Low dielectric compound, method of manufacturing the same, resin composition and article thereof

Abstract

The invention provides a compound with a structure as shown in a formula (I), a preparation method thereof, a resin composition containing the compound and a product prepared from the resin composition. The resin composition comprises a compound with a structure as shown in a formula (I), vinyl-containing polyphenyl ether resin and a vinyl-containing cross-linking agent. The articles include prepregs, resin films, laminates, printed circuit boards, or cured insulators, and may be improved in one or more aspects of glass transition temperature, dielectric constant, dielectric loss, heat resistance after moisture absorption, flame retardancy, in-board gummosis, and falling ball test.

Description

Technical Field

[0001] This invention relates to the field of compounds. In particular, it relates to a compound applicable to prepregs, resin films, laminates, printed circuit boards, or cured insulators, a method for manufacturing the same, resin compositions containing the compound, and articles made from the resin compositions. Background Technology

[0002] The signals used in mobile communication devices such as smartphones, base station equipment, network infrastructure equipment such as servers, and electronic devices such as mainframe computers are becoming increasingly faster and larger in capacity year by year. Consequently, the printed circuit boards (PCBs) mounted on these electronic devices must ensure the integrity of signal transmission, requiring copper-clad laminate (CCL) materials to have low dielectric loss. Due to the long-term operation of these devices, the heat resistance of CCL materials is also required. To cope with the complex processing of printed circuit boards, the toughness of CCLs has also become a focus of the industry.

[0003] In addition, during the manufacturing process of copper clad laminates, the rapid reactivity of the resin raw materials often leads to a shorter shelf life of the resin raw materials or their resin compositions. Therefore, developing stable resin raw materials and copper clad laminate materials with excellent heat resistance, electrical properties, and toughness has become an urgent problem to be solved. Summary of the Invention

[0004] In view of the problems encountered in the prior art, especially the inability of existing materials to meet one or more of the above-mentioned characteristic requirements, the main objective of the present invention is to provide a compound that can solve the above-mentioned problems, a method for manufacturing the same, a resin composition containing the compound, and articles made from the resin composition such as prepregs, resin films, laminates, printed circuit boards, or cured insulators.

[0005] In one aspect, the present invention provides a compound having the structure shown in formula (I):

[0006]

[0007] In equation (I), n is an integer from 3 to 6, X and T are the same or different, and X and T are each independent as shown in equation (1) or equation (2), with at least one of X and T being equation (2), where m is an integer from 0 to 4, and R a R is an alkyl group having 1 to 4 carbon atoms or hydrogen atoms. b R c R d It is independently selected from alkyl, phenyl, or naphthyl groups having 1 to 4 carbon atoms.

[0008]

[0009] The compound of formula (I) provided by this invention can simultaneously improve one or more of the following effects in a polyphenylene ether (PPO) system containing double bond resin: glass transition temperature, dielectric properties, heat resistance, in-plate resin flow rate, or drop ball test.

[0010] In one aspect, the present invention provides a method for manufacturing the compound, comprising the step of performing a hydrosilylation reaction of vinylphenoxycyclophosphonitrile with a silane compound containing silane bonds.

[0011] In one aspect, the present invention provides a resin composition comprising 80 to 120 parts by weight of a compound of formula (I), 100 parts by weight of a vinyl-containing polyphenylene ether resin, and 15 to 45 parts by weight of a vinyl-containing crosslinking agent.

[0012] In one aspect, the present invention also provides an article made from the above-described resin composition, the article comprising a prepreg, a resin film, a laminate, a printed circuit board, or a cured insulator.

[0013] The resin composition or its products provided by the present invention can improve one or more aspects such as glass transition temperature, dielectric constant, dielectric loss, heat resistance after moisture absorption, flame retardancy, amount of resin flowing into the plate, and drop ball test. Attached Figure Description

[0014] Figure 1 The FTIR spectra are of the raw material dimethylphenylsilane, the raw material hexa(4-vinylphenoxy)cyclotriphosphazene, and the product compound B.

[0015] Figure 2 The raw materials are dimethylphenylsilane, hexa(4-vinylphenoxy)cyclotriphosphazene, and product compound B. 1 H NMR spectrum.

[0016] Figure 3 This is the HPLC curve of product compound B. Detailed Implementation

[0017] To enable those skilled in the art to understand the features and effects of this 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 this invention, and in case of conflict, the definitions in this specification shall prevail.

[0018] In this document, the terms “comprising,” “including,” “having,” “containing,” or any similar terms are open-ended transitional phrases intended to encompass non-exclusive inclusions. For example, a composition or article containing a plurality of elements is not limited to those listed herein, but may also include other elements not explicitly listed but typically inherent to the composition or article. Furthermore, unless explicitly stated otherwise, the term “or” is inclusive, not exclusive. For example, the condition “P or Q” is satisfied in any of the following cases: P is true (or exists) and Q is false (or does not exist); P is false (or does not exist) and Q is true (or exists); both P and Q are true (or exist). Moreover, in this document, the terms “comprising,” “including,” “having,” and “containing” are interpreted as specifically revealing and simultaneously encompassing closed conjunctions such as “composed of” and conjunctions such as “substantially composed of.”

[0019] In this document, all features or conditions defined in the form of numerical ranges or percentage ranges are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as encompassing and specifically revealing all possible subranges and individual values ​​within those ranges, particularly integer values. For example, a range description of "1 to 8" should be considered as specifically revealing all subranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., particularly subranges defined by all integer values, and should be considered as specifically revealing individual values ​​within those ranges such as 1, 2, 3, 4, 5, 6, 7, 8, etc. Similarly, a range description of "between 1 and 8" should be considered as specifically revealing all ranges such as 1 to 8, 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., including endpoint values. Unless otherwise specified, the foregoing interpretation applies to all content throughout this invention, regardless of its scope.

[0020] If a quantity or other numerical value or parameter is expressed as a range, preferred range, or a series of upper and lower limits, it should be understood that this document has specifically disclosed all ranges consisting of any upper or preferred value of that range and the lower or preferred value of that range, whether such ranges are disclosed separately or not. Furthermore, when a range of numerical values ​​is mentioned herein, unless otherwise stated, the range shall include its endpoints and all integers and fractions within the range.

[0021] In this document, numerical values ​​are to be understood as having a precision with significant digits, provided that the purpose of the invention is achieved. For example, the number 40.0 should be understood to cover a range from 39.50 to 40.49.

[0022] 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 of all members within a Markush group or option list, or any individual member, 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 of all members within a Markush group or option list, or any individual member, 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 or X2 or X3 and Y is Y1 or Y2 or Y3 has been fully described. In this article, "or a combination thereof" means "or any combination thereof".

[0023] In this document, the phrase "a composition comprising A, B, and C, wherein A comprises a1, a2, or a3" is used, which is equivalent to "a composition comprising A, B, and C, wherein A comprises a1, a2, a3, or a combination thereof," that is, "a composition comprising A, B, and C, wherein A comprises a1, a2, a3, a combination of a1 and a2, a combination of a1 and a3, a combination of a2 and a3, or a combination of a1, a2, and a3."

[0024] In this paper, the term "isomer" refers to compounds that have the same molecular formula but differ in the bonding properties or sequence of their atoms or the spatial arrangement of their atoms.

[0025] In the structure of this paper, "*" represents the bonding site.

[0026] Unless otherwise specified, "resin" can generally be a common name for a synthetic polymer. However, in this invention, "resin" can be interpreted as monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and their polymers, etc., and is not limited thereto. For example, "maleimide resin" in this invention can be interpreted as maleimide monomers (maleimide small molecule compounds), maleimide polymers, combinations of maleimide monomers, combinations of maleimide polymers, or combinations of maleimide monomers and maleimide polymers.

[0027] 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 high molecular weight compounds. In this invention, the term "compound" 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. Furthermore, in this invention, a mixture refers to a combination of two or more compounds, and mixtures may also contain copolymers or other auxiliaries, etc., and are not limited thereto.

[0028] Unless otherwise specified, in this invention, a polymer refers to the product formed by the polymerization reaction of monomers, often including an aggregate of many high molecules, each of which is composed of many simple structural units linked by repeated covalent bonds. The monomer is the compound that synthesizes the polymer. Polymers may include homopolymers (also known as self-polymers), copolymers, prepolymers, etc., but are not limited to these.

[0029] Homopolymers are chemical substances formed by the polymerization, addition polymerization, or condensation polymerization of a single compound. Copolymers are chemical substances formed by the polymerization, addition polymerization, or condensation polymerization of two or more compounds, including 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-). Unless otherwise specified, in this invention, a prepolymer refers to a polymer with a lower molecular weight, between that of the monomer and the final polymer, and the prepolymer contains reactive functional groups that can be further polymerized to obtain a fully cross-linked or hardened product with a higher molecular weight.

[0030] Polymers certainly include oligomers, but are not limited to them. Oligomers, also known as low-molecular-weight polymers, are polymers composed of 2 to 20 repeating units, but are usually composed of 2 to 5 repeating units.

[0031] Unless otherwise specified, in this invention, modified products (also referred to as modified materials) 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 homopolymerization of each resin, products after copolymerization of each resin with other resins, etc. For example, but not limited to, modification may involve replacing the original hydroxyl groups with vinyl groups through a chemical reaction, or obtaining terminal hydroxyl groups by chemically reacting the original terminal vinyl groups with p-aminophenol.

[0032] Unless otherwise specified, the alkyl, alkenyl, and hydrocarbon groups mentioned in this invention are interpreted to include their various isomers. For example, propyl should be interpreted to include n-propyl and isopropyl.

[0033] Unless otherwise specified, "vinyl-containing" in this invention refers to a compound structure containing an vinyl carbon-carbon double bond (C=C) or a derivative functional group thereof. Therefore, examples of vinyl-containing compounds include, but are not limited to, compounds containing vinyl, allyl, vinyl benzyl, or methacrylate functional groups. Unless otherwise specified, the position of the aforementioned functional groups is not particularly limited; for example, they may be located at the end of a long chain structure. Therefore, for example, vinyl-containing polyphenylene ether resin represents, but is not limited to, polyphenylene ether resins containing vinyl, allyl, vinyl benzyl, or methacrylate functional groups.

[0034] 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.

[0035] In this document, parts by weight represent the number of parts of 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 vinyl polyphenylene ether resin can mean 100 kilograms of vinyl polyphenylene ether resin or 100 pounds of vinyl polyphenylene ether resin.

[0036] The following detailed embodiments are merely illustrative in nature and are not intended to limit the invention or its uses. Furthermore, this document is not limited to the foregoing prior art or the content of the invention, or any theory described in the following detailed embodiments or examples. Unless otherwise stated, the methods, reagents, and conditions used in the examples are conventional methods, reagents, and conditions in the art.

