Resin composition and article thereof

Abstract

A resin composition includes the following components or prepolymers thereof: (A) 100 parts by weight of a polyphenylene ether resin containing an unsaturated carbon-carbon double bond; and (B) 10 to 50 parts by weight of a compound of formula (1) having a pH of 10 or less. In formula (1), n is an integer of 3 to 6, each of Y and Z is independently selected from the group consisting of o-vinylphenoxy and phenoxy, and each of Y and Z is not simultaneously phenoxy. The prepolymer is obtained by pre-polymerization of a mixture including at least the (A) component and the (B) component. In addition, an article made from the resin composition is disclosed. The article includes a prepreg, a resin film, a laminate, or a printed circuit board, and can be improved in one or more of the following: adhesive uniformity, dielectric loss tangent thermal change rate, glass transition temperature, Z-axis thermal expansion rate, peel strength, and moisture absorption heat resistance.

Description

Technical Field

[0001] This invention relates to a resin composition and articles thereof, and particularly to a resin composition that can be used to prepare prepregs, resin films, laminates or printed circuit boards. Background Technology

[0002] With the rapid development of mobile communication technology, resin materials suitable for high-frequency, high-speed information transmission have become a major development direction for substrates. Technical requirements include the ability of substrate materials to maintain low dielectric loss under high temperature variations, ensuring the substrate can still operate normally and effectively in high-temperature environments. Therefore, developing a material suitable for such high-performance substrates is a current focus of industry efforts. Summary of the Invention

[0003] In view of the problems encountered in the prior art, especially the inability of existing resin materials to meet one or more of the above-mentioned characteristic requirements, the main objective of the present invention is to provide a resin composition that achieves at least one or more good characteristics such as high filler uniformity, low dielectric loss thermal change rate, high glass transition temperature, low Z-axis thermal expansion coefficient, high peel strength and high moisture absorption and heat resistance.

[0004] To achieve the above objectives, the present invention discloses a resin composition comprising the following components or their prepolymers:

[0005] (A) 100 parts by weight of a polyphenylene ether resin containing unsaturated carbon-carbon double bonds; and

[0006] (B) 10 to 50 parts by weight of the compound of formula (1) having a pH value of less than 10;

[0007]

[0008] In formula (1), n ​​is an integer from 3 to 6, each Y and Z is independently selected from o-vinylphenoxy and phenoxy, and each Y and Z is not simultaneously phenoxy;

[0009] The prepolymer is obtained by a prepolymerization reaction of a mixture, and the mixture includes at least component (A) and component (B).

[0010] For example, in one embodiment, the pH value of the compound of formula (1) is 5 to 10.

[0011] For example, in one embodiment, the aforementioned resin composition further comprises 0.001 parts by weight to 0.5 parts by weight of the compound of formula (2), the compound of formula (3), the compound of formula (4), or a combination thereof:

[0012]

[0013] Wherein, X1 is an oxygen free radical or a hydroxyl group; R2 to R5 are each independently a hydrogen atom or a C1 to C5 alkyl group, and R2 to R5 are not simultaneously hydrogen atoms; R1 is a hydrogen atom, a C1 to C5 alkyl group, an amino group, a hydroxyl group, a ketone group, or a carboxyl group;

[0014] Wherein, X2 is an oxygen free radical or a hydroxyl group; R7 to R 10 Each is independently a hydrogen atom or a C1 to C5 alkyl group, and R7 to R 10 Not both are hydrogen atoms; R6 and R 11 Each group is independently a hydrogen atom, a C1 to C5 alkyl, amino, hydroxyl, ketone, or carboxyl group, or an R6 and R group. 11 They collectively define a benzene ring structure;

[0015] Among them, X3 is an oxygen free radical or a hydroxyl group; R 12 To R 23 Each is independently a hydrogen atom or a C1 to C5 alkyl group, and R 12 To R 23 They are not both hydrogen atoms.

[0016] For example, in one embodiment, the compound of formula (2) includes compounds having any of the structures shown in formulas (5) to (9) or combinations thereof:

[0017]

[0018]

[0019] For example, in one embodiment, the compound of formula (3) includes compounds having any of the structures shown in formulas (10) to (13) or combinations thereof:

[0020]

[0021]

[0022] For example, in one embodiment, the compound of formula (4) includes a compound having any of the structures shown in formulas (14) to (15) or a combination thereof:

[0023]

[0024]

[0025] For example, in one embodiment, the prepolymer is formed by a prepolymerization reaction of component (A) and component (B), and the conversion rate of the prepolymerization reaction is between 10% and 99%.

[0026] For example, in one embodiment, the aforementioned resin composition further comprises 1,2-bis(vinylphenyl)ethane, divinylbenzyl ether, divinylbenzene, divinylnaphthalene, divinylbiphenyl, tert-butylstyrene, triallyl isocyanurate, triallyl cyanurate, 1,2,4-trivinylcyclohexane, diallyl bisphenol A, styrene, butadiene, decanadiene, octadiene, vinylcarbazole, acrylate, or combinations thereof.

[0027] For example, in one embodiment, the aforementioned resin composition further comprises benzoxazine resin, epoxy resin, polyester resin, phenolic resin, amine curing agent, polyamide, polyimide, polyolefin, styrene-maleic anhydride, maleimide resin, cyanate ester, maleimide triazine resin, or a combination thereof.

[0028] For example, in one embodiment, the aforementioned resin composition further includes a flame retardant, a curing accelerator, an inorganic filler, a surface treatment agent, a dye, a solvent, a toughening agent, or a combination thereof.

[0029] On the other hand, the present invention provides an article made from the aforementioned resin composition, comprising a prepreg, a resin film, a laminate, or a printed circuit board.

[0030] For example, in one embodiment, the aforementioned article has one, more, or all of the following characteristics:

[0031] There are no patterns on the copper-free surface of the inner layer circuit board;

[0032] After standing at a constant temperature of 188℃ for 48 hours, the dielectric loss thermal change rate calculated by measuring the dielectric loss at a frequency of 10GHz according to the method described in JIS C2565 is less than or equal to 30%.

[0033] The glass transition temperature measured according to the method described in IPC-TM-650 2.4.24.4 is greater than or equal to 226°C;

[0034] The Z-axis thermal expansion coefficient measured according to the method described in IPC-TM-650 2.4.24.5 is less than or equal to 1.82%;

[0035] The peel strength measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 4.5 lb / in; and

[0036] The moisture absorption and heat resistance test performed according to the methods described in IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23 did not result in plate bursting. Attached Figure Description

[0037] Figure 1This is a schematic diagram of the substrate pattern.

[0038] Figure 2 This is a schematic diagram showing the appearance of a normal substrate. Detailed Implementation

[0039] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in the event of any conflict, the definitions in this specification shall prevail.

[0040] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.

[0041] The present invention uses the terms "a," "an," "a," or similar expressions to describe the components and technical features described herein. Such descriptions are merely for convenience and to provide a general meaning regarding the scope of the invention. Therefore, such descriptions should be understood to include one or at least one, and the singular includes the plural, unless clearly otherwise indicated.

[0042] In this article, "or a combination thereof" means "or any combination thereof", and "any one", "any kind", "any one" means "any one", "any kind", "any one".

[0043] In this document, the terms “comprising,” “including,” “having,” “containing,” or any other similar terms are open-ended transitional phrases, intended to encompass non-exclusive inclusions. For example, a composition or article thereof containing multiple elements is not limited to the elements listed herein, but may also include other elements not explicitly listed but typically inherent to the composition or article thereof. Furthermore, unless explicitly stated to the contrary, the term “or” is an inclusive “or,” not an exclusive “or.” For example, the condition “A or B” is satisfied in any of the following cases: 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); or both A and B are true (or exist). Furthermore, in this article, the interpretation of the terms “contains,” “includes,” “has,” and “contains” should be regarded as having been specifically disclosed and simultaneously covering closed conjunctions such as “composed of,” “composed of,” and “remaining as,” as well as conjunctions such as “essentially composed of,” “mainly composed of,” “mainly composed of,” “basically containing,” “basically composed of,” “basically composed of,” and “essentially containing.”

[0044] In this document, all features or conditions defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible subranges and individual numerical values ​​(including integers and fractions) within the ranges, especially integer values. For example, range descriptions such as "1.0 to 8.0", "between 1.0 and 8.0", or "between 1.0 and 8.0" should be considered as specifically disclosing all subranges 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 as covering endpoint values, especially subranges defined by integer values, and should be considered as specifically disclosing individual numerical values ​​within the ranges such as 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, etc. Unless otherwise specified, the foregoing interpretation applies to all contents of this invention, whether broad or narrow.

[0045] If a quantity, concentration, or other numerical value or parameter is expressed as a range, preferred range (or better range), or a series of upper and lower limits, it should be understood that this document has specifically disclosed all ranges consisting of any pair of upper or preferred values ​​(or better values) and lower or preferred values ​​(or better values) of that range, regardless of whether such ranges are disclosed separately. Furthermore, when a range of numerical values ​​is mentioned herein, unless otherwise stated, the range should include its endpoints and all integers and fractions within the range.

[0046] In this document, numerical values ​​are to be understood as having a precision with significant digits, provided that the purpose of the invention can be achieved. For example, the number 40.0 should be understood to cover the range of 39.50 to 40.49.

[0047] In this document, when Markush groups or alternative terms are used to describe features or examples of the invention, those skilled in the art should understand that subgroups or any individual elements within a Markush group or option list can also be used to describe the invention. For example, if X is described as "selected from the group consisting of X1, X2, and X3," it also indicates that the claim that X is X1 and the claim that X is X1 and / or X2 and / or X3 have been fully described. Furthermore, when Markush groups or alternative terms are used to describe features or examples of the invention, those skilled in the art should understand that any combination of subgroups or individual members within a Markush group or option list can also be used to describe the 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 indicates that the claim that X is X1 and / or X2 and / or X3 and Y is Y1 and / or Y2 and / or Y3 has been fully described.

