a lamination pressure of 400 psi to 600 psi and a temperature of 190 °C to 210 °C for 120 minutes to 180 minutes to obtain a copper-clad laminate (composed of eight semi-cured sheets laminated). The eight mutually laminated semi-cured sheets are cured to form an insulating layer between the two copper foils, and the resin content of the insulating layer is approximately 70%.

[0129] 4. Copper-free laminate (composed of six semi-cured sheets laminated, used for measurement of the product of the present invention):

[0130] Etch the copper foils on both sides of the above copper-clad laminate composed of six semi-cured sheets to obtain a copper-free laminate (composed of six semi-cured sheets laminated).

[0131] 5. Copper-free laminate (composed of eight semi-cured sheets laminated, used for measurement of the product of the present invention):

[0132] Etch the copper foils on both sides of the above copper-clad laminate composed of eight semi-cured sheets to obtain a copper-free laminate (composed of eight semi-cured sheets laminated).

[0133] The testing methods for the products of the resin composition embodiments containing maleimide prepolymer resin or the products of the comparative examples are as described below:

[0134] 1. Glass transition temperature variation:

[0135] Prepare a copper-free substrate (laminated from six prepregs). Take two samples at adjacent positions on the copper-free substrate (the distance between the two is about 1 to 2 cm). Cut each sample into a rectangular sample with a width of 1.2 cm and a length of 3.5 cm. Using dynamic mechanical analysis (DMA), refer to the method described in IPC-TM-650 2.4.24.4 to measure the two samples to be tested respectively. Measure the glass transition temperature (unit: °C) of one sample to be tested at room temperature (about 25°C) to obtain Tg1, and measure the glass transition temperature (unit: °C) of the other sample to be tested after placing it in an environment of 85°C and relative humidity (RH) of 85% for 168 hours to obtain Tg2. Generally, the error range of measuring Tg1 and Tg2 by the DMA instrument is about ±1°C. The glass transition temperature variation (ΔTg) is defined as the difference between Tg1 and Tg2. For example, ΔTg = Tg1 - Tg2. The smaller the glass transition temperature variation, the better. Generally, when the glass transition temperature variation ≥ 3°C, there is a significant difference.

[0136] 2. Copper foil peeling strength (0.5 ounce) (Hoz)

[0137] Prepare a copper-free substrate (laminated from six prepregs). Cut it into a rectangular sample with a width of 24 mm and a length of 80 mm, and etch the surface copper foil, leaving only a long strip of copper foil with a width of 3.18 mm and a length greater than 60 mm. Use a universal tensile strength testing machine to measure at room temperature (about 25°C) according to the method described in IPC-TM-650 2.4.8 to measure the copper foil peeling strength (Hoz P / S) of 0.5 ounce (half-ounce), and the unit is lb / in. In the art, the higher the copper foil peeling strength, the better. Generally, when the copper foil peeling strength is (0.5 ounce) and the resin content is about 70%, when the difference ≥ 0.3 lb / in, there is a significant difference.

[0138] 3. Percentage of thermal expansion (PTE)

[0139] In the measurement of the thermal expansion rate (measuring in the Z-axis direction), a copper-free substrate (formed by laminating eight prepregs) is selected as the sample to be tested for thermal mechanical analysis (TMA). The sample is cut into a square with a width of 7 mm and a length of 7 mm. The sample is heated at a heating rate of 10 °C per minute, and in the temperature range from 35 °C to 270 °C, the Z-axis thermal expansion rate (unit: %) of each sample to be tested is measured in the temperature range from 50 °C to 260 °C according to the method described in IPC-TM-650 2.4.24.5. The lower the thermal expansion rate, the better. Generally, when the difference in the Z-axis thermal expansion rate ≥ 0.3%, it is a significant difference.

[0140] 4. Coefficient of thermal expansion (CTE)

[0141] In the measurement of the coefficient of thermal expansion (measuring in the Z-axis direction), a copper-free substrate (formed by laminating eight prepregs) is selected as the sample to be tested. The sample is cut into a square with a width of 7 mm and a length of 7 mm. The sample is heated at a heating rate of 10 °C per minute, and within the temperature range from 35 °C to 270 °C, using a thermal mechanical analyzer (TMA), the Z-axis coefficient of thermal expansion (α1) of each sample to be tested is measured in the temperature range from 50 °C to 110 °C according to the method described in IPC-TM-650 2.4.24.5. The unit is ppm / °C. The lower the coefficient of thermal expansion, the better. Generally, when the difference in the Z-axis coefficient of thermal expansion ≥ 5 ppm / °C, it is a significant difference.