[0037] Compounds:

[0038] In one embodiment, the compound provided by the present invention has the structure shown in formula (I):

[0039]

[0040] In equation (I), n is an integer from 3 to 6, X and T are the same or different, and X and T are each independent as shown in equation (1) or equation (2), with at least one of X and T being equation (2), where m is an integer from 0 to 4, and R a R is an alkyl group with 1 to 4 carbon atoms and hydrogen atoms. b R c R d It is independently selected from alkyl, phenyl, or naphthyl groups having 1 to 4 carbon atoms.

[0041]

[0042] Unless otherwise specified, the compounds of formula (I) described in this invention include their various isomers.

[0043] In one embodiment, the structures of X and Y in the compound of formula (I) are shown in formula (3) or formula (4):

[0044]

[0045] In one embodiment, in the compound of formula (I), X and Y have at least two formulas (3) and at least two formulas (4).

[0046] For example, when n is 3, and X of compound (1) is formula (3) and T is formula (4), the number of formulas (3) is 2, 3 or 4, and the number of formulas (4) is 4, 3 or 2.

[0047] When n is 4, and X of compound (1) is formula (3) and T is formula (4), the number of formulas (3) is 2, 3, 4, 5 or 6, and the number of formulas (4) is 6, 5, 4, 3 or 2.

[0048] When n is 5, and X of compound (1) is formula (3) and T is formula (4), the number of formulas (3) can be 2, 3, 4, 5, 6, 7 or 8, and the number of formulas (4) can be 8, 7, 6, 5, 4, 3 or 2.

[0049] When n is 6, and X of compound (1) is formula (3) and T is formula (4), the number of formulas (3) can be 2, 3, 4, 5, 6, 7, 8, 9 or 10, and the number of formulas (4) can be 10, 9, 8, 7, 6, 5, 4, 3 or 2.

[0050] In the structure of the compound of formula (I) provided by the present invention, the phosphorus atom and nitrogen atom form a phosphazene ring with flame retardancy, and the presence of silicon atoms can play a synergistic flame retardant role. During thermal decomposition, it promotes polymer dehydration and carbonization, and at the same time forms a Si-C carbonaceous protective layer, which can give the material good flame retardant properties. Therefore, the compound of formula (I) has better flame retardancy.

[0051] For example, compounds of formula (I) contain at least two vinyl reactive functional groups, which can participate in the reaction and can be used as crosslinking agents; for example, compounds of formula (I) can provide better flame retardancy in double bond-containing resin systems such as BMI and polyphenylene oxide (PPO) compared to divinylbenzene (DVB), triallyl isocyanate (TAIC) or other conventional crosslinking agents.

[0052] For example, the compound of formula (I) in a polyphenylene oxide (PPO) system containing double bond resin can simultaneously improve one or more of the following properties: glass transition temperature, dielectric properties, heat resistance after moisture absorption, flame retardancy, amount of resin flowing into the board, or drop ball test.

[0053] For example, in order to simultaneously take into account both reactivity and dielectric properties, the compound of formula (I) preferably has the following structure.

[0054] In one embodiment, when n is 3, the compound of formula (I) has the structure shown in formula (II), formula (III), or formula (IV):

[0055]

[0056]

[0057] In one embodiment, when n is 4, the aforementioned compound of formula (I) has the structure shown in formula (V):

[0058]

[0059] In one embodiment, when n is 5, the aforementioned compound of formula (I) has the structure shown in formula (VI):

[0060]

[0061] In one embodiment, when n is 6, the aforementioned compound of formula (I) has the structure shown in formula (VII):

[0062]

[0063] Methods for manufacturing compounds

[0064] In one embodiment, the present invention provides a method for manufacturing a compound of formula (I), the main steps of which include: a step of performing a hydrosilylation reaction of vinylphenoxycyclophosphonitrile with a silane compound containing silane bonds.

[0065] For example, vinylphenoxycyclophosphonitrile can be obtained by reacting a silane compound containing silane bonds with a catalyst in a solvent under a nitrogen atmosphere and by heating under reflux.

[0066] In one embodiment, the catalyst is a catalyst that enables vinylphenoxycyclophosphonitrile to react with a silane compound containing silane bonds, such as bis(1,3-divinyl-1,1,3,3-tetramethyldisiloxane)platinum (also known as Karstedt catalyst). The catalyst can be added in a conventional manner, such as dropwise addition or pouring. The addition time of the catalyst can be between 1 hour and 6 hours, for example, between 1 hour and 5 hours or between 1 hour and 4 hours. The amount added is not particularly limited, as long as it can catalyze the reaction, for example, between 2 ppm and 30 ppm or between 3 ppm and 20 ppm.

[0067] In one embodiment, the heating temperature of the reaction may be between 5°C and 100°C, for example between 10°C and 90°C or between 20°C and 80°C, for example 30°C, 40°C, 50°C, 60°C, or 70°C.

[0068] In one embodiment, the reaction reflux time may be between 1 hour and 12 hours, for example, between 1 hour and 11 hours or between 1 hour and 10 hours.

[0069] In one embodiment, suitable solvents include, but are not limited to, benzene, toluene (TL), xylene, dimethylacetamide (DMAC), dimethylformamide (DMF), 2-propanol methyl ether (PM), propylene glycol methyl ether acetate (PMA), cyclohexanone (CYC), acetone, butanone (MEK), or combinations thereof. The amount of solvent used is not limited and can be between 200 ml and 1500 ml, for example, between 300 ml and 1300 ml or between 400 ml and 1200 ml.

[0070] In one embodiment, after the reaction step, an alcohol solvent, such as but not limited to methanol, may be used as needed to wash the initial product to remove byproducts and impurities from the reaction, thereby improving the purity of the obtained compound.

[0071] The amounts of both vinylphenoxycyclophosphonitrile and the silane compound containing silane bonds are not particularly limited. In one embodiment, when n is an integer from 3 to 6 in the compound of formula (I), the molar ratio of vinylphenoxycyclophosphonitrile to the silane compound containing silane bonds is between 1:1 and 1:2n. Preferably, the molar ratio is between 1:2 and 1:(2n-2), and more preferably, the molar ratio is 1:n.

[0072] As one of the reactants, the vinylphenoxycyclophosphonitrile may have the structure of formula (A), wherein n is an integer from 3 to 6, m is an integer from 0 to 4, and R a It is an alkyl group with 1 to 4 hydrogen atoms.

[0073]

[0074] For example, the vinylphenoxy cyclophosphonitrile is hexa(vinylphenoxy)cyclotriphosphonitrile, octa(vinylphenoxy)cyclotetraphosphonitrile, deca(vinylphenoxy)cyclopentaphosphonitrile or dodeca(vinylphenoxy)cyclohexaphosphonitrile.

[0075] In one embodiment, the vinylphenoxycyclophosphonitrile is preferably vinylphenoxycyclophosphonitrile in the para position.

[0076] As one of the reactants, the silane compound containing silane bonds may have the following structure (B):

[0077]

[0078] Among them, R b R c R d The silane compounds are independently selected from alkyl, phenyl, or naphthyl groups having 1 to 4 carbon atoms. For example, silane compounds containing silane-hydrogen bonds include triethylsilane, triisopropylsilane, triisobutylsilane, triphenylsilane, diphenylmethylsilane, tert-butyldiphenylsilane, tert-butyldimethylsilane, dimethylphenylsilane, dimethylnaphthylsilane, or combinations thereof.

[0079] Synthesis and qualitative analysis of compounds

[0080] Synthesis Example 1: Preparation of Compound A

[0081] In a three-necked flask, a thermometer and a condenser were inserted, and approximately 500 mL of toluene, 1 mol (approximately 849 g) of hexa(4-vinylphenoxy)cyclotriphosphazene, and 2 mol (approximately 272 g) of dimethylphenylsilane were added. Under a nitrogen atmosphere, the solution was heated to 60 °C, and 10 ppm of Karstedt catalyst was slowly added dropwise to the flask over 2 hours. The mixture was refluxed for another 8 hours. After the reaction was complete, the solution was cooled to room temperature to obtain compound A (possessing the structure shown in formula (II)).

[0082] The solution was then thoroughly washed with methanol. The lower transparent liquid was separated and retained in a separatory funnel. The lower transparent liquid was then placed in a vacuum desiccator and dried at room temperature for 12 hours to obtain the purified viscous liquid. The yield of compound A was approximately 85.0%.

[0083] Synthesis Example 2: Preparation of Compound B

[0084] Referring to the preparation method of Synthesis Example 1, the amount of toluene was adjusted to 550 mL and the amount of dimethylphenylsilane was adjusted to 3 mol (about 408 g). The other steps were the same, and compound B (with the structure shown in formula (III)) was obtained. The viscous liquid with a purity of more than 95% was obtained by the purification method of Synthesis Example 1, and the yield was about 95.5%.

[0085] Synthesis Example 3: Preparation of Compound C

[0086] Following the preparation method of compound A, the amount of toluene was adjusted to 600 mL and the amount of dimethylphenylsilane was adjusted to 4 mol (approximately 544 g). The other steps were the same, and compound C (with the structure shown in formula (IV)) was obtained. After purification using the method of synthesis example 1, its yield was approximately 92.0%.

[0087] Synthesis Example 4: Preparation of Compound D

[0088] Following the preparation method of compound A, the amount of toluene was adjusted to 750 mL, 1 mole of hexa(4-vinylphenoxy)cyclotriphosphazene was replaced with 1 mole of octa(4-vinylphenoxy)cyclotetraphosphazene (approximately 1132 g), and the amount of dimethylphenylsilane was adjusted to 4 moles (approximately 544 g). The other steps were the same, and compound D (possessing the structure shown in formula (V)) was obtained. After purification using the method of synthesis example 1, its yield was approximately 88.0%.

[0089] Synthesis Example 5: Preparation of Compound E

[0090] Following the preparation method of compound A, the amount of toluene was adjusted to 900 mL, 1 mole of hexa(4-vinylphenoxy)cyclotriphosphazene was replaced with 1 mole of deca(4-vinylphenoxy)cyclopentaphosphazene (approximately 1415 g), and the amount of dimethylphenylsilane was adjusted to 5 moles (approximately 680 g). The other steps were the same, and compound E (possessing the structure shown in formula (VI)) was obtained. After purification using the method of synthesis example 1, its yield was approximately 92.0%.