[0048] Unless otherwise specified, in this invention, 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 macromolecules. The term "compound" in this document is not limited to a single chemical substance, but can also be interpreted as a class of chemical substances having the same component or the same properties.

[0049] Unless otherwise specified, in this invention, a polymer refers to the product formed by the polymerization reaction of monomers, often comprising an aggregate of many high molecules, each of which is composed of many simple structural units repeatedly linked by covalent bonds. The monomer is the compound that synthesizes the polymer. Polymers can include homopolymers, copolymers, prepolymers, etc., but are not limited to these. A homopolymer is a polymer polymerized from a single monomer. Copolymers include random copolymers (structures such as -AABABBBAAABBA-), alternating copolymers (structures such as -ABABABAB-), graft copolymers (structures such as -AA(A-BBBB)AA(A-BBBB)AAA-), and block copolymers (structures such as -AAAAA-BBBBBB-AAAAA-). For example, the styrene-butadiene copolymer described in this invention should be understood to include styrene-butadiene random copolymers, styrene-butadiene alternating copolymers, styrene-butadiene graft copolymers, styrene-butadiene block copolymers, or combinations thereof. Prepolymers are polymers with lower molecular weights, falling between those of monomers and the final polymer. Prepolymers contain reactive functional groups that allow for further polymerization to yield fully cross-linked or hardened products with higher molecular weights. Polymers include, but are not limited to, oligomers. Oligomers, also known as low-molecular-weight polymers, are polymers composed of 2 to 20 repeating units, typically 2 to 5 repeating units.

[0050] For those skilled in the art, a resin composition containing compounds A, B, and C and an additive (comprising four components in total) and a resin composition containing a prepolymer formed from compounds A, B, and C and an additive (comprising two components in total) are different resin compositions. They differ significantly in their preparation methods, physicochemical properties, and the characteristics of their products. For example, the former involves mixing A, B, C, and the additive to form the resin composition, while the latter requires first prepolymerizing the mixture containing A, B, and C under appropriate conditions to form a prepolymer, which is then mixed with the additive to obtain the resin composition. For example, for those skilled in the art, the aforementioned two resin compositions have completely different compositions, and since the prepolymer formed from compounds A, B, and C functions entirely differently from the individual or combined functions of A, B, and C in the resin composition, the two resin compositions should be considered completely different chemical substances with entirely different chemical statuses. For example, for those skilled in the art, since the aforementioned two resin compositions are completely different chemical substances, their products will not have the same characteristics. For example, in a resin composition comprising a prepolymer formed from compounds A, B, and C, and a crosslinking agent, since A, B, and C have already partially reacted or transformed to form the prepolymer during the prepolymerization reaction, when the resin composition is heated at high temperature to form a semi-cured state, a partial crosslinking reaction occurs between the prepolymer and the crosslinking agent, rather than each of A, B, and C undergoing a partial crosslinking reaction with the crosslinking agent. Therefore, the products formed from the two resin compositions will be completely different and have entirely different properties.

[0051] Unless otherwise specified, in this invention, specific examples of acrylate compounds are written in the form of "(methyl)". When interpreting, it should be understood to include both cases containing methyl and cases not containing methyl. For example, cyclohexanediethanol di(methyl)acrylate should be interpreted as including cyclohexanediethanol diacrylate and cyclohexanediethanol dimethylacrylate.

[0052] Unless otherwise specified, the alkyl groups mentioned in this invention are interpreted to include their various isomers; for example, propyl should be interpreted to include n-propyl and isopropyl.

[0053] Unless otherwise specified, "resin" in this invention is a common name for a synthetic polymer. When interpreted, it can include monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and their polymers, etc., and is not limited thereto.

[0054] For example, when interpreting "containing unsaturated carbon-carbon double bonds", the following functional groups are included, but not limited to:

[0055]

[0056] In this invention, preferred examples of unsaturated carbon-carbon double bonds include, but are not limited to, vinyl, vinylidene, allyl, (meth)acryloyl, or combinations thereof.

[0057] Unless otherwise specified, in this invention, the 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 crosslinking of each resin with other resins, products after copolymerization of each resin with other resins, etc.

[0058] Unless otherwise specified, the unsaturated bond referred to in this invention refers to a reactive unsaturated bond, such as, but not limited to, an unsaturated double bond that can undergo cross-linking reactions with other functional groups, such as, but not limited to, an unsaturated carbon-carbon double bond that can undergo cross-linking reactions with other functional groups.

[0059] Unless otherwise specified, in this invention, parts by weight represent the number of parts by weight, which can be any unit of weight, such as, but not limited to, kilograms, grams, pounds, etc. For example, 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds can represent 100 kilograms of polyphenylene ether resin containing unsaturated carbon-carbon double bonds or 100 pounds of polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

[0060] It should be understood that the features disclosed in the various embodiments herein can be arbitrarily combined to form the technical solution of this application, as long as there is no contradiction in the combination of these features.

[0061] The present invention will now be described with reference to specific embodiments and examples. It should be understood that these specific embodiments and examples are merely illustrative and are not intended to limit the scope or use of the invention. The methods, reagents, and conditions used in the examples are conventional methods, reagents, and conditions in the art, unless otherwise stated.

[0062] Generally speaking, this invention mainly discloses a resin composition comprising the following components or their prepolymers:

[0063] (A) 100 parts by weight of a polyphenylene ether resin containing unsaturated carbon-carbon double bonds; and

[0064] (B) 10 to 50 parts by weight of the compound of formula (1) having a pH value of less than 10;

[0065]

[0066] In formula (1), n ​​is an integer from 3 to 6, each Y and Z is independently selected from o-vinylphenoxy and phenoxy, and each Y and Z is not simultaneously phenoxy;

[0067] The prepolymer is obtained by a prepolymerization reaction of a mixture, and the mixture includes at least component (A) and component (B).

[0068] For example, in one embodiment, the resin composition comprises 100 parts by weight of a polyphenylene ether resin containing unsaturated carbon-carbon double bonds and 10 to 50 parts by weight of a compound of formula (1) (with a pH value of less than 10). For example, instead of 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition of the present invention may comprise 10, 18, 20, 25, 30, 35, 40, 45 or 50 parts by weight of a compound of formula (1) (with a pH value of less than 10), and is not limited thereto.

[0069] For example, in another embodiment, the resin composition includes a prepolymer formed by a prepolymerization reaction of 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds and 10 to 50 parts by weight of the compound of formula (1) (with a pH value of less than 10). The prepolymer of the present invention contains residual carbon-carbon unsaturated double bonds, and the conversion rate of the reactants and the molecular weight of the prepolymer are both within a controllable range. In one embodiment, the residual carbon-carbon unsaturated double bonds in the prepolymer can react with other components (such as crosslinking agents containing unsaturated carbon-carbon double bonds in the resin composition described herein), such as polymerization or crosslinking reactions. In the present invention, the presence and content of residual carbon-carbon unsaturated double bonds in the prepolymer are controlled by controlling the conversion rate of the compound of formula (1) and the polyphenylene ether resin containing unsaturated carbon-carbon double bonds. For example, the conversion rate of the compound of formula (1) can be between 10% and 99%, preferably between 30% and 95%, 50% and 95%, 50% and 90%, or 75% and 90%. For example, when the conversion rate of the compound of formula (1) is 0%, it means that the compound of formula (1) has not reacted at all and the prepolymer of the present invention cannot be formed. When the conversion rate of the compound of formula (1) is 100%, it means that the compound of formula (1) has reacted completely, and the prepolymer of the present invention cannot be formed at this time. For example, the prepolymer disclosed in the present invention can be prepared by prepolymerizing a mixture comprising at least 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds and 10 to 50 parts by weight of the compound of formula (1) (with a pH value of less than 10) under appropriate conditions. For example, the prepolymerization reaction can be carried out in the presence of a curing accelerator and / or a molecular weight regulator. The types of curing accelerators are detailed below. In one or more embodiments, the molecular weight regulator comprises: n-butylthiol, dodecylthiol, mercaptoacetic acid, mercaptopropionic acid, mercaptoethanol, 2,4-diphenyl-4-methyl-1-pentene, 4,4'-butylenebis(6-tert-butyl-3-methylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), or combinations thereof. There are no particular limitations on the amount of the curing accelerator and / or molecular weight regulator suitable for this invention; each may be independently 0.01 to 5 parts by weight, for example, 0.1 to 1 part by weight, relative to 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds and the total amount of the compound of formula (1), and is not limited thereto. Typically, the polyphenylene ether resin containing unsaturated carbon-carbon double bonds is prepolymerized in a solvent with the compound of formula (1) (with a pH value below 10) and optionally the curing accelerator and / or molecular weight regulator. The solvent may be a solvent commonly used in the art for polymerization reactions between monomers or oligomers containing unsaturated carbon-carbon double bonds and polyphenylene ether resins containing unsaturated carbon-carbon double bonds, including but not limited to toluene and / or methyl ethyl ketone.The temperature of the prepolymerization reaction is usually above room temperature, for example, between 40 and 140°C, preferably between 70 and 100°C. The reaction time is usually 0.5 to 6 hours, preferably 1 to 4 hours. The reaction is usually carried out under stirring. Usually, before the reaction begins, the reaction temperature is raised to above room temperature, and after reacting for a period of time, the temperature is lowered to room temperature (about 25°C) to obtain a solution. The solution is then filtered to remove impurities, and after purification, the prepolymerization product is obtained, which is the prepolymer obtained by prepolymerizing the compound of formula (1) (with a pH value below 10) with a polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

[0070] The polyphenylene ether resin containing unsaturated carbon-carbon double bonds applicable to this application is not particularly limited, and may be any one or more polyphenylene ether resins containing unsaturated carbon-carbon double bonds suitable for the manufacture of prepregs, resin films, laminates, or printed circuit boards, and may be any one or more commercially available products, homemade products, or combinations thereof. Examples include, but are not limited to, vinyl benzyl polyphenylene ether resin, (meth)acryloyl polyphenylene ether resin, vinyl polyphenylene ether resin, or combinations thereof.

