Resin composition and product thereof

Abstract

The present invention discloses a resin composition and a product thereof, the resin composition comprises a vinyl-containing resin and a phosphorus-containing compound having a structure represented by formula (1) or a prepolymer thereof, the content of the phosphorus-containing compound having the structure represented by formula (1) is 35-60 parts by weight relative to 100 parts by weight of the vinyl-containing resin, and the content of the phosphorus-containing compound having the structure represented by formula (1) is 30-60 parts by weight relative to 100 parts by weight of the vinyl-containing resin. Or relative to 100 parts by weight of the vinyl-containing resin, the content of the prepolymer of the phosphorus-containing compound with the structure shown in the formula (1) is 50-90 parts by weight. The resin composition can be made into various articles, including resin films, prepregs, laminates, or printed circuit boards, and can be improved in one or more characteristics. # imgabs0 #

Description

Technical Field

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

[0002] In recent years, as electronic signal transmission methods develop towards 5G, and electronic equipment, communication devices, personal computers, etc. become more functional and miniaturized, the circuit boards used in these applications are also developing towards multi-layering, high-density wiring, and high-speed signal transmission, which puts higher requirements on the comprehensive performance of circuit substrates such as copper foil substrates.

[0003] Therefore, there is a need to propose a novel material that can meet the requirements of current circuit board properties. 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 property requirements, the main purpose of the present invention is to provide a resin composition and products made from the resin composition, thereby improving at least one or more properties such as PCT water absorption, dielectric constant, dielectric loss, elongation, copper foil tension and glass transition temperature.

[0005] In order to achieve the above object, the present invention discloses a resin composition comprising:

[0006] Containing vinyl resins; and

[0007] A phosphorus-containing compound having a structure represented by formula (1) or a prepolymer thereof;

[0008] in:

[0009] The phosphorus-containing compound having the structure represented by formula (1) is contained in an amount of 35 to 60 parts by weight relative to 100 parts by weight of the vinyl-containing resin; or the phosphorus-containing compound prepolymer having the structure represented by formula (1) is contained in an amount of 50 to 90 parts by weight relative to 100 parts by weight of the vinyl-containing resin;

[0010]

[0011] Wherein, R1 each independently represents any divalent functional group represented by the following formula (a) to formula (d):

[0012]

[0013] wherein p and q are each independently positive integers, and p+q is between 2 and 11;

[0014] R2 each independently represents any one of the monovalent functional groups shown in the following formula (e) to formula (f):

[0015]

[0016] R3 represents a phenyl group; and

[0017] n represents the number of repetitions of the unit in the brackets, which can make the weight average molecular weight of the phosphorus-containing compound having the structure represented by formula (1) be between 500 and 10,000.

[0018] For example, in one embodiment, the vinyl-containing resin includes a vinyl-containing polyphenylene ether resin, a maleimide resin, a compound having a structure represented by formula (2), a vinyl-containing polyolefin resin, triallyl isocyanurate or a combination thereof.

[0019] wherein m is an integer from 1 to 20.

[0020] For example, in one embodiment, the prepolymer of the phosphorus-containing compound having the structure shown in formula (1) is prepared by a prepolymerization reaction of a mixture, and the mixture includes the phosphorus-containing compound having the structure shown in formula (1) and the vinyl polyphenylene ether resin in a molar ratio between 1:2 and 2:1.

[0021] For example, in one embodiment, the mixture is prepolymerized at a temperature of 60° C. to 95° C. for 4 to 6 hours to obtain a prepolymer of a phosphorus-containing compound having a structure represented by formula (1).

[0022] For example, in one embodiment, the conversion rate of the prepolymerization reaction is between 10% and 90%.

[0023] For example, in one embodiment, the resin composition includes 100 parts by weight of a vinyl resin and 35 to 60 parts by weight of a phosphorus-containing compound having a structure represented by formula (1).

[0024] For example, in one embodiment, the resin composition includes 100 parts by weight of a vinyl resin and 50 to 90 parts by weight of a prepolymer of a phosphorus-containing compound having a structure represented by formula (1).