[0091] Synthesis Example 6: Preparation of Compound F

[0092] Following the preparation method of compound A, the amount of toluene was adjusted to 1100 mL, 1 mole of hexa(4-vinylphenoxy)cyclotriphosphazene was replaced with 1 mole of dodeca(4-vinylphenoxy)cyclohexaphosphazene (approximately 1698 g), and the amount of dimethylphenylsilane was adjusted to 6 moles (approximately 816 g). The other steps were the same, and compound F (having the structure shown in formula (VII)) was obtained. After purification according to the purification method of synthesis example 1, its yield was approximately 90.0%.

[0093] Comparative Synthesis Example 1: Preparation of Compound 1

[0094] First, 40.2 g (0.3 mol) of 4-allylphenol was added to a three-necked flask equipped with a mechanical stirrer and nitrogen gas. 250 mL of dioxane was added and stirred until dissolved. Then, 0.26 g of tetrabutylammonium bromide was added and the mixture was stirred at room temperature for 30 minutes. Next, 11.73 g (0.3 mol) of sodium hydroxide was added to the flask, and the temperature was raised to 40 °C and maintained for 3 hours. Then, 15.62 g (0.045 mol) of hexachlorocyclotriphosphazene was dissolved in 80 mL of dioxane, and this solution was added dropwise to the reaction system. The temperature was raised to 70 °C and stirred for 48 hours. After the reaction was complete, the solution was cooled to room temperature and filtered to remove the solid. The filtrate was then concentrated by rotary evaporation to remove the solvent. The crude product was washed three times with ethanol to obtain a white solid powder.

[0095] Referring again to the method of Synthesis Example 2, 1 mole of hexa(4-vinylphenoxy)cyclotriphosphazene was replaced with 1 mole of white solid powder (about 891 g), and the other steps were the same, to obtain compound 1, as shown in formula (C-1).

[0096]

[0097] Comparative Synthesis Example 2: Preparation of Compound 2

[0098] Using hexachlorocyclotriphosphazene, 4-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 compound of p-vinylphenylcyclotriphosphazene, namely compound 2, with the structure shown in formula (C-2) below.

[0099]

[0100] Comparative Synthesis Example 3: Preparation of Compound 3

[0101] The structure obtained by referring to the preparation method in CN116003468A is shown in formula (C-3).

[0102]

[0103] Comparative Synthesis Example 4: Preparation of Compound 4

[0104] Referring to Synthesis Example 2, replace dimethylphenylsilane with phenyltris(dimethylsiloxane)silane (purchased from Suzhou Sisso), and follow the same steps to obtain compound 4.

[0105] Comparative Synthesis Example 5: Preparation of Compound 5

[0106] Referring to Synthesis Example 1, hexa(4-vinylphenoxy)cyclotriphosphazene was replaced with allylphosphazene SPV-100 (purchased from Otsuka Chemical), and the amount of dimethylphenylsilane was changed to 1 mole. The other steps were the same, and compound 5 was obtained, with the structure shown in formula (C-5) below.

[0107]

[0108] Characterization of compound B:

[0109] Compared to hexa(4-ethylenephenoxy)cyclotriphosphazene, which also contains a phosphazene ring and has a vinyl reactive functional group, compound (I) has a longer shelf life. For example, in one embodiment, hexa(4-ethylenephenoxy)cyclotriphosphazene has a shelf life of 8 weeks at a temperature of 0°C to 8°C, while compound B has a shelf life of more than 6 months. The longer shelf life indicates that compound B has stable properties and is also convenient for raw material preservation.

[0110] In addition, compound B and hexa(4-vinylphenoxy)cyclotriphosphazene were used as test samples, and their gel times (SG) were measured according to the method described in IPC-TM-6502.3.18. 2.0 mL of each test sample was placed on a heated plate at a temperature of 171±0.5℃. A pointed bamboo stick was used to stir from the center of the gel towards the edge, maintaining a gel area diameter of 1.90 to 2.19 cm. The mixture was stirred until the test samples began to clump together, and stirring continued until the largest gel block broke. The timer was stopped and the time was recorded, accurate to the second. The gel time was then measured using the same method at heated plate temperatures of 131±0.5℃ and 151±0.5℃.

[0111] The gel times (SG) of compound B and hexa(4-vinylphenoxy)cyclotriphosphazene obtained according to the above method are as follows:

[0112] SG / 131℃ SG / 151℃ SG / 171℃ Compound B >10 minutes 177 seconds 88 seconds Hexa(4-vinylphenoxy)cyclotriphosphazene 55 seconds 20 seconds 10 seconds

[0113] The test results above show that compound B has a longer gel time than hexa(4-ethylenephenoxy)cyclotriphosphazene at all temperatures, indicating that compound B is more reactive and can provide a longer reaction window.

[0114] The purified compound B was subjected to infrared (FTIR) and nuclear magnetic resonance (NMR) analyses. 1 Analysis by ¹H NMR and high performance liquid chromatography (HPLC):

[0115] Figure 1 The upper, middle, and lower curves are, in order, the FTIR spectra of the raw material dimethylphenylsilane, the raw material hexa(4-vinylphenoxy)cyclotriphosphazene, and the product compound B.

[0116] In the FTIR spectrum of dimethylphenylsilane, a 2200 cm⁻¹ can be observed. -1 The peak at 2200 cm⁻¹ corresponds to the stretching vibration absorption of the Si-H bond. Comparison revealed that in the FTIR spectrum of compound B, the peak at 2200 cm⁻¹ is... -1 The disappearance of the Si-H bond stretching vibration absorption peak at 800 cm⁻¹ indicates that the Si-H bond in dimethylphenylsilane has undergone a near-complete reaction. -1 and 960cm -1 The addition of characteristic Si-C peaks proves that dimethylphenylsilane and hexa(4-vinylphenoxy)cyclotriphosphazene reacted, consistent with the expected structure of the compound.

[0117] Figure 2 The upper, middle, and lower curves represent, in order, the raw material dimethylphenylsilane, the raw material hexa(4-vinylphenoxy)cyclotriphosphazene, and the product compound B. 1 H NMR spectrum.

[0118] Among them, the dimethylphenylsilane above 1 In the 1H NMR spectrum, the chemical shift δ = 0.0–1.0 ppm represents the -CH3 proton peak in dimethylphenylsilane; the δ = 4.0–5.0 ppm represents the Si-H proton peak in dimethylphenylsilane; comparing the middle hexa(4-vinylphenoxy)cyclotriphosphazene and the lower compound B... 1 1H NMR spectrum, compound B 1 The 1H NMR spectrum revealed a proton peak on the benzene ring at δ = 7.0–7.5 ppm; proton peaks at δ = 5–6 ppm and δ = 6.5–7.0 ppm were observed on the carbon-carbon double bond, which is consistent with the proton peak chemical shift of hexa(4-vinylphenoxy)cyclotriphosphazene; a newly added methyl and methylene region appeared at δ = 1.0–2.0 ppm, and the Si-H proton peak at δ = 4.0–5.0 ppm disappeared. This indicates that the Si-H bond in dimethylphenylsilane has been reacted and undergone a hydrosilylation reaction with hexa(4-vinylphenoxy)cyclotriphosphazene to give compound B.

[0119] Figure 3 This is the high-performance liquid chromatography (HPLC) curve of product compound B. The HPLC curve shows the strongest peak at a retention time of 6.821 minutes, with a peak area of ​​95.26%, confirming that the purity of compound B exceeds 95%.

[0120] Another major object of the present invention is to provide a resin composition comprising a compound of formula (I), a vinyl-containing polyphenylene ether resin, and a vinyl-containing crosslinking agent, wherein:

[0121] The content of the vinyl polyphenylene ether resin is 100 parts by weight, the content of the vinyl crosslinking agent is 15 to 45 parts by weight, and the content of the compound of formula (I) is 80 to 120 parts by weight.

[0122] For example, in one embodiment, the vinyl-containing polyphenylene ether resin used in this invention refers to a polyphenylene ether compound or mixture having an vinyl carbon-carbon double bond (C=C) or its derivative functional groups. Examples of the aforementioned vinyl carbon-carbon double bond (C=C) or its derivative functional groups may include, but are not limited to, functional groups containing vinyl, vinylidene, allyl, vinylbenzyl, methacrylate, etc., in the structure. Unless otherwise specified, the position of the aforementioned functional groups is not particularly limited; for example, they may be located at the end of a long chain structure. In other words, in this invention, for example, a vinyl-containing polyphenylene ether resin represents a polyphenylene ether resin containing reactive vinyl or its derivative functional groups, examples of which may include, but are not limited to, polyphenylene ether resins containing vinyl, vinylidene, allyl, vinylbenzyl, or methacrylate.

[0123] For example, in one embodiment, the vinyl-containing polyphenylene ether resin used in this invention includes terminal vinyl benzyl polyphenylene ether resin, terminal methacrylate polyphenylene ether resin (i.e., terminal methacryloyl polyphenylene ether resin), terminal allyl polyphenylene ether resin, or a combination thereof.

[0124] For example, the terminal vinyl benzyl polyphenylene ether resin and the terminal methacrylate polyphenylene ether resin respectively comprise the structures shown in formula (A-1) and formula (A-2):

[0125]

[0126]

[0127] Among them, R1 to R 14 Each is independently H or -CH3, and W1 and W2 are independently C1 to C3 divalent aliphatic groups;

[0128] b1 is an integer from 0 to 8;

[0129] Q1 includes any one or a combination of the structures shown in equations (B-1) to (B-3):

[0130]

[0131] Y1 and Y2 each independently include the structure shown in equation (B-4):

[0132]

[0133] Among them, R 15 To R 30 Each is independently H or -CH3; m1 and n1 are each independently an integer from 1 to 30; and A1 is selected from covalent bonds, -CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -S-, -SO2- and carbonyl groups.

[0134] For example, the vinyl polyphenylene ether resin may be a methacrylate polyphenylene ether resin (e.g., SA9000, available from Sabic Corporation), a vinyl benzyl polyphenylene ether resin with a number average molecular weight of approximately 1200 (e.g., OPE-2st 1200, available from Mitsubishi Gas Chemical Corporation), a vinyl benzyl polyphenylene ether resin with a number average molecular weight of approximately 2200 (e.g., OPE-2st 2200, available from Mitsubishi Gas Chemical Corporation), a vinyl benzyl modified bisphenol A polyphenylene ether resin with a number average molecular weight of approximately 2400 to 2800, a vinyl chain-extended polyphenylene ether resin with a number average molecular weight of approximately 2200 to 3000, or a combination thereof. The vinyl chain-extended polyphenylene ether resin may include various polyphenylene ether resins disclosed in U.S. Patent Application Publication No. 2016 / 0185904A1, the entire contents of which are incorporated herein by reference.