[0071] The polyphenylene ether resins used in this application all possess unsaturated carbon-carbon double bonds and a phenylene ether backbone. The unsaturated carbon-carbon double bonds are reactive functional groups, capable of self-polymerization upon heating, or undergoing free radical polymerization with other unsaturated components in the resin composition, ultimately resulting in cross-linking and curing. The cured product exhibits high heat resistance and low dielectric properties. Preferably, the polyphenylene ether resins containing unsaturated carbon-carbon double bonds include those with 2,6-dimethyl substitution on the phenylene ether backbone. The methyl group, after substitution, forms a steric hindrance, making it difficult for the oxygen atoms on the ether to form hydrogen bonds or van der Waals forces, thus reducing hygroscopicity and resulting in even lower dielectric properties.

[0072] In some embodiments, the polyphenylene ether resin containing unsaturated carbon-carbon double bonds includes, but is not limited to, vinyl benzyl polyphenylene ether resins with a number average molecular weight of about 1200 (e.g., OPE-2st 1200, available from Mitsubishi Gas Chemical Company), vinyl benzyl polyphenylene ether resins with a number average molecular weight of about 2200 (e.g., OPE-2st 2200, available from Mitsubishi Gas Chemical Company), vinyl benzyl polyphenylene ether resins with a number average molecular weight of about 2400 to 2800 (e.g., vinyl benzyl bisphenol A polyphenylene ether resin), (meth)acryloyl polyphenylene ether resins with a number average molecular weight of about 1900 to 2300 (e.g., SA9000, available from Sabic Company), vinyl polyphenylene ether resins with a number average molecular weight of about 2200 to 3000, or combinations thereof. The vinyl polyphenylene ether resin may include various polyphenylene ether resins disclosed in U.S. Patent Application US20160185904A1, all of which are incorporated herein by reference. Among them, ethylene benzyl polyphenylene ether resin includes, but is not limited to, ethylene benzyl biphenyl polyphenylene ether resin, ethylene benzyl bisphenol A polyphenylene ether resin, or combinations thereof.

[0073] In this invention, the compound of formula (1) is a cyclic phosphazene compound containing P=N bonds in its structure, where n represents the number of P=N bonds and is an integer from 3 to 6. In other words, when n is 3, the compound of formula (1) has a six-membered ring cyclic phosphazene structure, and when n is 6, the compound of formula (1) has a twelve-membered ring cyclic phosphazene structure. Furthermore, the phosphorus atom in the cyclic phosphazene structure of the compound of formula (1) is replaced by an o-vinylphenoxy or phenoxy group.

[0074] o-vinylphenoxy: phenoxy:

[0075] In this invention, for example, when n is 3, the number of o-vinylphenoxy groups in the cyclic phosphazene structure of the compound of formula (1) can be 1, 2, 3, 4, 5 or 6. When n is 6, the number of o-vinylphenoxy groups in the cyclic phosphazene structure of the compound of formula (1) can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

[0076] In this invention, various compounds of formula (1) can be prepared by the methods described below, and the pH values ​​of various compounds of formula (1) applicable to this invention are all below 10. In this invention, unless otherwise specified, the pH value of the compound can be determined by measuring instruments known in the art, such as, but not limited to, using a pH meter, or, for example, by acid-base titration. In one embodiment, for example, the compound of formula (1) and deionized water with a pH of 7 are mixed in a weight ratio of 1:10, the mixture is filtered and extracted at room temperature, and the pH value of the extract is measured using a pH meter to obtain the pH value of the compound of formula (1). In one embodiment, for example, the pH value of the compound of formula (1) can be from 5 to 10, for example, but not limited to, the pH value of the compound of formula (1) can be 5, 6, 7, 8, 9 or 10. When measured by a pH meter, the pH value of the compound of formula (1) can also be a small value, for example, but not limited to, 5.5, 6.5 or 7.3, and is not limited thereto.

[0077] Compared to 100 parts by weight of a polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition of the present invention comprises 10 to 50 parts by weight of a compound of formula (1) (with a pH value of less than 10), for example, but not limited to 10, 20, 25, 30, 33, 40 or 50 parts by weight of a compound of formula (1) (with a pH value of less than 10).

[0078] For example, in one embodiment, the resin composition of the present invention may also include other components as needed.

[0079] For example, in one embodiment, to further improve one or more properties of the resin composition article, the resin composition of the present invention may, as needed, add compound (2), compound (3), compound (4), or a combination thereof, wherein the specific structures of compound (2), compound (3), and compound (4) are as described above, and their amounts are not particularly limited, for example, from 0.001 parts by weight to 0.5 parts by weight, compared to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds. In one embodiment, the resin composition of the present invention may include 0.001 to 0.5 parts by weight of compound (2), compound (3), compound (4), or a combination thereof. For example, compared to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition of the present invention may include 0.001, 0.003, 0.008, 0.01, 0.05, 0.1, or 0.5 parts by weight of compound (2), compound (3), or compound (4), and is not limited thereto.

[0080] In the resin composition of the present invention, the compound of formula (2) preferably includes, but is not limited to, compounds having any of the structures shown in formulas (5) to (9) or combinations thereof. Unless otherwise specified, in the structure shown in formula (2), the cases where the X1 position is an oxygen radical and the X1 position is a hydroxyl group are chemically equivalent. For example, the structure shown in formula (5) and the structure shown in formula (6) are equivalent to each other, that is, the structure shown in formula (5) may exist in the form of the structure shown in (6), and the structure shown in formula (6) may exist in the form of the structure shown in (5).

[0081] On the other hand, in the resin composition of the present invention, the compound of formula (3) is preferably including, but not limited to, the compounds having any of the structures shown in formulas (10) to (13) or combinations thereof. Similarly, unless otherwise specified, in the structure shown in formula (3), the cases where the X2 position is an oxygen radical and the X2 position is a hydroxyl group are chemically equivalent.

[0082] Furthermore, in the resin composition of the present invention, the compound of formula (4) preferably includes, but is not limited to, compounds having any of the structures shown in formulas (14) to (15) or combinations thereof. Similarly, unless otherwise specified, in the structure shown in formula (4), the cases where the X3 position is an oxygen radical and the X3 position is a hydroxyl group are chemically equivalent. For example, the structure shown in formula (14) and the structure shown in formula (15) are equivalent to each other, that is, the structure shown in formula (14) may exist in the form of the structure shown in formula (15), and the structure shown in formula (15) may exist in the form of the structure shown in formula (14).

[0083] In other words, in this invention, unless otherwise specified, for compounds of formula (2), (3), or (4), any form or chemical structure that reveals an oxygen radical at any of the X1 to X3 positions shall be considered as sufficiently and specifically revealing a hydroxyl group at any of the X1 to X3 positions. For example, if the structure shown in formula (5) is disclosed herein, it shall be considered as also revealing the structure shown in formula (6), and vice versa.

[0084] For example, in one embodiment, the resin composition of the present invention may further include other crosslinking agents containing unsaturated carbon-carbon double bonds as needed. The crosslinking agents containing unsaturated carbon-carbon double bonds used in the present invention are not particularly limited and may be any one or more crosslinking agents containing unsaturated carbon-carbon double bonds suitable for the manufacture of prepregs, resin films, laminates, or printed circuit boards. For example, crosslinking agents containing unsaturated carbon-carbon double bonds may include 1,2-bis(vinylphenyl)ethane, divinylbenzyl ether, divinylbenzene, divinylnaphthalene, divinylbiphenyl, tert-butylstyrene, triallyl isocyanurate, triallyl cyanurate, 1,2,4-trivinylcyclohexane, diallyl bisphenol A, styrene, butadiene, decanadiene, octadiene, vinylcarbazole, acrylates, or combinations thereof. Unless otherwise specified, crosslinking agents containing unsaturated carbon-carbon double bonds also include isomers or prepolymers of these components when interpreted. The amount of the aforementioned crosslinking agent containing unsaturated carbon-carbon double bonds is not particularly limited. For example, compared to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the amount of the crosslinking agent containing unsaturated carbon-carbon double bonds can be from 5 parts by weight to 30 parts by weight, and is not limited thereto. Preferably, the amount of the crosslinking agent containing unsaturated carbon-carbon double bonds is from 5 parts by weight to 10 parts by weight.

[0085] For example, in one embodiment, the resin composition of the present invention may also contain, as needed, benzoxazine resin, epoxy resin, polyester resin, phenolic resin, amine curing agent, polyamide, polyimide, polyolefin, styrene-maleic anhydride, maleimide resin, cyanate ester, maleimide triazine resin, or a combination thereof.

[0086] In this invention, for example, the benzoxazine resin may be any type of benzoxazine resin known in the art. Specific examples include, but are not limited to, bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, phenolphthalein type benzoxazine resin, dicyclopentadiene type benzoxazine resin, phosphorus-containing benzoxazine resin, diamine type benzoxazine resin, and phenyl, vinyl, or allyl modified benzoxazine resin. Applicable commercially available products include, for example, Huntsman's trade names LZ-8270 (phenolphthalein type benzoxazine resin), LZ-8298 (phenolphthalein type benzoxazine resin), LZ-8280 (bisphenol F type benzoxazine resin), LZ-8290 (bisphenol A type benzoxazine resin), or Kolon Industries' trade names KZH-5031 (vinyl modified benzoxazine resin) and KZH-5032 (phenyl modified benzoxazine resin). The diamine-type benzoxazine resin may be a diaminodiphenylmethane benzoxazine resin, a diaminodiphenyl ether type benzoxazine resin, a diaminodiphenyl sulfone benzoxazine resin, a diaminodiphenyl sulfide benzoxazine resin, or a combination thereof, and is not limited thereto.