[0142] 5. Substrate appearance

[0143] A copper-free substrate (formed by laminating eight prepregs) is selected, and the surface appearance of its insulating layer is visually observed by personnel to check whether there are any exposed dry plates or textures. If there are no exposed dry plates or textures, it means the appearance of the substrate is normal (as shown in Figure 1 ), and "OK" is marked in the test result. If there are exposed dry plates and textures (as shown in Figure 2 ), it is marked as "NG".

[0144] According to the above test methods, the test results of Examples E1 to E16 and Comparative Examples C1 to C14 of the resin composition containing maleimide prepolymer resin of the present invention applied to products are shown in Table 4 and Table 5 respectively:

[0145] Table 4 Test results of Examples E1 to E16 of the resin composition containing maleimide prepolymer resin of the present invention applied to products

[0146] Characteristic Unit E1 E2 E3 E4 E5 E6 E7 E8 E9 E10 E11 E12 E13 E14 E15 E16 Tg1 ℃ 200 193 196 202 203 201 201 203 201 197 203 199 201 202 201 201 Tg2 ℃ 200 192 194 200 201 200 200 202 201 196 201 197 200 202 200 200 △Tg ℃ 0 1 2 2 2 1 1 1 0 1 2 2 1 0 1 1 Hoz P / S lb / in 3.3 3.4 3.2 3.3 3.2 3.3 3.3 3.2 3.5 3.3 3.2 3.2 3.2 3.3 3.3 3.4 Z-PTE ％ 2.4 2.4 2.5 2.4 2.4 2.4 2.4 2.4 2.3 2.5 2.4 2.4 2.4 2.3 2.4 2.5 Z-CTE ppm / ℃ 40 38 45 38 37 39 42 35 35 43 41 39 38 39 40 41 Substrate Appearance OK OK OK OK OK OK OK OK OK OK OK OK OK OK OK OK

[0147] Table 5 Test Results of Comparative Examples C1 to C14 of the Present Invention Applied to Articles

[0148] Characteristic Unit C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 Tg1 ℃ 199 193 196 208 198 201 198 204 175 214 224 193 188 201 Tg2 ℃ 189 186 194 201 192 190 186 192 168 212 210 186 178 192 △Tg ℃ 10 7 2 7 6 11 12 12 7 2 14 7 10 9 Hoz P / S lb / in 2.4 3.5 2.8 2.8 3.4 2.2 2.3 2.2 3.5 2.6 2.1 3.3 2.3 2.3 Z-PTE ％ 3.1 2.4 3.3 2.5 2.9 2.8 2.8 2.8 2.7 2.2 2.2 2.9 2.8 2.9 Z-CTE ppm / ℃ 57 40 62 44 54 52 54 56 50 35 37 56 53 58 Substrate Appearance NG OK OK NG OK NG NG NG OK OK NG OK NG NG

[0149] In Table 4, for Examples E1 to E16 of the resin composition containing the maleimide prepolymer resin of the present invention applied to articles, it is possible to simultaneously achieve a glass transition temperature variation of ≤3°C, a tensile strength against copper foil of ≥3.2 lb / in, a thermal expansion rate of ≤2.5%, a thermal expansion coefficient of ≤45 ppm / °C, and no phenomenon of dry plate and texture exposure on the surface appearance.

[0150] Compared with Examples E1 to E16, if the maleimide prepolymer resin of the present invention is not used in the resin composition, such as Comparative Examples C1, C6 to C8, C13, C14, or if the maleimide prepolymer resin of the present invention is used, but its addition amount falls outside the range of 30 parts by weight to 60 parts by weight, such as Comparative Examples C2, C3, or if a maleimide prepolymer resin obtained by pre-polymerization reaction of an aromatic maleimide resin and a long-chain maleimide resin other than the present invention is used, such as Comparative Examples C4, C5, at least one of the properties such as glass transition temperature variation, tensile strength against copper foil, thermal expansion rate, and thermal expansion coefficient cannot meet the requirements.