[0135] For example, in one embodiment, the vinyl-containing crosslinking agent used in this invention refers to a compound, polymer, or mixture having an vinyl carbon-carbon double bond (C=C) or its derived functional groups in its molecule, and capable of undergoing a crosslinking reaction with a vinyl-containing polyphenylene ether resin. Furthermore, the vinyl-containing crosslinking agent is different from the aforementioned vinyl-containing polyphenylene ether resin.

[0136] For example, the vinyl crosslinking agent refers to a vinyl compound or polymer with a molecular weight of less than or equal to 5,000, preferably with a molecular weight between 100 and 4,000, and more preferably with a molecular weight between 100 and 3,000. The vinyl-containing crosslinking agents include, but are not limited to, styrene, divinylbenzene, divinylnaphthalene, divinylbiphenyl, tert-butylstyrene, bis(vinylbenzyl)ether, 1,2,4-trivinylcyclohexane (TVCH), bis(vinylphenyl)ethane (BVPE), di(vinylphenyl)hexane, divinylphenyldimethyl ether, divinylphenyldimethylbenzene, triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), diallyl bisphenol A, butadiene, decanadiene, octadiene, vinylcarbazole, acrylates, or combinations thereof. Isomeric or polymeric forms of these components are also included in the interpretation.

[0137] For example, in one embodiment, the resin composition may further comprise a polyolefin resin. The polyolefin includes any one or a combination of polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene terpolymer, ethylene-divinylbenzene-styrene polymer, styrene-divinylbenzene-ethylstyrene polymer, styrene-butadiene-styrene copolymer, maleic anhydride-added styrene-butadiene copolymer, vinyl-polybutadiene-urea polymer, maleic anhydride-added polybutadiene, polymethylstyrene, hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated styrene-butadiene-divinylbenzene terpolymer, hydrogenated styrene-butadiene-styrene copolymer, hydrogenated maleic anhydride-added styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, and hydrogenated styrene-isoprene copolymer.

[0138] The amount of the polyolefin resin is not particularly limited. In one embodiment, the resin composition may contain 20 to 60 parts by weight of polyolefin resin relative to a total of 100 parts by weight of vinyl polyphenylene ether resin, preferably 30 to 50 parts by weight of polyolefin resin.

[0139] Unless otherwise specified, the resin compositions of the present invention may also include, as needed, maleimide resin, maleimide triazine resin, styrene maleic anhydride resin, epoxy resin, phenolic resin, benzoxazine resin, cyanate ester resin, polyester resin, polyamide resin, polyimide resin, or combinations thereof.

[0140] In one embodiment, the resin composition comprises a maleimide resin. The maleimide resin may be a multifunctional maleimide resin. The multifunctional maleimide resin may include, but is not limited to, 4,4′-diphenylmethane bismaleimide, benzene maleimide oligomers, biphenyl aryl bismaleimide, indane-containing bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, multifunctional maleimide resins containing aliphatic long-chain structures, or combinations thereof.

[0141] For example, the maleimide resin may be a maleimide resin produced by Daiwa Kasei Corporation under trade names such as 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 produced by KI Chemicals Corporation under trade names such as BMI-70 and BMI-80; or a maleimide resin produced by Nippon Kayaku Co., Ltd. under trade name such as MIR-3000; or a maleimide resin produced by DIC (Dai Nippon Ink Chemicals) Co., Ltd. under trade names such as X9-470, NE-X-9470S, and NE-X-9480.

[0142] For example, the maleimide resin containing an aliphatic long-chain structure may be a maleimide resin manufactured by the designer's subsidiary under trade names such as BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000, and BMI-6000. The maleimide resin containing the aliphatic long-chain structure may have at least one maleimide functional group linked to a substituted or unsubstituted long-chain aliphatic group. The long-chain aliphatic group may have a carbon number from C5 to C6. 50 Aliphatic groups, such as those with a carbon number of C 10 To C 50 C 20 To C 50 C 30 To C 50 C 20 To C 40 Or C 30 To C 40 However, it is not limited to this.

[0143] In one embodiment, the resin composition comprises a maleimide triazine resin. The maleimide triazine resin may be any one or more suitable for manufacturing prepregs, resin films, laminates, printed circuit boards, or cured insulators. The maleimide triazine resin may be obtained by polymerizing a cyanate ester resin with a maleimide resin, particularly by polymerizing a bisphenol A cyanate ester resin with a maleimide resin, a bisphenol F cyanate ester resin with a maleimide resin, a phenolic phenolic cyanate ester resin with a maleimide resin, or a dicyclopentadiene-containing cyanate ester resin with a maleimide resin. Maleimide triazine resin can be obtained by polymerization of cyanate resin and maleimide resin in any molar ratio, particularly by polymerization of cyanate resin and maleimide resin in a molar ratio of (1-10):1, especially (1-6):1, and even more particularly 1:1, 2:1, 4:1, or 6:1.

[0144] In one embodiment, the resin composition comprises a styrene-maleic anhydride resin. The molar ratio of styrene to maleic anhydride in the styrene-maleic anhydride resin can be (1–8):1, for example, 1:1, 2:1, 3:1, 4:1, 6:1, or 8:1. The styrene-maleic anhydride resin can be a styrene-maleic anhydride copolymer. The styrene-maleic anhydride copolymer can be a styrene-maleic anhydride copolymer purchased from Cray Valley under trade names such as SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60, EF-80, etc., or a styrene-maleic anhydride copolymer sold by Polyscope under trade names such as C400, C500, C700, C900, etc., but is not limited thereto. The styrene-maleic anhydride resin can be an esterified styrene-maleic anhydride copolymer. The esterified styrene-maleic anhydride copolymer may be, but is not limited to, esterified styrene-maleic anhydride copolymers purchased from Cray Valley under trade names such as SMA1440, SMA17352, SMA2625, SMA3840, and SMA31890. The resin composition may include one of the styrene-maleic anhydride resins, or a combination of multiple styrene-maleic anhydride resins.

[0145] In one embodiment, the resin composition may further comprise an epoxy resin. For example, the epoxy resin may be any type of epoxy resin known in the art, including but not limited to bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD ​​epoxy resin, phenolic (novolac) epoxy resin (e.g., multifunctional phenolic epoxy resin), trifunctional epoxy resin, tetrafunctional 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.

[0146] Phenolic epoxy resins may be phenol novolac epoxy resins, bisphenol A novolac epoxy resins, bisphenol F novolac epoxy resins, biphenylnovolac epoxy resins, phenol benzaldehyde epoxy resins, phenolaralkyl novolac epoxy resins, or o-cresol novolac epoxy resins, or combinations thereof.

[0147] 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 phenolic novolac epoxy resin, DOPO-containing cresol novolac epoxy resin, and DOPO-containing bisphenol-Anovolac epoxy resin; the aforementioned DOPO-HQ epoxy resin may be selected from at least one of the following: DOPO-containing phenolic novolacepoxy resin, DOPO-HQ-containing cresol novolacepoxy resin, and DOPO-HQ-containing bisphenol-Anovolac epoxy resin.

[0148] In one embodiment, the epoxy resin may include biphenyl-type phenolic epoxy resin, dicyclopentadiene epoxy resin, o-methylphenolic epoxy resin, naphthol-type epoxy resin, or a combination thereof.

[0149] In one embodiment, the resin composition comprises a phenolic resin. The phenolic resin may be a monofunctional phenolic resin, a polyfunctional phenolic resin, or a combination thereof, but is not limited thereto. The phenolic resin may include phenoxy resin, phenolic resin, or a combination thereof, but is not limited thereto.

[0150] In one embodiment, the resin composition comprises a benzoxazine resin. The benzoxazine resin may include, but is not limited to, bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, phenolphthalein type benzoxazine resin, dicyclopentadiene benzoxazine resin, phosphorus-containing benzoxazine resin, diamine type benzoxazine resin, and vinyl or allyl modified benzoxazine resins or combinations thereof. Examples of benzoxazine resins include, for instance, Huntsman's trade name LZ-8270 (phenolphthalein type benzoxazine resin), LZ-8280 (bisphenol F type benzoxazine resin), LZ-8290 (bisphenol A type benzoxazine resin), or Showa Polymer's trade name HFB-2006M. The diamine-type benzoxazine resin may be a diaminodiphenylmethane benzoxazine resin, a diaminodiphenyl ether benzoxazine resin, a diaminodiphenyl sulfone benzoxazine resin, a diaminodiphenyl sulfide benzoxazine resin, or a combination thereof.

[0151] In one embodiment, the resin composition comprises a cyanate ester resin. The cyanate ester resin may be any type of cyanate ester resin known in the art. The cyanate ester resin may include, but is not limited to, a cyanate ester resin having an Ar-OC≡N structure (where Ar is an aromatic group, such as benzene, naphthalene, or anthracene). The cyanate ester resin may include, but is not limited to, phenolic cyanate ester resins, bisphenol A cyanate ester resins, bisphenol A phenolic cyanate ester resins, bisphenol F cyanate ester resins, bisphenol F phenolic cyanate ester resins, cyanate ester resins containing a dicyclopentadiene structure, cyanate ester resins containing a naphthalene ring structure, phenolphthalein cyanate ester resins, or combinations thereof. Cyanate ester resins may include, but are not limited to, 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, LeCy, etc.

[0152] In one embodiment, the resin composition comprises a polyester resin. The polyester resin is formed by esterification of an aromatic compound having a dicarboxylic acid group with an aromatic compound having a dihydroxyl group. The polyester resin may be, but is not limited to, HPC-8000, HPC-8150, HPC-8200, or combinations thereof, available from Dai Nippon Ink Chemical Co., Ltd.

[0153] In one embodiment, the resin composition comprises a polyamide resin. The polyamide resin may be any type of polyamide resin known in the art, including but not limited to various commercially available polyamide resin products.

[0154] In one embodiment, the resin composition comprises a polyimide resin. The polyimide resin may be any type of polyimide resin known in the art, including but not limited to various commercially available polyimide resin products.

[0155] In one embodiment, the resin composition disclosed in this invention may further include, as needed, amine curing agents, flame retardants, inorganic fillers, curing accelerators, polymerization inhibitors, colorants, solvents, toughening agents, silane coupling agents, or combinations thereof.

[0156] In one embodiment, the resin composition includes an amine curing agent. The amine curing agent may include, but is not limited to, dicyandiamide, diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfide, or combinations thereof.

[0157] In one embodiment, the resin composition includes a flame retardant. The flame retardant may be any one or more flame retardants suitable for the manufacture of prepregs, resin films, laminates, printed circuit boards, or cured insulators.