[0087] Unless otherwise specified, the amount of benzoxazine resin used in this invention can be adjusted as needed. For example, but not limited to, the amount of benzoxazine resin can be 10 to 100 parts by weight, such as 10 parts by weight, 15 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, or 100 parts by weight, compared to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

[0088] In this invention, for example, the epoxy resin can be any type of epoxy resin known in the art. From the perspective of improving the heat resistance of the resin composition, the epoxy resins mentioned above include, but are not limited to, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD ​​epoxy resin, phenolic (novolac) epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, multifunctional phenolic epoxy resin, dicyclopentadiene (DCPD) epoxy resin, phosphorus-containing epoxy resin, p-xylene epoxy resin, naphthalene-type epoxy resin (e.g., naphthol-type epoxy resin), benzofuran-type epoxy resin, isocyanate-modified epoxy resin, or combinations thereof. The phenolic epoxy resin may be phenol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, biphenyl novolac epoxy resin, phenol benzaldehyde epoxy resin, phenol aralkyl novolac epoxy resin, or o-cresol novolac epoxy resin; the phosphorus-containing epoxy resin may be DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) epoxy resin, DOPO-HQ epoxy resin, or a combination thereof.The aforementioned DOPO epoxy resin may be selected from one or more of the following: DOPO-containing phenol novolac epoxy resin, DOPO-containing o-cresol novolac epoxy resin, and DOPO-containing bisphenol-A novolac epoxy resin; the aforementioned DOPO-HQ epoxy resin may be selected from one or more of the following: DOPO-containing phenol novolac epoxy resin, DOPO-HQ-containing o-cresol novolacepoxy resin, and DOPO-HQ-containing bisphenol-Anovolac epoxy resin, and is not limited thereto.

[0089] Unless otherwise specified, the amount of epoxy resin used in this invention can be adjusted as needed. For example, but not limited to, the amount of epoxy resin can be 10 to 100 parts by weight, such as 10 parts by weight, 15 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, or 100 parts by weight, compared to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

[0090] In this invention, for example, the polyester resin may be any type of polyester resin known in the art. Specific examples include, but are not limited to, polyester resins containing a dicyclopentadiene structure and polyester resins containing a naphthalene ring structure. Specific examples include, but are not limited to, HPC-8000 or HPC-8150 sold by Dai Nippon Ink Chemical. Unless otherwise specified, the amount of polyester resin used in this invention may be adjusted as needed. For example, but not limited to, the amount of polyester resin may be 10 to 80 parts by weight, such as 10 parts by weight, 15 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, or 80 parts by weight, compared to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

[0091] In this invention, for example, the phenolic resin can be any type of phenolic resin known in the art, including but not limited to phenolic resin or phenoxy resin, wherein the phenolic resin includes phenolic resin, naphthol phenolic resin, biphenyl phenolic resin and dicyclopentadienol resin, but is not limited thereto. Unless otherwise specified, the amount of phenolic resin used in this invention can be adjusted as needed, for example, but not limited to, the amount of phenolic resin can be 10 to 80 parts by weight, such as 10 parts by weight, 15 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight or 80 parts by weight, compared to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

[0092] In this invention, for example, the amine curing agent can be any type of amine curing agent known in the art. Specific examples include, but are not limited to, at least one or a combination of diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfide, and dicyandiamide. Unless otherwise specified, the amount of amine curing agent used in this invention can be adjusted as needed. For example, but not limited to, the amount of amine curing agent can be 1 to 15 parts by weight relative to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds, such as 1 part by weight, 4 parts by weight, 7.5 parts by weight, 12 parts by weight, or 15 parts by weight.

[0093] In this invention, for example, the polyamide may be any polyamide known in the art, including but not limited to various commercially available polyamide resin products.

[0094] In this invention, for example, the polyimide may be any polyimide known in the art, including but not limited to various commercially available polyimide resin products.

[0095] In this invention, the type of polyolefin is not limited and may include various olefin polymers known in the art, such as, but not limited to, polyolefins including polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene terpolymer, styrene-butadiene-maleic anhydride terpolymer, vinyl-polybutadiene-urea oligomer, maleic anhydride-butadiene copolymer, polymethylstyrene, hydrogenated polybutadiene, hydrogenated styrene-butadiene-divinylbenzene terpolymer, hydrogenated styrene-butadiene-maleic anhydride terpolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, or combinations thereof. Unless otherwise specified, the amount of polyolefin used in this invention can be adjusted as needed. For example, but not limited to, the amount of polyolefin can be 1 to 55 parts by weight relative to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds, such as 1 part by weight, 4 parts by weight, 7.5 parts by weight, 12 parts by weight, 25 parts by weight, 35 parts by weight, 40 parts by weight, or 55 parts by weight. Preferably, the amount of polyolefin is 3 to 13 parts by weight.

[0096] In some embodiments, the styrene-butadiene copolymer is preferably a styrene-butadiene random copolymer.

[0097] In some embodiments, the hydrogenated styrene-butadiene copolymer is preferably a hydrogenated styrene-butadiene block copolymer, and specific examples include, but are not limited to, hydrogenated styrene-butadiene diblock copolymers or hydrogenated styrene-butadiene-styrene triblock copolymers (SEBS).

[0098] In some embodiments, the polyolefin is preferably polybutadiene (B3000) manufactured by Nippon Soda, styrene-butadiene random copolymer (Ricon 100) manufactured by Cray Valley, and hydrogenated styrene-butadiene-styrene triblock copolymer (G1726) manufactured by Kraton.

[0099] In this invention, for example, the styrene-maleic anhydride can be any type of styrene-maleic anhydride known in the art, wherein the ratio of styrene (S) to maleic anhydride (MA) can be 1 / 1, 2 / 1, 3 / 1, 4 / 1, 6 / 1, 8 / 1, or 12 / 1. Specific examples include styrene-maleic anhydride copolymers such as SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60, and EF-80 sold by Cray Valley, or styrene-maleic anhydride copolymers such as C400, C500, C700, and C900 sold by Polyscope, and are not limited thereto.

[0100] For example, the maleimide resin described in this invention may be a maleimide resin manufactured by Daiwakasei Corporation under the trade names BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000H, BMI-5000, BMI-5100, BMI-7000, and BMI-7000H, or a maleimide resin manufactured by KI Chemicals Corporation under the trade names BMI-70 and BMI-80. For example, the maleimide resin described in this invention may be a maleimide resin containing an aliphatic long-chain structure. Maleimide resins containing aliphatic long-chain structures can be trade names such as BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000 and BMI-6000, which are produced by the designer's subsidiary.

[0101] In this invention, for example, the cyanate ester can be any one or more cyanate ester resins suitable for manufacturing prepregs, resin films, laminates, or printed circuit boards, such as compounds having an Ar-OC≡N structure, wherein Ar can be a substituted or unsubstituted aromatic group. From the perspective of improving the heat resistance of the resin composition, specific examples of cyanate ester resins include, but are not limited to, phenolic cyanate ester resins, bisphenol A cyanate ester resins, bisphenol F cyanate ester resins, cyanate ester resins containing a dicyclopentadiene structure, cyanate ester resins containing a naphthalene ring structure, phenolphthalein cyanate ester resins, adamantane cyanate ester resins, fluorene cyanate ester resins, or combinations thereof. Among them, the phenolic cyanate ester resin can be bisphenol A phenolic cyanate ester resin, bisphenol F phenolic cyanate ester resin, or combinations thereof. For example, cyanate ester resins may be cyanate ester resins manufactured by Lonza under trade names such as Primaset PT-15, PT-30S, PT-60S, BA-200, BA-230S, BA-3000S, BTP-2500, BTP-6020S, DT-4000, DT-7000, ULL950S, HTL-300, CE-320, LVT-50, and LeCy.

[0102] For example, unless otherwise specified, the maleimide triazine resin used in this invention is not particularly limited and can be any one or more maleimide triazine resins suitable for manufacturing prepregs, resin films, laminates, or printed circuit boards. For example, the maleimide triazine resin can be obtained by polymerizing the aforementioned cyanate resin and the aforementioned maleimide resin. The maleimide triazine resin can be, for example, but not limited to, polymerized from bisphenol A type cyanate resin and maleimide resin, bisphenol F type cyanate resin and maleimide resin, phenolic phenolic cyanate resin and maleimide resin, or cyanate resin containing a dicyclopentadiene structure and maleimide resin. For example, the maleimide triazine resin can be obtained by polymerizing cyanate resin and maleimide resin in any molar ratio. For example, relative to 1 mole of maleimide resin, the cyanate resin can be 1 to 10 moles. For example, but not limited to, the cyanate resin is 1, 2, 4 or 6 moles relative to 1 mole of maleimide resin.

[0103] For example, in one embodiment, the resin composition of the present invention may also contain flame retardants, curing accelerators, inorganic fillers, surface treatment agents, dyes, solvents, toughening agents, or combinations thereof, as needed.

[0104] For example, the flame retardant suitable for use in this invention may be any one or more flame retardants suitable for the manufacture of prepregs, resin films, laminates or printed circuit boards, such as, but not limited to, phosphorus-containing flame retardants or bromine-containing flame retardants. Bromine-containing flame retardants preferably include decabromodiphenyl ethane, and phosphorus-containing flame retardants preferably include: ammonium polyphosphate, hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenyl phosphate), tri(2-carboxyethyl)phosphine (TCEP), trichloroisopropyl phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), resorcinol bis(dixylenyl phosphate), RDXP (such as commercially available products like PX-200, PX-201, PX-202), melamine polyphosphate, and DPPO (diphenylphosphine). (Oxide) and its derivatives (e.g., bisDPPO compounds) or resins, melamine cyanurate and tri-hydroxyethyl isocyanurate, aluminum phosphonates (e.g., OP-930, OP-935, etc.) or combinations thereof.