[0025] For example, in one embodiment, the resin composition further includes a phosphorus-containing maleimide resin.

[0026] For example, in one embodiment, the resin composition includes 100 parts by weight of a vinyl resin, 35 to 60 parts by weight of a phosphorus-containing compound having a structure represented by formula (1), and 5 to 60 parts by weight of a phosphorus-containing maleimide resin.

[0027] For example, in one embodiment, the resin composition includes 100 parts by weight of a vinyl resin, 50 to 90 parts by weight of a prepolymer of a phosphorus-containing compound having a structure represented by formula (1), and 5 to 45 parts by weight of a phosphorus-containing maleimide resin.

[0028] For example, in one embodiment, the resin composition further includes an inorganic filler, a hardening accelerator, an inhibitor, a solvent, a silane coupling agent, a surfactant, a colorant, a toughening agent or a combination thereof.

[0029] In addition, the present invention also provides a product made of the above resin composition, which includes a prepreg, a resin film, a laminate or a printed circuit board.

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

[0031] The water absorption calculated according to the method described in IPC-TM-6502.6.16.1 is less than or equal to 0.31%;

[0032] The dielectric constant measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 3.27;

[0033] The dielectric loss measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 0.00287;

[0034] The elongation measured according to the method described in ASTM D412 is greater than or equal to 6.95%;

[0035] A copper foil pull force greater than or equal to 3.07 lb / in as measured by the method described in IPC-TM-6502.4.8; and

[0036] The glass transition temperature measured according to the method described in IPC-TM-6502.4.24.4 is greater than or equal to 182°C. DETAILED DESCRIPTION

[0037] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the text have the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definitions in this specification shall prevail.

[0038] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0039] The use of "one", "a", "an" or similar expressions to describe the components and technical features of the present invention is merely for the convenience of expression and to provide a general meaning to the scope of the present invention. Therefore, such description should be understood to include one or at least one, and the singular also includes the plural, unless it is obvious that it refers to another meaning.

[0040] In this document, "or its combination" means "or any combination thereof", and "any one", "any one" means "any one", "any one" or "any one".

[0041] As used herein, the terms "include", "comprising", "having", "containing" or any other similar terms are open-ended transitional phrases, which are intended to cover non-exclusive inclusions. For example, a composition or article containing multiple elements is not limited to those elements listed herein, but may also include other elements that are not explicitly listed but are generally inherent to the composition or article. In addition, unless otherwise expressly stated, the term "or" refers to an inclusive "or" rather than an exclusive "or". For example, any of the following situations satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist). In addition, as used herein, the interpretation of the terms "include", "comprising", "having", and "containing" should be considered to have specifically disclosed and simultaneously cover transitional terms such as "consisting of" and "consisting essentially of".

[0042] In this article, the terms "and", "with", "and", "as well as" or other similar terms are used to connect parallel sentence components, and there is no distinction between the previous and subsequent components. The meaning of the parallel sentence components does not change after the positions of the parallel sentence components are exchanged in grammatical sense.

[0043] In this article, all features or conditions defined in the form of numerical ranges or percentage ranges are only for simplicity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be deemed to have covered and specifically disclosed all possible sub-ranges and individual values ​​within the range, especially integer values. For example, the range description of "1 to 8" should be deemed to have specifically disclosed all sub-ranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., especially the sub-ranges defined by all integer values, and should be deemed to have specifically disclosed individual values ​​such as 1, 2, 3, 4, 5, 6, 7, 8, etc. in the range. Similarly, the range description of "between 1 and 8" should be deemed to have specifically disclosed all ranges such as 1 to 8, 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., and include endpoint values. Unless otherwise specified, the above interpretation method is applicable to all contents of the full text of the present invention, regardless of whether the scope is extensive or not.

[0044] If the quantity or other numerical value or parameter is expressed as a range, a preferred range or a series of upper and lower limits, it should be understood that all ranges consisting of any upper limit or preferred value of the range and the lower limit or preferred value of the range have been specifically disclosed herein, regardless of whether such ranges are disclosed separately. In addition, if a numerical range is mentioned herein, unless otherwise specified, the range should include its endpoints and all integers and fractions within the range.