[0158] The flame retardant may be a phosphorus-containing flame retardant. Flame retardants may include ammonium polyphosphate, hydroquinone bis-(diphenylphosphate), bisphenol A bis-(diphenylphosphate), tri(2-carboxyethyl)phosphine (TCEP), trichloroisopropyl phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), resorcinol bis(dixylenyl phosphate) (RDXP, such as commercially available products PX-200, PX-201, PX-202, etc.), phosphazene compounds (such as commercially available products SPB-100, SPH-100, SPV-100, etc.), and melamine polyphosphate. Polyphosphate, DOPO and its derivatives or resins, diphenylphosphine oxide (DPPO) and its derivatives or resins, melamine cyanurate, tri-hydroxyethyl isocyanurate, aluminum phosphonates (e.g., OP-930, OP-935, etc.) or combinations thereof, but not limited to these.

[0159] The flame retardant may be a DPPO compound (such as a bisDPPO compound), a DOPO compound (such as a bisDOPO compound), a DOPO resin (such as DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN), a DOPO-bonded epoxy resin, or a combination thereof, but is not limited thereto. Specifically, DOPO-PN is a DOPO phenolic compound, and DOPO-BPN may be a bisphenolic compound such as DOPO-BPAN (DOPO-bisphenol Anovolac), DOPO-BPFN (DOPO-bisphenol F novolac), or DOPO-BPSN (DOPO-bisphenol S novolac). For example, in one embodiment, relative to 100 parts by weight of the vinyl polyphenylene ether resin, the resin composition of the present invention may further include 1 to 20 parts by weight of a flame retardant, preferably 5 to 10 parts by weight, but not limited thereto.

[0160] In one embodiment, the resin composition includes an inorganic filler. The inorganic filler may be any one or more fillers suitable for making resin films, prepregs, laminates, printed circuit boards, or cured insulators. The inorganic filler may be 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, zinc oxide, zirconium oxide, mica, boehmite (AlOOH), calcined talc, talc, silicon nitride, calcined kaolin, or combinations thereof, but is not limited thereto. The inorganic filler may be spherical, fibrous, plate-like, granular, flake-like, or needle-like. The inorganic filler may be pretreated with a silane coupling agent (especially an aminosilane coupling agent). The inorganic filler may be spherical silica with a surface treated with an aminosilane coupling agent.

[0161] The amount of the inorganic filler is not particularly limited. In one embodiment, the resin composition may contain 20 to 200 parts by weight of inorganic filler, preferably 50 to 150 parts by weight, but not limited to 100 parts by weight of all resins in the resin composition (excluding silane coupling agents, curing accelerators, solvents and inorganic fillers).

[0162] In one embodiment, the resin composition includes a curing accelerator. The curing accelerator may include catalysts such as Lewis bases and Lewis acids. Lewis bases may include, but are not limited to, imidazole, boron trifluoride amine complexes, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP), 4-dimethylaminopyridine (DMAP), or combinations thereof. Lewis acids may include metal salt compounds, such as manganese, iron, cobalt, nickel, copper, and zinc salts, particularly metal catalysts such as zinc octoate and cobalt octoate. The curing accelerator may include a curing initiator (i.e., a curing starter). The curing initiator may include a peroxide capable of generating free radicals. The curing initiator includes, but is not limited to, 2,3-dimethyl-2,3-diphenylbutane, dicumyl peroxide, tert-butyl peroxide, tert-butyl isopropyl percarbonate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B), bis(tert-butylperoxyisopropyl)benzene, azobisisobutyronitrile, or combinations thereof. For example, in one embodiment, the resin composition of the present invention may further include 0.001 parts by weight to 1 part by weight of a curing accelerator, preferably 0.01 parts by weight to 1.0 parts by weight, more preferably 0.15 parts by weight to 0.6 parts by weight of a curing accelerator, relative to 100 parts by weight of the vinyl-containing polyphenylene ether resin.

[0163] In one embodiment, the resin composition includes a polymerization inhibitor. The polymerization inhibitor may be any type of polymerization inhibitor known in the art, including but not limited to various commercially available polymerization inhibitor products. The polymerization inhibitor may include, but is not limited to, 1,1-diphenyl-2-trinitrophenylhydrazine, methacrylonitrile, disulfide, nitroxide-stabilized free radicals, triphenylmethyl free radicals, metal ion free radicals, sulfur free radicals, hydroquinone, p-methoxyphenol, p-benzoquinone, phenthiazide, β-phenylnaphthylamine, p-tert-butylcatechol, methylene blue, 4,4′-butylenebis(6-tert-butyl-3-methylphenol), 2,2′-methylenebis(4-ethyl-6-tert-butylphenol), or combinations thereof, but is not limited thereto. The polymerization inhibitor may include or consist of nitroxide-stabilized free radicals. Nitrogen oxide-stabilized free radicals may include, but are not limited to, 2,2,6,6-tetrasubstituted piperidine-1-oxo radicals, 2,2,5,5-tetrasubstituted pyrrolidine-1-oxo radicals, or combinations thereof derived from cyclic hydroxylamines. The term "substituent" here refers to alkyl groups having 4 or fewer carbon atoms, such as methyl, ethyl, propyl, butyl, particularly methyl or ethyl. Nitrogen oxide-stabilized free radicals may be, but are not limited to, 2,2,6,6-tetramethylpiperidine-1-oxo radicals, 2,2,6,6-tetraethylpiperidine-1-oxo radicals, 2,2,6,6-tetramethyl-4-oxopiridine-1-oxo radicals, 2,2,5,5-tetramethylpyrrolidine-1-oxo radicals, 1,1,3,3-tetramethylisoindoline-2-oxo radicals, N,N-di-tert-butylamine-oxo radicals, or combinations thereof. Stable free radicals such as galvinoxyl radicals can also be used to replace nitrogen and oxygen free radicals. The polymerization inhibitor can also be a product derived from the substitution of hydrogen atoms or groups in the aforementioned polymerization inhibitor by other atoms or groups, such as products derived from the substitution of hydrogen atoms in the polymerization inhibitor by amino, hydroxyl, or ketone carbonyl groups.

[0164] In one embodiment, the resin composition includes a dyeing agent. The dyeing agent may include, but is not limited to, dyes or pigments.

[0165] In one embodiment, the resin composition includes a solvent. Adding a solvent can alter the solid content of the resin composition and adjust its viscosity. Solvents 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, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide, propylene glycol methyl ether, or combinations thereof. The solvent added to the resin composition may evaporate and be removed during the processing of the resin composition into a prepreg or resin film, so that the insulating layer of the prepreg or resin film contains no solvent or only trace amounts of solvent less than or equal to 3 wt% (i.e., 3% by weight). Therefore, the presence or absence of solvent in the resin composition does not affect the properties of the product.

[0166] In one embodiment, the resin composition includes a toughening agent. The toughening agent can improve the toughness of the resin composition. The toughening agent may include, but is not limited to, carboxyl-terminated butadiene acrylonitrile rubber (CTBN), core-shell rubber, or combinations thereof.

[0167] In one embodiment, the resin composition includes a silane coupling agent. The silane coupling agent may include silane compounds, including but not limited to siloxane compounds. Silane coupling agents may include, but are not limited to, amino silane compounds, epoxide silane compounds, vinyl silane compounds, acrylate silane compounds, methacrylate silane compounds, hydroxy silane compounds, isocyanate silane compounds, methacryloxy silane compounds, acryloyloxy silane compounds, or combinations thereof.

[0168] The resin compositions of the foregoing embodiments can be made into various articles, such as components used in various electronic products, including but not limited to prepregs, resin films, laminates, printed circuit boards, or cured insulators.

[0169] The article may include the resin composition in a semi-cured (B-stage) or cured (C-stage) state. The article may include a resin layer, which is the resin composition in a semi-cured or cured state. The article may include an insulating layer, which is the resin composition in a cured state.

[0170] In one embodiment, the present invention provides a prepreg. The prepreg may include a reinforcing material and a semi-cured layer disposed on the reinforcing material, wherein the semi-cured layer is a semi-cured resin composition. The semi-cured layer can be obtained by heating the resin composition to form a semi-cured state. In one embodiment, the present invention provides a method for preparing a prepreg, comprising: disposing a resin composition on a reinforcing material, semi-curing the resin composition, particularly heating the resin composition to form a prepreg comprising the reinforcing material and the semi-cured layer. Disposing the resin composition on the reinforcing material may include coating the resin composition onto the reinforcing material. The heating may be baking heating. The heating may be heating to a semi-curing temperature. The semi-curing temperature may be between 100°C and 200°C. The reinforcing material may be a fibrous material, woven fabric, nonwoven fabric, or a combination thereof, and is not limited thereto. The woven fabric may include fiberglass cloth. There is no particular limitation on the type of fiberglass cloth; it may be commercially available fiberglass cloth suitable for various printed circuit boards. The fiberglass cloth can be type E, type D, type S, type T, type L, or type Q, wherein the fiber type includes yarn or roving, and the form can include open or closed fibers. The woven fabric can include liquid crystal resin woven fabric. Liquid crystal resin woven fabric can include polyester woven fabric, polyurethane woven fabric, or combinations thereof, and is not limited thereto. The nonwoven fabric can include liquid crystal resin nonwoven fabric. Liquid crystal resin nonwoven fabric can include polyester nonwoven fabric, polyurethane nonwoven fabric, or combinations thereof, and is not limited thereto. The reinforcing material can, for example, increase the mechanical strength of the prepreg; in one embodiment, the reinforcing material can also be pretreated with a silane coupling agent.

[0171] In one embodiment, the present invention provides a resin film. The resin film may comprise a semi-cured resin composition. In one aspect, the present invention provides a method for preparing a resin film, comprising semi-curing the resin composition, particularly heating the resin composition. The method for preparing the resin film may further comprise coating the resin composition onto a substrate. In one embodiment, the present invention provides a resin film assembly comprising a substrate and the resin film disposed on the substrate. In another aspect, the present invention provides a method for preparing a resin film assembly, comprising providing a substrate and disposing the resin film on the substrate. In one embodiment, disposing the resin film on the substrate comprises: coating the resin composition onto the substrate, and semi-curing the resin composition, particularly heating the resin composition. The substrate may be a polyethylene terephthalate film (PET film), a polyimide film (PI film), copper foil, adhesive-backed copper foil, or a combination thereof, but is not limited thereto. The heating may be, for example, baking heating. The heating may be heating to a semi-curing temperature. The semi-curing temperature may be between 100°C and 200°C.