[0105] In one embodiment, for example, the flame retardant may also be a flame retardant sold by Katayama Chemical Industry Co., Ltd., such as, but not limited to, V1, V2, V3, V4, V5, V7, S-2, S-4, E-4c, E-7c, E-8g, E-9g, E-10g, E-100, B-3, W-1o, W-2h, W-2o, W-3o, W-4o, OX-1, OX-2, OX-4, OX-6, OX-6+, OX-7, OX-7+, OX-13, BPE-1, BPE-3, HyP-2, API-9, CMPO, ME-20, C-1R, C-1S, C-3R, C-3S, or C-11R. The flame retardant of the present invention may include one or more of the above.

[0106] The flame retardants of the present invention preferably include RDXP (such as commercially available products such as PX-200, PX-201, PX-202) and flame retardants sold by Katayama Chemical Industry Co., Ltd., such as the flame retardant with the trade name S-2.

[0107] In one embodiment, for example, the curing accelerator (including the curing initiator) suitable for the present invention 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, ethyltriphenyl phosphonium 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 metal salt compounds, such as metal salt compounds of manganese, iron, cobalt, nickel, copper, zinc, etc., and metal catalysts such as zinc octanoate, cobalt octanoate, etc. Curing accelerators also include curing initiators, such as peroxides that can generate free radicals. Curing initiators include, but are not limited to, diisopropylbenzene peroxide, tert-butyl peroxybenzoate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B), and bis(tert-butylperoxyisopropyl)benzene or combinations thereof.

[0108] In one embodiment, for example, the inorganic filler suitable for the present invention may include, but is not limited to: silica (molten, non-molten, porous or hollow), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, silicon aluminum 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, zinc molybdate-modified talc, zinc oxide, zirconium oxide, mica, boehmite (AlOOH), calcined talc, talc, silicon nitride, calcined kaolin, or combinations thereof. Furthermore, the inorganic filler may be spherical (including solid or hollow spheres), fibrous, plate-like, granular, flake-like, or needle-like, and may be selectively pretreated with compounds containing unsaturated bonds or silane coupling agents.

[0109] In one embodiment, for example, the surface treatment agent suitable for the present invention includes silane coupling agents, organosilicon oligomers, titanate coupling agents, or combinations thereof. Adding a surface treatment agent can improve the dispersibility of inorganic fillers and their adhesion to resin components. For example, the silane coupling agent may include silane compounds (e.g., but not limited to siloxane compounds), which, depending on the type of functional group, can be further classified into aminosilane compounds, epoxysilane compounds, vinylsilane compounds, ester silane compounds, hydroxysilane compounds, isocyanate silane compounds, methacryloxysilane compounds, and acryloxysilane compounds. Preferably, vinylsilane compounds, methacryloxysilane compounds, and acryloxysilane compounds are used for surface treatment.

[0110] In one embodiment, for example, the dyeing agent suitable for the present invention may include, but is not limited to, dyes or pigments.

[0111] In one embodiment, for example, solvents suitable for use in this invention may include, but are not limited to, methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, N-methylpyrrolidone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide, propylene glycol methyl ether, and other solvents or mixtures thereof.

[0112] In addition to the foregoing components, the resin composition of the present invention may further include, as needed, a toughening agent. In one embodiment, for example, the toughening agent includes, but is not limited to, core-shell rubber, ethylene propylene rubber, or a combination thereof.

[0113] Unless otherwise specified, the amount of each component in the resin composition of the present invention can be adjusted as needed.

[0114] The resin compositions of the foregoing embodiments can be made into various articles, such as components for various electronic products, including but not limited to prepregs, resin films, laminates or printed circuit boards.

[0115] For example, the resin compositions of various embodiments of the present invention can be made into prepregs (also called prepregs), which include reinforcing materials and layers disposed on the reinforcing materials. The layers are 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 120°C and 180°C. The reinforcing material can be any of fiber materials, woven fabrics, or nonwoven fabrics, and the woven fabric preferably includes fiberglass cloth. There are no particular limitations on the type of fiberglass cloth; it can be commercially available fiberglass cloth suitable for various printed circuit boards, such as E-type fiberglass cloth, D-type fiberglass cloth, S-type fiberglass cloth, T-type fiberglass cloth, L-type fiberglass cloth, or Q-type fiberglass cloth. The fiber types include yarns and rovings, and the form can include open or closed fibers. The aforementioned nonwoven fabric preferably includes liquid crystal resin nonwoven fabrics, such as polyester nonwoven fabrics, polyurethane nonwoven fabrics, etc., but is not limited thereto. The aforementioned woven fabrics may also include liquid crystal resin woven fabrics, such as polyester woven fabrics or polyurethane woven fabrics, etc., but are not limited thereto. This reinforcing material increases the mechanical strength of the prepreg. In a preferred embodiment, the reinforcing material may also be selectively pretreated with a silane coupling agent. The prepreg subsequently undergoes heating and curing (C-stage) to form an insulating layer.

[0116] In one embodiment, the resin compositions are mixed uniformly to form a varnish, which is then placed in an impregnation tank. Fiberglass cloth is then immersed in the impregnation tank to allow the resin composition to adhere to the fiberglass cloth. Finally, the cloth is heated and baked at an appropriate temperature until it reaches a semi-cured state to obtain a semi-cured sheet.

[0117] For example, the resin compositions of various embodiments of the present invention can be used to form resin films, which are formed by baking and heating the resin compositions to a semi-cured state. For instance, the resin compositions of various embodiments of the present invention can be selectively coated onto a liquid crystal resin film, a polytetrafluoroethylene film, a polyethylene terephthalate film (PET film), or a polyimide film, and then baked at an appropriate temperature to a semi-cured state to form a resin film. As another example, the resin compositions of various embodiments of the present invention can be coated onto copper foil to ensure uniform adhesion, and then baked at an appropriate temperature to a semi-cured state to obtain a resin film.

[0118] For example, the resin compositions of various embodiments of the present invention can be used to form various laminates comprising at least two metal foils and at least one insulating layer, wherein the insulating layer is disposed between the two metal foils, and the insulating layer can be formed by curing the aforementioned resin composition under high temperature and high pressure (C-stage). Applicable curing temperatures are, for example, between 150°C and 320°C, preferably between 180°C and 250°C, and the curing time is 100 to 300 minutes, preferably 120 to 250 minutes. The aforementioned insulating layer can be obtained by curing the aforementioned prepreg or resin film. The aforementioned metal foils can be made of copper, aluminum, nickel, platinum, silver, gold, or alloys thereof, such as copper foil. In a preferred embodiment, the laminate is a copper foil substrate (also known as copper-clad laminate).

[0119] For example, the resin compositions of various embodiments of the present invention can be used to make printed circuit boards. One method of manufacturing the printed circuit board of the present invention is to use a double-sided copper-clad laminate (e.g., product EM-827, available from Taikwang Electronic Materials Co., Ltd.) with a thickness of 28 mils and 1 ounce HTE (High Temperature Elongation) copper foil, drill holes, and then electroplate to create electrical conductivity between the upper and lower copper foils. The upper and lower copper foils are then etched to form the inner layer circuitry. Next, the inner layer circuitry undergoes a browning roughening treatment to create an uneven surface structure to increase roughness. Then, the copper foil, the aforementioned prepreg, the aforementioned inner layer circuit board, the aforementioned prepreg, and the copper foil are stacked sequentially, and then heated at 180°C to 320°C for 100 to 300 minutes using a vacuum lamination apparatus to cure the insulating layer material of the prepreg. Next, various circuit board processes known in the art, such as blackening, drilling, and copper plating, are performed on the outermost copper foil to obtain a printed circuit board.

[0120] Preferably, the resin composition or its product provided by the present invention can be improved in one or more aspects such as filler uniformity, dielectric loss thermal change rate, glass transition temperature, Z-axis thermal expansion coefficient, peel strength, and moisture absorption and heat resistance.

[0121] For example, the resin composition or articles thereof provided by the present invention may satisfy one, more or all of the following characteristics:

[0122] There are no patterns on the copper-free surface of the inner layer circuit board;

[0123] After standing at a constant temperature of 188°C for 48 hours, the dielectric loss heat change rate calculated by measuring the dielectric loss at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 30%, for example, the dielectric loss heat change rate is between 9% and 28%.

[0124] The glass transition temperature measured according to the method described in IPC-TM-650 2.4.24.4 is greater than or equal to 226°C, for example, the glass transition temperature is between 226°C and 252°C;

[0125] The Z-axis thermal expansion coefficient measured according to the method described in IPC-TM-650 2.4.24.5 is less than or equal to 1.82%, for example, the Z-axis thermal expansion coefficient is between 1.39% and 1.82%.

[0126] A peel strength measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 4.5 lb / in, for example, a peel strength between 4.5 lb / in and 5.2 lb / in; and

[0127] The moisture absorption and heat resistance test performed according to the methods described in IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23 did not result in plate bursting.

[0128] The resin compositions of the embodiments and comparative examples of the present invention were prepared according to the amounts specified in Tables 1 to 3 using various raw materials from the following sources, and were further prepared into various test samples.

[0129] The chemical raw materials used in the embodiments and comparative examples of this invention are as follows:

[0130] SA9000: Methacrylamide polyphenylene ether resin, purchased from Sabic.

[0131] OPE-2st 2200: Ethylene benzyl polyphenylene ether resin, purchased from Mitsubishi Gas Chemical Company.

[0132] OPE-2st 1200: Ethylene benzyl polyphenylene ether resin, purchased from Mitsubishi Gas Chemical Company.

[0133] Compounds A1 to A6 with the structure of formula (1): self-made, detailed below.

[0134] Prepolymers 1-3: self-made, detailed below.

[0135] Compounds B, C, and D: self-made, detailed below.

[0136] SPV-100: Allylphosphazene, purchased from Otsuka Chemical.