[0151] Compared with Examples E1 to E16, if the addition amount of bis(vinylphenyl)ethane in the resin composition falls outside the range of 35 parts by weight to 45 parts by weight, such as Comparative Examples C9, C10, at least one of the properties such as glass transition temperature variation, tensile strength against copper foil, and thermal expansion coefficient cannot meet the requirements.

[0152] Compared with Examples E1 to E16, if the weight ratio of the aromatic maleimide resin and the long-chain maleimide resin in the maleimide prepolymer resin of the resin composition falls outside the range of 1:3 to 1:5, such as Comparative Examples C11, C12, at least one of the properties such as glass transition temperature variation, tensile strength against copper foil, thermal expansion rate, thermal expansion coefficient, and surface appearance also cannot meet the requirements.

[0153] The resin composition containing the maleimide prepolymer resin of the present invention and its articles are prepared by first subjecting an aromatic maleimide resin and a long-chain maleimide resin to a pre-polymerization reaction to form a maleimide prepolymer resin, and then, with an appropriate part by weight, combining it with a vinylpolyphenylene ether resin and bis(vinylphenyl)ethane to form the resin composition containing the maleimide prepolymer resin and its articles, which can improve at least one of the properties of glass transition temperature variation, tensile strength against copper foil, thermal expansion rate, thermal expansion coefficient, and surface appearance.

[0154] In addition, although at least one exemplary embodiment or comparative example has been presented in the foregoing embodiments, it should be understood that numerous variations of the present invention are possible. It should also be understood that the embodiments described herein are not intended to limit in any way the scope, use, or configuration of the claimed subject matter. On the contrary, the foregoing embodiments will provide those of ordinary skill in the art with a convenient guide for implementing one or more of the embodiments. Furthermore, various changes can be made to the functions and arrangements of the components without departing from the scope defined by the patent application scope, and the patent application scope includes known equivalents and all foreseeable equivalents at the time of filing this patent application.

Claims

1. A resin composition containing a maleimide prepolymer resin, characterized in that, Comprising: 100 parts by weight of a vinyl-containing polyphenylene ether resin; 35 to 45 parts by weight of bis(vinylphenyl)ethane; and 30 to 60 parts by weight of a maleimide prepolymer resin; Wherein the maleimide prepolymer resin is a prepolymer obtained by a prepolymerization reaction of an aromatic maleimide resin and a long-chain maleimide resin, and the long-chain maleimide resin contains a structure represented by any one of Formula (1) to Formula (4); Formula (1) Formula (2) Formula (3) Formula (4) Wherein, in Formula (1) and Formula (2), n is an integer from 1 to 10 respectively; in Formula (3), m1 is an integer from 1 to 5, and m2 is an integer from 1 to 5; in Formula (4), n is an integer from 1 to 3; and the weight ratio of the aromatic maleimide resin to the long-chain maleimide resin is 1:3 to 1:

5.

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

3. The resin composition containing maleimide prepolymer resin according to claim 1, wherein The aromatic maleimide resin includes bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bisphenol A diphenyl ether bismaleimide, polyphenylmethane maleimide, and 4,4'-diphenylmethane bismaleimide, or a combination thereof.

4. The resin composition containing the maleimide prepolymer resin according to claim 1, further comprising a flame retardant, a crosslinking agent, an inorganic filler, a curing accelerator, a solvent, a polymerization inhibitor, a silane coupling agent, a dye, a toughening agent, or a combination thereof.

5. An article comprising a resin composition containing a maleimide prepolymer resin as described in claim 1, characterized in that, Comprising: a resin film, a prepreg, a laminate, or a printed circuit board.

6. The article according to claim 5, characterized in that, Measured according to the method described in IPC-TM-650 2.4.24.4, and the variation in glass transition temperature ≤ 3°C.

7. The article according to claim 5, characterized in that, Measured according to the method described in IPC-TM-650 2.4.8, and the tensile strength against copper foil ≥ 3.2 lb / in.

8. The article according to claim 5, characterized in that, Measured according to the method described in IPC-TM-650 2.4.24.5, and the Z-axis thermal expansion rate ≤ 2.5%.

9. The article according to claim 5, characterized in that, Measured according to the method described in IPC-TM-650 2.4.24.5, and the Z-axis thermal expansion coefficient ≤ 45 ppm / °C.

10. The article according to claim 5, characterized in that, Tested by visual inspection of the appearance, there is no dry plate and no texture phenomenon, and the appearance is normal.

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