[0172] In one embodiment, the present invention provides a laminate. The laminate may include at least two metal foils and an insulating layer disposed between the metal foils. In one embodiment, the insulating layer separates the metal foils. The metal foils may include copper, aluminum, nickel, platinum, silver, gold, or alloys thereof, particularly copper foil. The insulating layer may be obtained by heating and curing the aforementioned resin composition or the aforementioned semi-cured resin composition. The heating may be, for example, baking. The heating and curing may be heating to a curing temperature. The curing temperature may be between 180°C and 250°C, particularly between 210°C and 240°C. The curing time may be between 80 minutes and 180 minutes, particularly between 100 minutes and 150 minutes. The curing may further include applying pressure to the semi-cured resin composition. The insulating layer may be formed by curing the aforementioned semi-cured sheet or resin film (C-stage). The laminate may be, for example, a copper clad laminate (CCL).

[0173] The multilayer board can be further processed into a circuit board, such as a printed circuit board, through circuit technology. One method of manufacturing the printed circuit board of the present invention involves using a double-sided copper-clad laminate (e.g., product EM-890, available from Taikoo Electronic Materials) of a certain thickness, for example 28 mil, with 0.5 ounce (oz) HVLP (hyper very low profile), with copper foil on both sides. After drilling, electroplating is performed to create electrical conductivity between the upper and lower copper foil layers. The upper and lower copper foil layers are then etched to form the inner layer circuitry. Next, the inner layer circuitry undergoes a browning and 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 in a vacuum lamination apparatus at a temperature of 180°C to 250°C for 80 to 180 minutes to cure the insulating 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.

[0174] In one embodiment, the present invention provides a cured insulator. In another embodiment, the present invention provides a method for preparing a cured insulator, comprising: curing the resin composition once or curing the resin composition through a multiple curing process. Multiple curing refers to two or more curing processes. For example, the resin composition may be semi-cured first, particularly by heating the resin composition to obtain a semi-cured resin composition; then the semi-cured resin composition may be further cured, particularly by heating the semi-cured resin composition. The cured insulator may include the cured resin composition, the cured resin composition containing reinforcing materials, or a combination thereof. Heating may be, for example, baking. In one embodiment, the semi-curing of the resin composition is achieved by heating to a semi-curing temperature. The semi-curing temperature may be 100°C to 200°C.

[0175] In one embodiment, the primary curing of the resin composition or the curing of the semi-cured resin composition is performed by heating to a curing temperature. The curing temperature may be between 180°C and 250°C, preferably between 210°C and 240°C. In one embodiment, the curing time is between 80 minutes and 180 minutes, particularly 100 minutes to 150 minutes. The curing may further include applying pressure to the resin composition or the semi-cured resin composition.

[0176] The cured insulator may include the cured resin composition. In one embodiment, the present invention provides a method for preparing a cured insulator, comprising: curing the resin film, particularly heating the resin film. The method for preparing a cured insulator may further comprise coating the resin composition onto a substrate, and / or semi-curing the resin composition to form a resin film.

[0177] The cured insulator may include the cured resin composition in a cured state containing reinforcing material. In one embodiment, the present invention provides a method for preparing a cured insulator, comprising: curing the prepreg, particularly heating the prepreg. The method for preparing a cured insulator may further comprise disposing the resin composition on a reinforcing material, prepreg, particularly heating the resin composition, to form a prepreg comprising the reinforcing material and a prepreg layer.

[0178] The method for preparing the cured insulator may further include molding. For example, the resin composition or semi-cured resin composition may be placed in a mold, and the resin composition or semi-cured resin composition may be formed and cured in the mold under curing temperature and certain pressure to obtain a cured insulator of a specific shape.

[0179] The cured insulator may be an insulating layer with a metal-free surface obtained by removing the surface metal foil from the aforementioned laminate or printed circuit board.

[0180] Preferably, the resin composition or its product provided by the present invention can be improved in one or more aspects such as glass transition temperature, dielectric constant, dielectric loss, heat resistance after moisture absorption, flame retardancy, amount of resin flowing into the plate, and drop ball test.

[0181] For example, the resin composition or articles thereof provided by the present invention may satisfy one, more or all of the following characteristics:

[0182] The glass transition temperature, measured using a thermomechanical analyzer with reference to the method described in IPC-TM-650 2.4.24.4, is greater than or equal to 185°C, for example, between 185°C and 232°C.

[0183] The dielectric constant measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 3.30, for example, between 2.70 and 3.30;

[0184] The dielectric loss measured at a frequency of 10 GHz using the method described in IPC-TM-6502.4.24.5 is less than or equal to 0.0030, for example, between 0.0013 and 0.0030.

[0185] Following the methods described in IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23, the heat resistance test after 5 hours of moisture absorption did not result in board explosion (industry specifications require that after 1 hour of moisture absorption, the heat resistance test should not result in board explosion).

[0186] Flame retardancy measured according to the method described in UL 94 is rated as V-1 or V-0.

[0187] The amount of adhesive flowing into the board after the product (e.g., a sample with adhesive flow inside the board) is greater than or equal to 5 mm, for example, between 5 mm and 10 mm.

[0188] The drop test height that causes damage to the product (e.g., drop test sample) is greater than or equal to 35 cm, for example, between 35 and 70 cm.

[0189] The resin compositions of the embodiments and comparative examples of the present invention were prepared according to the amounts specified in Tables 1 to 5 using various raw materials from the following sources, and further processed into various test samples or articles. The composition and test results of the resin compositions of the embodiments and comparative examples are shown in Tables 1 to 5 (all units are parts by weight).

[0190] Compound A: prepared by the method of Synthesis Example 1.

[0191] Compound B: prepared by the method in Synthesis Example 2.

[0192] Compound C: prepared by the method of Synthesis Example 3.

[0193] Compound D: prepared by the method in Synthesis Example 4.

[0194] Compound E: prepared by the method in Synthesis Example 5.

[0195] Compound F: prepared by the method of Synthesis Example 6.

[0196] Hexa(4-vinylphenoxy)cyclotriphosphazene: purchased from Weihai Jinwei Chemical;

[0197] Dimethylphenylsilane: purchased from Suzhou Sisso.

[0198] Compounds 1 to 3 were prepared by the methods described in Comparative Synthesis Examples 1 to 3, respectively.

[0199] Phenylacetylsilane: purchased from Suzhou Sisso.

[0200] Compounds 4 to 5: were prepared by the method described in Comparative Synthesis Examples 4 to 5.

[0201] OPE-2st 2200: Terminal ethylene benzyl polyphenylene ether resin, purchased from Mitsubishi Gas Chemical Co., Ltd.

[0202] SA9000: Terminal methacrylate polyphenylene ether resin, purchased from Sabic.

[0203] TAIC: Triallyl isocyanurate, purchased from Chin Yu Enterprise Co., Ltd.

[0204] DVB: Divinylbenzene, purchased from Merck.

[0205] B-1000: Polybutadiene, purchased from Japan Soda.

[0206] SBS-C: Styrene-butadiene block copolymer, purchased from Nippon Soda.

[0207] D1118: Styrene-butadiene-styrene block copolymer (SBS), purchased from KRATON, wherein the mass ratio of styrene units to butadiene units is 30:70.

[0208] H1051: Hydrogenated styrene-butadiene-styrene block copolymer (SEBS), purchased from Asahi KASEI.

[0209] PX-200: Resorcinol bis-(xylyl phosphate) (condensation polymer), or tetra(2,6-dimethylphenyl) phosphate (condensation polymer), purchased from Daihachi Chemical, Japan.

[0210] S-2: Diethyl-p-vinylbenzyl phosphate, purchased from Katayama Chemical Co., Ltd.

[0211] SC-2500SMJ: Spherical silica treated with acrylate-based silane coupling agent, purchased from Admatechs.

[0212] 25B: 2,5-Dimethyl-2,5-Di(tert-butylperoxy)-3-hexyne, purchased from Nippon Oil Co., Ltd.

[0213] MEK: Butyl ketone, commercially available, source is not limited.

[0214] Toluene: Purchased from Qiangdi.

[0215] In the table, "Z" represents the total amount of all components in the resin composition of each example or comparative example, excluding (i.e., not containing) curing accelerators, inorganic fillers, and solvents. For example, "Z*1.0" means that the amount of inorganic filler added is 1.0 times the aforementioned Z. For example, "Z*1.0" in Example E1 means that the amount of inorganic filler added is 230 parts by weight (230 parts by weight multiplied by 1.0).

[0216] In the table, "appropriate amount" for solvent addition means the amount of solvent used to achieve the ideal solid content of the overall resin composition. For resin compositions using both methyl ethyl ketone (MEK) and toluene as solvents, "appropriate amount" means the total amount of these two solvents is sufficient to achieve the ideal solid content of the overall resin composition, for example, but not limited to, a solid content of 70% by weight.

[0217] The composition and test results of the resin compositions in the examples and comparative examples are shown in Tables 1 to 5 (all units are parts by weight):

[0218] Table 1. Composition (parts by weight) and property test results of the resin compositions in Examples E1 to E7.

[0219]

[0220]

[0221] Table 2. Composition (parts by weight) and property test results of the resin compositions of Examples E8 to E14

[0222]

[0223]

[0224] Table 3. Composition (parts by weight) and property test results of the resin compositions of Examples E15 to E21

[0225]

[0226]

[0227] Table 4. Composition (parts by weight) and property test results of resin compositions of comparative examples C1 to C7

[0228]

[0229]

[0230] Table 5. Composition (parts by weight) and property test results of resin compositions of comparative examples C8 to C13

[0231]

[0232]

[0233] The various resin compositions shown in Tables 1 to 5 were prepared with varnish and various test samples according to the following methods, and the characteristics were measured according to specific test conditions to obtain test results.

[0234] Varnish (or adhesive)

[0235] Each embodiment (represented by E, such as E1 to E21) or comparative example (represented by C, such as C1 to C13) is added to a mixing tank according to the amounts in Tables 1 to 5 and stirred. The resulting resin composition is called resin varnish.

[0236] Taking Example E1 as an example, 100 parts by weight of compound A, 100 parts by weight of vinyl-containing polyphenylene ether resin (SA9000), and 30 parts by weight of vinyl-containing crosslinking agent (TAIC) were added to a stirrer containing an appropriate amount of toluene and an appropriate amount of methyl ethyl ketone (the solvent "appropriate amount" in Tables 1 to 5 represents the amount of solvent used to obtain the ideal solid content of the resin composition, for example, the solid content of the varnish is 70% by weight). The mixture was stirred until all solid components were dissolved into a homogeneous liquid phase. Then, "Z*1.0" parts by weight of spherical silica SC-2500SMJ (i.e., 230 parts by weight) were added and stirred until completely dispersed. Then, 0.3 parts by weight of curing accelerator (25B, which was first dissolved in an appropriate amount of solvent) was added and stirred for 1 hour to obtain the varnish of resin composition E1.