[0137] Di-DOPO: bis9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, with the following structural formula.

[0138]

[0139] PX-200: Tetra(2,6-dimethylphenyl) 1,3-phenylene phosphate (condensate), purchased from Daihachi Chemical, Japan.

[0140] S-2: Diethyl-p-vinylbenzyl phosphate, purchased from Katayama Chemical Co., Ltd.

[0141] Compound A7: self-made, detailed below.

[0142] Compound B1: Compound of formula (5), purchased from Changzhou Jianna.

[0143] Compound B2: Compound of formula (7), purchased from Changzhou Yipintang Chemical.

[0144] Compound C1: Compound of formula (10), purchased from Changzhou Yipintang Chemical.

[0145] Compound C2: Compound of formula (11), purchased from Changzhou Yipintang Chemical.

[0146] Compound D1: Compound of formula (15), purchased from Wuxi Fu'an Chemical Plant.

[0147] DVB: Divinylbenzene, purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0148] TAIC: Triallyl isocyanurate, purchased from Chin Yu Enterprise Co., Ltd.

[0149] Ricon 100: Styrene-butadiene random copolymer, purchased from Cray Valley.

[0150] B-3000: Polybutadiene, purchased from Caoda Company.

[0151] G1726: Hydrogenated styrene-butadiene-styrene triblock copolymer (SEBS), purchased from Kraton Corporation.

[0152] SC-2500-SVJ: Inorganic filler, spherical silica with a silane coupling agent surface treatment, purchased from Admatechs.

[0153] 25B: Hardening initiator, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, purchased from Nippon Oils & Fats Co., Ltd.

[0154] Toluene: Solvent, purchased from Sinopec. The toluene content is expressed as "appropriate amount", which means that the toluene content is adjusted to the total solid content (S / C = 65%) of the resin composition.

[0155] Chemical raw material preparation examples

[0156] Homemade compound A1:

[0157] Add 31.2 g of NaH and 400 mL of anhydrous tetrahydrofuran (THF) to a 1 L three-necked flask, purge with N2, stir and heat to 50 °C, dissolve 97.7 g of o-hydroxybenzaldehyde in 200 mL of anhydrous THF, and slowly add it dropwise to the three-necked flask. After the addition is complete, continue the reaction for 4 hours. Dissolve 34.7 g of hexachlorocyclotriphosphazene in 200 mL of anhydrous THF and add it to the three-necked flask. Heat to 65 °C and react for 48 hours. Centrifuge, filter several times and dry to obtain the intermediate product.

[0158] This reaction is highly sensitive to oxygen and water in the air, therefore it needs to be carried out in a dry and inert atmosphere, and the containers and solvents must be kept very dry. Dry methyltriphenylphosphine bromide (150% excess) and calcium hydride (150% excess) were added to anhydrous THF, followed by the intermediate product. After the reaction was complete, acetic acid was added and stirred for 1 hour. The mixture was then filtered to obtain the self-made compound A1, of which 95% had the structure shown in formula (1). At this point, n = 3, the pH was measured to be 8, and Y and Z were both o-vinylphenoxy compounds, with a total of 6 Y and Z. The specific structure of the self-made compound A1 is shown below:

[0159]

[0160] Unless otherwise specified, in this invention, the method for determining the pH value of the compound is as follows: the compound and deionized water with a pH value of 7 are mixed at a weight ratio of 1:10, the mixture is filtered and extracted at room temperature, and the pH value of the extract is measured using a pH meter, which is the pH value of the compound.

[0161] Homemade compound A2:

[0162] Add 31.2 g of NaH and 400 mL of anhydrous THF to a 1 L three-necked flask, purge with N2, stir and heat to 50 °C, dissolve 97.7 g of o-hydroxybenzaldehyde in 200 mL of anhydrous THF, and slowly add it dropwise to the three-necked flask. After the addition is complete, continue the reaction for 4 hours. Dissolve 34.7 g of hexachlorocyclotriphosphazene in 200 mL of anhydrous THF and add it to the three-necked flask. Heat to 65 °C and react for 48 hours. Centrifuge, filter several times and dry to obtain the intermediate product.

[0163] The reaction is highly sensitive to oxygen and water in the air, therefore it needs to be carried out in a dry and inert atmosphere, and the containers and solvents must be kept very dry. Dry methyltriphenylphosphine bromide (150% excess) and calcium hydride (160% excess) were added to anhydrous THF, followed by the intermediate product. After the reaction was complete, acetic acid was added and stirred for 1 hour. The mixture was then filtered to obtain the self-made compound A2, of which 90% had the structure shown in formula (1). At this point, n=3, the pH was measured to be 10, and Y and Z were both o-vinylphenoxy compounds, with a total number of Y and Z of 6.

[0164] Homemade compound A3:

[0165] Add 31.2 g of NaH and 400 mL of anhydrous THF to a 1 L three-necked flask, purge with N2, stir and heat to 50 °C, dissolve 97.7 g of o-hydroxybenzaldehyde in 200 mL of anhydrous THF, and slowly add it dropwise to the three-necked flask. After the addition is complete, continue the reaction for 4 hours. Dissolve 34.7 g of hexachlorocyclotriphosphazene in 200 mL of anhydrous THF and add it to the three-necked flask. Heat to 65 °C and react for 48 hours. Centrifuge, filter several times and dry to obtain the intermediate product.

[0166] The reaction is highly sensitive to oxygen and water in the air, therefore it needs to be carried out in a dry and inert atmosphere, and the containers and solvents must be kept very dry. Dry methyltriphenylphosphine bromide (150% excess) and calcium hydride (130% excess) were added to anhydrous THF, followed by the addition of the intermediate product. After the reaction was complete, acetic acid was added and stirred for 1 hour. The mixture was then filtered to obtain the self-made compound A3, which has 100% of the structure shown in formula (1). At this point, n = 3, the pH was measured to be 5, and Y and Z are both o-vinylphenoxy compounds with a total number of 6.

[0167] Homemade compound A4:

[0168] Add 62.4 g of NaH and 400 mL of anhydrous THF to a 1 L three-necked flask, purge with N2, stir and heat to 50 °C. Dissolve 195.4 g of o-hydroxybenzaldehyde in 200 mL of anhydrous THF and slowly add it dropwise to the three-necked flask. After the addition is complete, continue the reaction for 4 hours. Dissolve 69.4 g of dodecyl cyclophosphine in 200 mL of anhydrous THF and add it to the three-necked flask. Heat to 65 °C and react for 48 hours. Centrifuge, filter several times and dry to obtain the intermediate product.

[0169] The reaction is highly sensitive to oxygen and water in the air, therefore it needs to be carried out in a dry and inert atmosphere, and the containers and solvents must be kept very dry. Dry methyltriphenylphosphine bromide (150% excess) and calcium hydride (150% excess) were added to anhydrous THF, followed by the addition of the intermediate product. After the reaction was complete, acetic acid was added and stirred for 1 hour. The mixture was then filtered to obtain the self-made compound A4, of which 95% had the structure shown in formula (1). At this point, n = 6, the pH was measured to be 8, and Y and Z were both o-vinylphenoxy compounds, with a total number of Y and Z of 12.

[0170] Homemade compound A5:

[0171] Add 31.2 g of NaH and 400 mL of anhydrous THF to a 1 L three-necked flask, purge with N2, stir and heat to 50 °C, dissolve 97.7 g of o-hydroxybenzaldehyde in 200 mL of anhydrous THF, and slowly add it dropwise to the three-necked flask. After the addition is complete, continue the reaction for 4 hours. Dissolve 34.7 g of hexachlorocyclotriphosphazene in 200 mL of anhydrous THF and add it to the three-necked flask. Heat to 65 °C and react for 48 hours. Centrifuge, filter several times and dry to obtain the intermediate product.

[0172] The reaction is highly sensitive to oxygen and water in the air, therefore it needs to be carried out in a dry and inert atmosphere, and the containers and solvents must be kept very dry. Dry methyltriphenylphosphine bromide (150% excess) and calcium hydride (180% excess) were added to anhydrous THF, followed by the addition of the intermediate product. After the reaction was complete, acetic acid was added and stirred for 1 hour. The mixture was then filtered to obtain the self-made compound A5, of which 75% had the structure shown in formula (1). At this point, n=3, the pH was measured to be 12, and Y and Z were both o-vinylphenoxy compounds, with a total number of Y and Z of 6.

[0173] Homemade compound A6:

[0174] Add 31.2 g of NaH and 400 mL of anhydrous THF to a 1 L three-necked flask, purge with N2, stir and heat to 50 °C. Dissolve 48.85 g of o-hydroxybenzaldehyde and 37.6 g of phenol in 200 mL of anhydrous THF and slowly add the solution dropwise to the three-necked flask. After the addition is complete, continue the reaction for 4 hours. Dissolve 34.7 g of hexachlorocyclotriphosphazene in 200 mL of anhydrous THF and add the solution to the three-necked flask. Heat to 65 °C and react for 48 hours. Centrifuge, filter multiple times and dry to obtain the intermediate product.

[0175] The reaction is highly sensitive to oxygen and water in the air, therefore it needs to be carried out in a dry and inert atmosphere, and the containers and solvents must be kept very dry. Dry methyltriphenylphosphine bromide (150% excess) and calcium hydride (140% excess) were added to anhydrous THF, followed by the intermediate product. After the reaction was complete, acetic acid was added and stirred for 1 hour. The mixture was then filtered to obtain the self-made compound A6, of which 95% had the structure shown in formula (1). At this point, n=3, the pH was measured to be 8, Y was o-vinylphenoxy, Z was phenoxy, the number of Y and Z were 3, and the total number of Y and Z was 6.