[0237] In addition, in accordance with the ingredient amounts listed in Tables 1 to 5 and the method for preparing the varnish of Example E1, varnishes of other Examples E2 to E21 and Comparative Examples C1 to C13 were prepared.

[0238] Prepreg 1 (using 2116E-glass fiber cloth)

[0239] The resin compositions of the different examples (E1 to E21) and comparative examples (C1 to C13) listed in Tables 1 to 5 were added to a mixing tank in batches, mixed evenly, and stirred until completely dissolved into varnish. The resin compositions were then placed in an impregnation tank. Fiberglass cloth (e.g., E-fiberglass cloth of specification 2116) was passed through the impregnation tank to adhere the resin composition to the fiberglass cloth. The mixture was then heated at 120°C to 150°C to a semi-cured state (B-Stage) to obtain a semi-cured sheet (resin content approximately 52%).

[0240] Prepreg 2 (using 1080E-glass fiber cloth)

[0241] The resin compositions of the different examples (E1 to E21) and comparative examples (C1 to C13) listed in Tables 1 to 5 were added to a mixing tank in batches, mixed evenly, and stirred until completely dissolved into varnish. The resin compositions were then placed in an impregnation tank. Fiberglass cloth (e.g., E-fiberglass cloth of specification 1080) was passed through the impregnation tank to adhere the resin composition to the fiberglass cloth. The mixture was then heated at 120°C to 150°C to a semi-cured state (B-Stage) to obtain a semi-cured sheet (resin content approximately 70%).

[0242] Copper foil substrate 1 (formed by laminating eight prepreg sheets 1)

[0243] Two 18-micron-thickness reverse-treat copper foils (RTF copper foils) and eight prepreg sheets (using 2116E-glass fiber cloth) made from various resin compositions are prepared in batches. Each prepreg sheet has a resin content of approximately 52%. The copper foil, the eight prepreg sheets, and the copper foil are stacked in that order and pressed together under vacuum at 210°C for 2 hours to form the copper foil substrates. The eight stacked prepreg sheets are then cured (C-stage) to form an insulating layer between the two copper foils, with the insulating layer having a resin content of approximately 52%.

[0244] Copper foil substrate 2 (formed by laminating two prepreg sheets 2)

[0245] Two 18-micron-thickness reverse-treat copper foils (RTF copper foils) and two prepregs (using 1080E-glass fiber cloth) made from various resin compositions are prepared in batches. Each prepreg has a resin content of approximately 70%. The copper foil, two prepregs, and copper foil are stacked in that order and pressed under vacuum at 210°C for 2 hours to form the copper foil substrates. The two stacked prepregs undergo a curing (C-stage) process to form an insulating layer between the two copper foils; this insulating layer has a resin content of approximately 70%.

[0246] Copper foil substrate 3 (composed of six prepreg sheets 1 laminated together)

[0247] Two 18-micron-thickness reverse-treat copper foils (RTF copper foils) and six prepregs (using 2116E-glass fiber cloth) made from various resin compositions are prepared in batches. Each prepreg has a resin content of approximately 52%. The copper foils, six prepregs, and copper foils are stacked in that order and pressed under vacuum at 210°C for 2 hours to form the copper foil substrates. The six stacked prepregs are then cured (C-stage) to form an insulating layer between the two copper foils, with the insulating layer having a resin content of approximately 52%.

[0248] Copper-free substrate 1 (composed of eight prepreg sheets laminated together)

[0249] The copper foil substrate 1 is etched to remove the copper foil on both sides to obtain a copper-free substrate, which is made of eight prepreg sheets 1 laminated together and has a resin content of about 52%.

[0250] Copper-free substrate 2 (made by laminating two prepreg sheets 2)

[0251] The copper foil substrate 2 is etched to remove the copper foil on both sides to obtain a copper-free substrate, which is formed by pressing two prepreg sheets 2 together and has a resin content of about 70%.

[0252] Copper-free substrate 3 (composed of six prepreg sheets laminated together)

[0253] The copper foil substrate 3 is etched to remove the copper foil on both sides to obtain a copper-free substrate, which is made of six prepreg sheets 1 and has a resin content of about 52%.

[0254] The test methods and their characteristic analysis items are described below.

[0255] 1. Glass transition temperature (Tg)

[0256] In the glass transition temperature test, the copper-free substrate 1 mentioned above was selected as the test sample. Using a dynamic mechanical analyzer (DMA), the sample was heated at a rate of 2°C per minute, from 50°C to 400°C, according to the method described in IPC-TM-6502.4.24.4, and the glass transition temperature (in °C, denoted as DMA-Tg) was measured. A higher glass transition temperature is better, and a difference of 5°C or more between the glass transition temperatures of different test samples is considered significant (presenting significant technical difficulty).

[0257] For example, an article made from the resin composition disclosed in this invention has a glass transition temperature greater than or equal to 185°C, measured with reference to the method described in IPC-TM-6502.4.24.4, for example, between 185°C and 232°C, or between 185°C and 226°C, or between 192°C and 226°C.

[0258] 2. Dielectric constant (Dk) and dielectric loss (Df)

[0259] In the measurement of dielectric constant and dielectric loss, the copper-free substrate 2 mentioned above was selected as the test sample. A microwave dielectric constant analyzer (purchased from AET Corporation, Japan) was used, and measurements were taken at a frequency of 10 GHz according to the method described in JIS C2565. Lower dielectric constants or lower dielectric losses indicate better dielectric properties of the test sample. At a measurement frequency of 10 GHz, with Dk values ​​less than or equal to 3.60 and Df values ​​less than or equal to 0.004, a difference in Dk values ​​greater than or equal to 0.05 indicates a significant difference in dielectric constant between different substrates (presenting significant technical difficulty); a difference in Dk values ​​less than 0.05 indicates no significant difference in dielectric constant between substrates; a difference in Df values ​​less than 0.0001 indicates no significant difference in dielectric loss between substrates; and a difference in Df values ​​greater than or equal to 0.0001 indicates a significant difference in dielectric loss between different substrates (presenting significant technical difficulty).

[0260] For example, an article made from the resin composition disclosed in this invention has a dielectric constant less than or equal to 3.30, for example, between 2.70 and 3.30, or between 2.70 and 3.00, or between 2.70 and 2.85, as measured at a frequency of 10 GHz with reference to the method described in JIS C2565; and a dielectric loss less than or equal to 0.0030, for example, between 0.0013 and 0.0030, or between 0.0013 and 0.0018, or between 0.0013 and 0.0017.

[0261] 3. Heat resistance after moisture absorption (PCT)

[0262] Using the aforementioned copper-free substrate 1 as the test sample, and following the method described in IPC-TM-650 2.6.16.1, the sample underwent a pressure cooking test (PCT) for 5 hours (test temperature 121°C, relative humidity 100%). Then, following the method described in IPC-TM-650 2.4.23, it was immersed in a tin bath at a constant temperature of 288°C. After immersion for 20 seconds, the sample was removed and observed for any board bursting. For example, interlayer peeling between insulating layers constitutes board bursting. Interlayer peeling can cause bubbling and separation between any layers of the substrate (visible to the naked eye). For instance, articles made from the resin composition disclosed in this invention, after absorbing moisture for 5 hours according to the methods described in IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23, did not exhibit board bursting in the heat resistance test (industry standards require that multilayer boards or printed circuit boards not exhibit board bursting in the heat resistance test after absorbing moisture for 1 hour).

[0263] 4. Flame retardancy

[0264] In the flame retardancy test, the copper-free substrate 1 mentioned above was selected as the test sample. Measurements were performed according to the method described in UL 94. The flame retardancy analysis results are expressed as V-0, V-1, and V-2 ratings, where V-0 has better flame retardancy than V-1, and V-1 has better flame retardancy than V-2.

[0265] For example, an article made from the resin composition disclosed in this invention has a flame retardancy rating of V-0 or V-1 when measured with reference to the method described in UL 94 specification.

[0266] 5. Inner resin flow

[0267] First, prepare a copper-containing substrate of EM-827 as a copper-containing core board (available from Zhongshan Taiguang Electronic Materials Co., Ltd., which uses 7628E-glass fiber cloth and 1 ounce HTE copper foil). The thickness of the copper-containing core board is 28 mil. The surface copper foil of this copper-containing core board can be processed by existing browning treatment process to obtain a browned core board.

[0268] Prepare a prepreg 2 obtained from the aforementioned embodiments (E1 to E21) and comparative examples (C1 to C13) in batches, and a brown core board with a thickness of 28 mil and a length and width of 18 inches and 16 inches respectively. The prepreg has a diamond-shaped opening with a length and width of 4 inches in the center (a 4-inch * 4-inch diamond-shaped space is punched out in the center of the prepreg using an existing punching machine).

[0269] A copper-containing multilayer board is obtained by sequentially stacking a 0.5 oz HTE copper foil (back-pressed, i.e., the bright side of the copper foil contacts the prepreg 2), a prepreg 2, and a browned core board, and then pressing and curing it under vacuum, high temperature (200°C), and high pressure (360 psi) for 2 hours. After removing the back-pressed copper foil from the surface of this copper-containing multilayer board, an in-board adhesive flow sample is obtained. Taking the in-board adhesive flow sample, a 4-inch x 4-inch rhombus is used as the baseline. Each side is divided into four equal parts by three bisecting points. The adhesive flow amount at each of the 12 points (i.e., the vertical adhesive flow distance at each of the 12 points) is measured, and the average of the adhesive flow amounts at the 12 points is calculated. The in-board adhesive flow amount (average value) is then obtained, in millimeters (mm). In the art, a larger measured in-board adhesive flow amount indicates better prepreg flowability. A difference in in-board adhesive flow amount greater than or equal to 1 mm is considered significant (presenting significant technical difficulty). Generally, the amount of adhesive flowing into the board is preferably between 5.0 mm and 20.0 mm. An amount of adhesive flowing into the board less than 5.0 mm indicates insufficient adhesive flow, which may result in ineffective adhesive filling of vias when using prepreg for overlay, easily leading to adhesive shortages or board bursting. Articles made from the resin composition disclosed in this invention have an amount of adhesive flowing into the board greater than or equal to 5.0 mm, for example, between 5.0 mm and 10.0 mm, or between 5.0 mm and 9.5 mm, or between 5.5 mm and 7.5 mm.