[0176] Homemade prepolymer 1:

[0177] First, 60 parts by weight of SA9000, 60 parts by weight of OPE-2st 2200, and 12 parts by weight of self-made compound A1 were added to 120 parts by weight of toluene solvent under stirring. Then, 0.12 parts by weight of peroxide (BPO) was added as a prepolymerization initiator. The mixture was stirred continuously at 70°C and reacted for 1 hour. After the reaction was completed, the mixture was cooled and purified by filtration to obtain self-made prepolymer 1 with a solid content of 100% and a conversion rate between 10% and 99%.

[0178] Homemade prepolymer 2:

[0179] The preparation steps of self-made prepolymer 1 were followed to prepare self-made prepolymer 2, except that SA9000, OPE-2st 2200, and self-made compound A1 were 60 parts by weight. Self-made prepolymer 2 was finally obtained with a solid content of 100% and a conversion rate between 10% and 99%.

[0180] Homemade prepolymer 3:

[0181] Self-made prepolymer 3 was prepared following the same preparation steps as self-made prepolymer 1, except that SA9000 was 72 parts by weight, OPE-2st 2200 was 36 parts by weight, OPE-2st 1200 was 12 parts by weight, self-made compound A1 was 24 parts by weight, self-made compound A2 was 6 parts by weight, self-made compound A3 was 6 parts by weight, and self-made compound A4 was 3.6 parts by weight. Self-made prepolymer 3 was finally obtained with a solid content of 100%, and the conversion rate of self-made prepolymer 3 was between 10% and 99%.

[0182] Homemade compound B:

[0183] Using 4-allyloxy-4'-hydroxydiphenyl sulfone and sodium as the main raw materials, 4-allyloxy-4'-oxosodium diphenyl sulfone was first prepared by adding tetrahydrofuran at 25°C for substitution reaction. Then, appropriate amounts of hexachlorocyclotriphosphazene and tetrahydrofuran were added, and NaCl was removed at 60°C to obtain compound B, with the following structure.

[0184]

[0185] Homemade compound C:

[0186] Using hexachlorocyclotriphosphazene, 3-vinylphenol and phenol as the main raw materials, a two-step nucleophilic substitution reaction was carried out by a stepwise dropwise addition method to synthesize a p-vinylbenzenecyclotriphosphazene compound, namely compound C, with the following structure.

[0187] Homemade compound D:

[0188] In the synthesis of the self-made compound A1, o-hydroxybenzaldehyde was replaced with p-hydroxybenzaldehyde, while the remaining steps and conditions remained the same.

[0189]

[0190] Homemade compound A7:

[0191] Add 31.2 g of NaH and 400 mL of anhydrous THF to a 1 L three-necked flask, purge with N2, stir and heat to 50 °C, dissolve 97.7 g of o-hydroxybenzaldehyde in 200 mL of anhydrous THF, and slowly add it dropwise to the three-necked flask. After the addition is complete, continue the reaction for 4 hours. Dissolve 34.7 g of hexachlorocyclotriphosphazene in 200 mL of anhydrous THF and add it to the three-necked flask. Heat to 65 °C and react for 48 hours. Centrifuge, filter several times and dry to obtain hexa(2-aldehydephenoxy)cyclotriphosphazene.

[0192] Dry methyltriphenylphosphine bromide and calcium hydride were added to anhydrous THF to prepare an active phosphorus ylide. Then, hexa(2-aldehyde phenoxy)cyclotriphosphazene was added. The molar ratio of aldehyde group to phosphorus ylide was 1:0.6, and the ratio of aldehyde group to vinyl group was close to 1:1. After the reaction was complete, acetic acid was added and stirred for 1 hour. The mixture was filtered to obtain the self-made compound A7, which has the structure shown in formula (16). At this time, n=3, the pH was measured to be 7, J is o-vinylphenoxy, K is the group shown in formula (17), the number of J is 3, and the total number of J and K is 6.

[0193]

[0194] The resin compositions (all in parts by weight) and the results of property tests for the examples and comparative examples are shown in the table below:

[0195] [Table 1] Composition (parts by weight) and property test results of the resin compositions in the examples

[0196]

[0197]

[0198] [Table 2] Composition (parts by weight) and property test results of the resin compositions in the examples

[0199]

[0200]

[0201] [Table 3] Composition (parts by weight) and property test results of comparative example resin compositions

[0202]

[0203]

[0204] The formulation methods of the resin compositions of each embodiment and comparative example are described below (the solid content of each component added in each embodiment and comparative example is 100%).

[0205] Example E1

[0206] First, 50 parts by weight of SA9000, 50 parts by weight of OPE-2st 2200, and 10 parts by weight of compound A1 were added to an appropriate amount of toluene (to control the overall solid content of the resin composition to be 65%), and stirred until all solid components were dissolved to obtain a homogeneous liquid phase. Then, 100 parts by weight of SC-2500-SVJ were added and stirred until completely dispersed. Finally, 0.1 parts by weight of 25B were added, and the mixture was stirred at room temperature for 1 hour to obtain resin composition E1.

[0207] Example E12

[0208] Take 110 parts by weight of prepolymer 1 and add it to an appropriate amount of toluene (controlling the overall solid content of the resin composition to 65%). Stir until all solid components are dissolved to obtain a homogeneous liquid phase. Then add 100 parts by weight of SC-2500-SVJ and stir until completely dispersed. Add 0.01 parts by weight of compound B1 of formula (2) and 0.1 parts by weight of 25B. Stir at room temperature for 1 hour to obtain resin composition E12.

[0209] Examples E2 to E11, E15, E16 and Comparative Examples C1 to C8 were prepared using the formulation method of Example E1, and Examples E13 and E14 were prepared using the formulation method of Example E12.

[0210] In addition, the analyte (sample) should be prepared according to the following method, and then its characteristics should be analyzed according to the specific conditions.

[0211] 1. Prepreg: The resin compositions of the above embodiments and the comparative examples (in parts by weight) were selected respectively. The resin compositions were uniformly mixed in a mixing tank to form a varnish (or adhesive or liquid). Next, the varnish was placed in an impregnation tank, and then glass fiber cloth (e.g., L-glass fiber fabric of specifications 2116, 1080 or 1017, purchased from Asahi Corporation) was immersed in the impregnation tank to allow the resin composition to adhere to the glass fiber cloth. Then, it was heated and baked at 140°C for about 6 minutes to obtain a prepreg.

[0212] 2. Copper-containing substrate (or copper foil substrate, 5-ply, made by laminating five prepreg sheets): Prepare two 18-micron thick RTF copper foils (reverse treated copper foil) and five L-glass fiber cloths of specification 2116 impregnated with prepreg sheets made from each test sample (each set of examples or comparative examples). The resin content of each prepreg sheet is approximately 55%. The prepreg sheets are laminated in the order of copper foil, five prepreg sheets, and copper foil, under vacuum conditions and a pressure of 32 kgf / cm². 2 A copper-containing substrate is formed by laminating at 200°C for 120 minutes. Five prepreg sheets are then cured to form an insulating layer between the two copper foils; the resin content of this insulating layer is approximately 55%.

[0213] 3. Copper-containing substrate (or copper foil substrate, 2-ply, formed by laminating two prepreg sheets): Prepare two 18-micron thick RTF copper foils (reverse treated copper foil) and two 1080 L-glass fiber cloths impregnated with prepreg sheets made from the test samples (each set of examples or comparative examples). Each prepreg sheet has a resin content of approximately 70%. The prepreg sheets are laminated in the following order: copper foil, two prepreg sheets, and copper foil. The laminations are then subjected to vacuum conditions and a pressure of 32 kgf / cm². 2 A copper-containing substrate is formed by laminating the two prepregs at 200°C for 120 minutes. During this process, two overlapping prepregs cure to form an insulating layer between the two copper foils; the resin content of this insulating layer is approximately 70%.

[0214] 4. Copper-free substrate (5 layers, made of five prepreg sheets laminated together): The copper-containing substrate (5 layers) above is etched to remove the copper foil on both sides to obtain a copper-free substrate (5 layers). The copper-free substrate is made of five prepreg sheets laminated together. The resin content of the copper-free substrate is about 55%.

[0215] 5. Copper-free substrate (2 layers, made of two prepregs laminated together): The copper-containing substrate (2 layers) described above is etched to remove the copper foil on both sides to obtain a copper-free substrate (2 layers). The copper-free substrate is made of two prepregs laminated together, and the resin content of the copper-free substrate is about 70%.

[0216] For the aforementioned analyte (sample), the characteristics were analyzed in the following manner.

[0217] 1. Uniformity of adhesive filling

[0218] A 2.5 mil thick copper-containing substrate (e.g., product EM-827, available from Taikwang Electronic Materials Co., Ltd.) was processed into a browned circuit board as the inner layer using a conventional browning process. The ability of the prepreg to fill the empty areas between circuits during lamination was evaluated. A prepreg was prepared by impregnating 1017 L-glass fiber cloth with a varnish of the resin composition of each of the examples or comparative examples, and baking at 140°C for 4 minutes. The resin content of the prepreg was approximately 79%. One of the aforementioned prepregs (prepregs prepared by impregnating each test sample (each example or comparative example) with 1017 L-glass fiber cloth) was stacked on each side of the 2.5 mil thick browned circuit board, and an RTF copper foil (18 micrometers thick) was then stacked on the outer layer. The inner layer circuit board with a copper surface was formed by lamination in a vacuum press at 450 psi and 210°C for 2 hours. The outer copper foil was then etched away to obtain an inner layer circuit board without copper surface. Visually inspect the copper-free surface of the inner layer circuit board for any patterns. If patterns are present after lamination, it indicates poor filler uniformity, which will result in the scrapping of subsequent circuit boards. If patterns are present (e.g....) Figure 1 (As shown) is recorded as "pattern", if there is no pattern (such as...) Figure 2 (As shown) is marked as OK, indicating excellent glue filling uniformity.

[0219] 2. Dielectric loss thermal change rate (Df thermal aging rate)

[0220] The copper-free substrate (composed of two prepreg sheets laminated together) was selected as the test sample. A microwave dielectric analyzer (purchased from AET Corporation, Japan) was used, and the dielectric loss of each sample was measured at room temperature (approximately 25°C) and a frequency of 10 GHz, following the method described in JIS C2565. This result was recorded as Df1. After cleaning the sample with distilled water, it was placed at 188°C for 48 hours, and its dielectric loss was measured again and recorded as Df2. Therefore, the thermal aging rate Df = ((Df2 - Df1) / Df1) * 100%.

[0221] 3. Glass transition temperature (Tg)

[0222] In the glass transition temperature test, the copper-free substrate (composed of five prepreg sheets laminated together) was selected as the test sample. Dynamic mechanical analysis (DMA) was used to measure the glass transition temperature (in °C) of the test sample according to the method described in IPC-TM-6502.4.24.4. The measurement temperature range was 35 °C to 270 °C, with a temperature rise rate of 2 °C / min. A higher glass transition temperature indicates better properties.

[0223] 4. Z-axis thermal expansion coefficient (percent thermal expansion, z-axis, Z-PTE)

[0224] In the measurement of Z-axis thermal expansion coefficient, a copper-free substrate (composed of five prepreg sheets laminated together) was selected as the test sample for thermomechanical analysis (TMA). The sample was heated at a rate of 10°C per minute, from 50°C to 260°C. The Z-axis thermal expansion coefficient (in %) of each test sample within the temperature range of 50°C to 260°C was measured according to the method of IPC-TM-6502.4.24.5. A lower Z-axis thermal expansion coefficient is better.

[0225] 5. Peeling strength (P / S)

[0226] The copper substrate (made by laminating five prepreg sheets) was selected and cut into rectangular samples with a width of 24 mm and a length greater than 60 mm. The copper foil on the surface was 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 testing machine, at room temperature (approximately 25°C), the force required to pull the copper foil away from the surface of the substrate insulation layer was measured according to the method described in IPC-TM-650 2.4.8, and the unit was lb / in.

[0227] 6. Moisture absorption and heat resistance (pressure cooking test, PCT)

[0228] In the moisture absorption and heat resistance test, the copper-free substrate (composed of five prepreg sheets laminated together) was selected as the test sample. Following the method described in IPC-TM-650 2.6.16.1, a pressure cooking test (PCT) was performed for 5 hours (test temperature 121℃, relative humidity 100%). Then, following the method described in IPC-TM-650 2.4.23, the sample was immersed in a solder bath at a constant temperature of 288℃, and removed after 20 seconds to observe for any board bursting. Three samples of the same specifications were tested in each group. If any sample showed board bursting (marked as X), it indicated interlayer separation or blistering of the substrate's insulating layer. If the test result was no board bursting (marked as O), it indicated no interlayer delamination or blistering occurred. OOO represents that none of the three samples burst, XXX represents that all three samples burst, OOX represents that one of the three samples burst and two did not burst, and OXX represents that two of the three samples burst and one did not burst.

[0229] Based on the test results above, the following phenomena can be observed.

[0230] By comparing Examples E12 to E14 with other examples, it can be confirmed that the resin composition of the present invention, whether it is a technical solution including a polyphenylene ether resin containing unsaturated carbon-carbon double bonds and a compound of formula (1) (with a pH value of 10 or less), or a technical solution including a prepolymer obtained by prepolymerization reaction of a polyphenylene ether resin containing unsaturated carbon-carbon double bonds and a compound of formula (1) (with a pH value of 10 or less), can also improve one or more aspects such as filler uniformity, dielectric loss heat change rate, glass transition temperature, Z-axis thermal expansion coefficient, peel strength, and moisture absorption and heat resistance.

[0231] By comparing Examples E1 and E3 with Comparative Examples C1 and C2, it can be found that if the amount of compound of formula (1) is not in the range of 10 parts by weight to 50 parts by weight, the properties such as dielectric loss thermal change rate and peel strength cannot be significantly improved.

[0232] By observing the various examples and comparative example C3, it can be found that if the pH value of the compound of formula (1) is greater than 10, the properties such as dielectric loss heat change rate, glass transition temperature, Z-axis thermal expansion coefficient, peel strength and moisture absorption heat resistance cannot be significantly improved.

[0233] By observing the various examples and comparative examples C4 to C8, it can be found that if the compound of formula (1) is not used (its pH value is below 10) but only other compounds with different structures from the compound of formula (1) are used, the properties such as filler uniformity, dielectric loss heat change rate, glass transition temperature, Z-axis thermal expansion coefficient, peel strength and moisture absorption heat resistance cannot be significantly improved.

[0234] By comparing all embodiments E1-E16 of the present invention with all comparative examples C1-C8, it can be confirmed that the articles made using the resin composition of the present invention can simultaneously achieve significant improvements in properties such as filler uniformity, dielectric loss thermal change rate, glass transition temperature, Z-axis thermal expansion coefficient, peel strength, and moisture absorption and heat resistance. Conversely, comparative examples C1-C8, which did not use the technical solution of the present invention, could not achieve the aforementioned technical effects.

[0235] The above embodiments are merely illustrative in nature and are not intended to limit the embodiments of the subject matter or the application or use of such embodiments. In this document, the term "illustrative" means "as an example, illustration, or description." No illustrative embodiment herein should necessarily be construed as preferred or advantageous over other embodiments.

[0236] Furthermore, although at least one exemplary embodiment or comparative example has been presented in the foregoing embodiments, it should be understood that numerous variations are possible with respect to the invention. 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. Rather, the foregoing embodiments will provide a simple guide for those skilled in the art to implement one or more of the described embodiments. Moreover, various changes can be made to the function and arrangement of the elements without departing from the scope defined by the claims, and the claims include known equivalents and all foreseeable equivalents at the time of filing of this patent application.

Claims

1. A resin composition, characterized in that, Includes the following components or their prepolymers: (A) 100 parts by weight of a polyphenylene ether resin containing unsaturated carbon-carbon double bonds; and (B) 10 to 50 parts by weight of the compound of formula (1) having a pH value of less than 10; Equation (1) In formula (1), n ​​is an integer from 3 to 6, each Y and Z is independently selected from o-vinylphenoxy and phenoxy, and each Y and Z is not simultaneously phenoxy; The prepolymer is obtained by a prepolymerization reaction of a mixture, and the mixture includes at least component (A) and component (B). The compound of formula (1) and deionized water with a pH of 7 are mixed at a weight ratio of 1:

10. The mixture is filtered and extracted at room temperature. The pH value of the extract is obtained by measuring the pH value of the extract using a pH meter.

2. The resin composition according to claim 1, characterized in that, The pH value of the compound of formula (1) is 5 to 10.

3. The resin composition according to claim 1, characterized in that, It further includes 0.001 to 0.5 parts by weight of compounds of formula (2), (3), (4), or combinations thereof: Equation (2) Equation (3) Equation (4) Wherein, X1 is an oxygen free radical or a hydroxyl group; R2 to R5 are each independently a hydrogen atom or a C1 to C5 alkyl group, and R2 to R5 are not simultaneously hydrogen atoms; R1 is a hydrogen atom, a C1 to C5 alkyl group, an amino group, a hydroxyl group, a ketone group, or a carboxyl group; Wherein, X2 is an oxygen free radical or a hydroxyl group; R7 to R 10 Each is independently a hydrogen atom or a C1 to C5 alkyl group, and R7 to R 10 Not both are hydrogen atoms; R6 and R 11 Each group is independently a hydrogen atom, a C1 to C5 alkyl, amino, hydroxyl, ketone, or carboxyl group, or an R6 and R group. 11 They collectively define a benzene ring structure; Among them, X3 is an oxygen free radical or a hydroxyl group; R 12 To R 23 Each is independently a hydrogen atom or a C1 to C5 alkyl group, and R 12 To R 23 They are not both hydrogen atoms.

4. The resin composition according to claim 1, characterized in that, The prepolymer is formed by a prepolymerization reaction of component (A) and component (B), and the conversion rate of the prepolymerization reaction is between 10% and 99%.

5. The resin composition according to claim 1, characterized in that, It further includes 1,2-bis(vinylphenyl)ethane, divinylbenzyl ether, divinylbenzene, divinylnaphthalene, divinylbiphenyl, tert-butylstyrene, triallyl isocyanurate, triallyl cyanurate, 1,2,4-trivinylcyclohexane, diallyl bisphenol A, styrene, butadiene, decanadiene, octadiene, vinylcarbazole, acrylates or combinations thereof.

6. The resin composition according to claim 1, characterized in that, It also includes benzoxazine resins, epoxy resins, polyester resins, phenolic resins, amine curing agents, polyamides, polyimides, polyolefins, styrene-maleic anhydride copolymers, maleimide resins, cyanate esters, or combinations thereof.

7. The resin composition according to claim 1, characterized in that, It also includes flame retardants, hardening accelerators, inorganic fillers, surface treatment agents, dyes, solvents, toughening agents, or combinations thereof.

8. An article made from the resin composition of claim 1, characterized in that, This includes prepregs, resin films, laminates, or printed circuit boards.

9. The article of claim 8, characterized in that, After being left to stand at a constant temperature of 188°C for 48 hours, the dielectric loss thermal change rate calculated by measuring the dielectric loss at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 30%.

10. The article of claim 8, characterized in that, The glass transition temperature, as measured according to the method described in IPC-TM-650 2.4.24.4, is greater than or equal to 226°C.

11. The article of claim 8, characterized in that, The Z-axis thermal expansion coefficient, measured according to the method described in IPC-TM-650 2.4.24.5, is less than or equal to 1.82%.

12. The article of claim 8, characterized in that, Its peel strength, measured according to the method described in IPC-TM-650 2.4.8, is greater than or equal to 4.5 lb / in.

13. The article of claim 8, characterized in that, The moisture absorption and heat resistance test performed according to the methods described in IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23 did not result in plate bursting.

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