[0270] 6. Ball Drop Test

[0271] The copper-free substrate 3 described above was selected as the test sample. A 20*20 mm grid was drawn on the surface of the 60*160 mm copper-free substrate 3. It was then placed on the test bench of a DuPont impact testing machine. A 100-gram hammer was dropped freely from a certain height onto a 7.9 mm radius arc-shaped impact head. After impact, the degree of damage was observed. The same sample was tested three times at each height. If there was no damage to the sample surface, the hammer height was increased. Damage refers to issues such as, but not limited to, cracks, fissures, whitening, white spots, or impact marks on the surface of the copper-free substrate 3. The test samples were tested starting from a height of 1 cm, and repeated until the number of damaged areas on the sample surface exceeded two. At this height, the sample was considered damaged, and the current height was recorded. For example, when the number of whitening areas on the sample surface exceeded two, the sample was considered damaged at this height, and the current height was recorded. In this field, a higher measured drop ball height indicates better impact toughness of the sample. A difference of 5 cm or more in drop ball height is considered significant (indicating significant technical difficulty). Generally, a drop ball height of 35 cm or more indicates a qualified sample (e.g., between 30 cm and 70 cm); a drop ball height of 50 cm or more is considered good (e.g., between 50 cm and 70 cm); and a drop ball height of 60 cm or more is considered even better (e.g., between 60 cm and 70 cm). When a sample passes the drop ball test, it indicates good toughness and impact resistance, which is beneficial for subsequent PCB manufacturing.

[0272] Based on the test results in Tables 1 to 5, the following phenomena can be observed.

[0273] By comparing Examples E1-E3, E6-E8 with Comparative Example C6, it can be confirmed that the compound of Formula (I) of the present invention, compared with Compound 1, can achieve one or more technical effects such as a glass transition temperature greater than or equal to 185°C, a dielectric loss less than or equal to 3.30, or passing the PCT heat resistance test.

[0274] By comparing the examples E1-E3, E6-E8 with the comparative examples C7-C11, it can be confirmed that, compared with other phosphorus-containing compounds, the compound of formula (I) of the present invention can simultaneously achieve one, multiple, or all of the technical effects of increasing glass transition temperature, reducing dielectric constant, reducing dielectric loss, passing PCT heat resistance, improving flame retardancy, increasing the amount of adhesive flowing into the plate, and increasing the drop ball test height.

[0275] By comparing Comparative Examples E2 and C3-C5, it can be confirmed that the compound of Formula (I) of the present invention, compared with the addition of raw material hexa(4-vinylphenoxy)cyclotriphosphazene alone, the addition of raw material phenyldimethylsilane alone, or the combination of (unprepolymerized) hexa(4-vinylphenoxy)cyclotriphosphazene and phenyldimethylsilane, simultaneously achieves one, multiple, or all of the technical effects of increasing glass transition temperature, reducing dielectric constant, reducing dielectric loss, passing PCT heat resistance, improving flame retardancy, increasing the amount of adhesive flowing into the board, and increasing the drop ball test height.

[0276] By comparing Examples E2, E4-E5 with Comparative Examples C1-C2, or by comparing Examples E1-E8 with Comparative Examples C1-C2, it can be confirmed that, within the range of 80 to 120 parts by weight of compound of formula (I) of the present invention, compared to outside the range, compound of formula (I) of the present invention can simultaneously achieve one, multiple, or all of the technical effects of increasing glass transition temperature, passing PCT heat resistance, improving flame retardancy, increasing the amount of adhesive flowing into the plate, and increasing the drop ball test height.

[0277] By comparing Examples E1-E21 with Comparative Examples C1-C13, it can be confirmed that the articles made from the compound of formula (I) of the present invention can simultaneously achieve one, more, or all of the technical effects of a glass transition temperature greater than or equal to 185°C, a dielectric constant less than or equal to 3.30, a dielectric loss less than or equal to 0.0030, an in-plate flow rate greater than or equal to 5.0 mm, and a drop ball test height greater than or equal to 35 cm. Conversely, Comparative Examples C1-C7, which do not use the technical solution of the present invention, cannot simultaneously achieve the aforementioned technical effects.

[0278] 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.

[0279] 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 compound having the structure shown in formula (I): Its features are, n is an integer from 3 to 6, and X and T are each independently represented by equation (1) or equation (2), with at least one of X and T being equation (2), where m is an integer from 0 to 4, and R a R is an alkyl group having 1 to 4 carbon atoms or hydrogen atoms. b R c R d Each can be an alkyl, phenyl, or naphthyl group having 1 to 4 carbon atoms.

2. The compound according to claim 1, characterized in that, The structures of X and T in the compound of formula (I) are shown in formula (3) or formula (4):

3. The compound according to claim 2, characterized in that, In the compound of formula (I), X and T contain at least two formulas (3), and X and T contain at least two formulas (4).

4. The compound according to claim 1, characterized in that, The compound of formula (I) has a structure shown in any of the following formulas (II), (III), (IV), (V), (VI), or (VII):

5. A method for manufacturing the compound according to claim 1, characterized in that, The method includes the step of performing a hydrosilylation reaction between vinylphenoxycyclophosphonitrile and a silane compound containing silane bonds at a temperature between 5°C and 100°C to obtain the compound of formula (I).

6. The method for manufacturing the compound according to claim 5, characterized in that, The molar ratio of the vinylphenoxycyclophosphonitrile to the silane compound containing silane bonds is between 1:1 and 1:2n.

7. The method for manufacturing the compound according to claim 5, characterized in that, The vinylphenoxycyclophosphonitrile has the structure of formula (A), where n is an integer from 3 to 6, m is an integer from 0 to 4, and R a It is a hydrogen or an alkyl group having 1 to 4 carbon atoms.

8. The method for manufacturing the compound according to claim 5, characterized in that, The vinylphenoxy cyclophosphonitrile is hexa(vinylphenoxy)cyclotriphosphonitrile, octa(vinylphenoxy)cyclotetraphosphonitrile, deca(vinylphenoxy)cyclopentaphosphonitrile or dodeca(vinylphenoxy)cyclohexaphosphonitrile.

9. The method for manufacturing the compound according to claim 5, characterized in that, The vinylphenoxycyclophosphonitrile is a vinylphenoxycyclophosphonitrile with a vinyl group at the para position.

10. The method for manufacturing the compound according to claim 5, characterized in that, The silane compound containing silane bonds may have the following structure (B): Among them, R b R c R d It is independently selected from alkyl, phenyl, or naphthyl groups having 1 to 4 carbon atoms.

11. The method for manufacturing the compound according to claim 5, characterized in that, The silane compounds containing silane bonds include triethylsilane, triisopropylsilane, triisobutylsilane, triphenylsilane, diphenylmethylsilane, tert-butyldiphenylsilane, tert-butyldimethylsilane, dimethylphenylsilane, or dimethylnaphthylsilane.

12. A resin composition, characterized in that, It includes 80 to 120 parts by weight of the compound of formula (I) according to claim 1, 100 parts by weight of the vinyl-containing polyphenylene ether resin, and 15 to 45 parts by weight of the vinyl-containing crosslinking agent.

13. The resin composition according to claim 12, characterized in that, The vinyl-containing polyphenylene ether resin includes terminal vinyl benzyl polyphenylene ether resin, terminal methacrylate polyphenylene ether resin, or terminal allyl polyphenylene ether resin.

14. The resin composition according to claim 13, characterized in that, The terminal vinyl benzyl polyphenylene ether resin and the terminal methacrylate polyphenylene ether resin respectively comprise the structures shown in formula (A-1) and formula (A-2): Among them, R1 to R 14 Each is independently H or -CH3, and W1 and W2 are independently C1 to C3 divalent aliphatic groups; b1 is an integer from 0 to 8; Q1 includes the structure shown in formula (B-1), formula (B-2), or formula (B-3): Y1 and Y2 each independently include the structure shown in equation (B-4): Among them, R 15 To R 30 Each is independently H or -CH3; m1 and n1 are each independently an integer from 1 to 30; and A1 is selected from covalent bonds, -CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -S-, -SO2- and carbonyl groups.

15. The resin composition according to claim 12, characterized in that, The vinyl crosslinking agent includes styrene, divinylbenzene, divinylnaphthalene, divinylbiphenyl, tert-butylstyrene, di(vinylbenzyl) ether, 1,2,4-trivinylcyclohexane, di(vinylphenyl)ethane, di(vinylphenyl)hexane, divinylphenyldimethylene ether, divinylphenyldimethylenebenzene, triallyl isocyanurate, triallyl cyanurate, diallyl bisphenol A, butadiene, decanadiene, octadiene, vinylcarbazole, or acrylate.

16. The resin composition according to claim 12, characterized in that, The resin composition further comprises 20 to 60 parts by weight of a polyolefin resin.

17. The resin composition according to claim 16, characterized in that, The polyolefin resins include polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene terpolymer, ethylene-divinylbenzene-styrene polymer, styrene-divinylbenzene-ethylstyrene polymer, styrene-butadiene-styrene copolymer, maleic anhydride-added styrene-butadiene copolymer, vinyl-polybutadiene-urea polymer, maleic anhydride-added polybutadiene, polymethylstyrene, ethylene propylene diene monomer (EPDM) rubber, petroleum resin, cyclic olefin copolymer, hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated styrene-butadiene-divinylbenzene terpolymer, hydrogenated styrene-butadiene-styrene copolymer, hydrogenated maleic anhydride-added styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, or hydrogenated styrene-isoprene copolymer.

18. The resin composition according to claim 12, characterized in that, The resin composition further includes amine curing agents, flame retardants, inorganic fillers, curing accelerators, polymerization inhibitors, colorants, solvents, toughening agents, or silane coupling agents.

19. An article characterized in that, The article is made of the resin composition according to any one of claims 12 to 18, and the article includes a prepreg, a resin film, a laminate, a printed circuit board, or a cured insulator.

20. The article of claim 19, characterized in that, The article satisfies one, more, or all of the following characteristics: The glass transition temperature measured using a thermomechanical analyzer with reference to the method described in IPC-TM-650 2.4.24.4 is greater than or equal to 185°C. The dielectric constant measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 3.30; The dielectric loss measured at a frequency of 10 GHz using the method described in IPC-TM-6502.4.24.5 is less than or equal to 0.0030. After absorbing moisture for 5 hours according to the methods described in IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23, no heat resistance test was performed and no plate bursting occurred. Flame retardancy measured according to the method described in UL 94 is rated as V-1 or V-0. The amount of adhesive flowing into the board after lamination is greater than or equal to 5 mm. The drop height that causes damage is greater than or equal to 35 cm.

Images