[0045] In this document, numerical values ​​should be understood to have the accuracy of the significant digits of the numerical value, provided that the purpose of the invention can be achieved. For example, the number 40.0 should be understood to cover the range from 39.50 to 40.49.

[0046] In this article, for the use of Markush groups or optional terms to describe the features or examples of the present invention, those skilled in the art should understand that subgroups or any individual members of all members in the Markush group or option list can also be used to describe the present invention. For example, if X is described as "selected from the group consisting of X1, X2 and X3", it also means that the claim that X is X1 and the claim that X is X1 and / or X2 and / or X3 have been fully described. Furthermore, for those who use Markush groups or optional terms to describe the features or examples of the present invention, those skilled in the art should understand that any combination of subgroups or individual members of all members in the Markush group or option list can also be used to describe the present invention. Accordingly, for example, if X is described as "selected from the group consisting of X1, X2 and X3", and Y is described as "selected from the group consisting of Y1, Y2 and Y3", it means that the claim that X is X1 or X2 or X3 and Y is Y1 or Y2 or Y3 has been fully described.

[0047] Unless otherwise specified, in the present invention, a compound refers to a chemical substance formed by two or more elements connected by chemical bonds, including small molecule compounds and polymer compounds, and is not limited thereto. The compound herein is not limited to a single chemical substance when interpreted, but can also be interpreted as the same type of chemical substance with the same composition or the same properties. In addition, in the present invention, a mixture refers to a combination of two or more compounds.

[0048] If not otherwise specified, the "resin" in the present invention is a customary name for a synthetic polymer, which may include monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and polymers thereof, etc., and is not limited thereto.

[0049] If not otherwise specified, in the present invention, modified products (also referred to as modified products) include: products after modification of the reactive functional groups of each resin, products after prepolymerization of each resin with other resins, products after cross-linking of each resin with other resins, products after homopolymerization of each resin, products after copolymerization of each resin with other resins, and the like.

[0050] In this article, prepolymer refers to a product that still contains reactive functional groups or has polymerization potential after a compound or mixture (monomer) undergoes prepolymerization (partial polymerization) reaction. For example, the molecular weight or viscosity can be used to assist in confirming whether the reaction degree of the prepolymerization reaction meets the requirements. The prepolymerization method used in this article, for example but not limited to, uses solvent heating to initiate the prepolymerization reaction, or uses hot melt reaction to initiate the prepolymerization reaction. For example, solvent heating prepolymerization is to add raw materials to the solvent to dissolve, and optionally add catalysts or inhibitors, and then heat the reaction until all raw materials are dissolved in the solvent, thereby initiating the prepolymerization reaction. Hot melt reaction prepolymerization is to directly heat and melt the raw materials to initiate the prepolymerization reaction. The product (prepolymer) after prepolymerization has a larger molecular weight than the compound monomer or mixture monomer that has not been prepolymerized, and can be analyzed by gel permeation chromatography (GPC). The result graph of residence time (X axis) and molecular weight (Y axis) distribution shows that the molecular weight distribution peak of the prepolymer is located at the front end (shorter residence time), while the molecular weight distribution peak of the monomer is located at the back end (longer residence time). In addition, the obtained prepolymer has a wider molecular weight distribution peak containing multiple peaks connected continuously, while the monomer has a narrower molecular weight distribution peak containing only a single molecular weight distribution peak.

[0051] For those skilled in the art, a resin composition containing two compounds A and B and an additive (comprising three components in total), and a resin composition containing a prepolymer formed by two compounds A and B and an additive (comprising two components in total) are different resin compositions, and the two are completely different in many aspects such as the preparation method, the physical and chemical properties of the compounds, and the properties of the products thereof. For example, the former is to mix A, B and the additive to form a resin composition, while the latter is to first prepolymerize the mixture including A and B under appropriate conditions to form a prepolymer, and then mix the prepolymer with the additive to obtain the resin composition. For example, for those skilled in the art, the aforementioned two resin compositions have completely different compositions, and since the function of the prepolymer formed by the two compounds A and B in the resin composition is completely different from the function of A and B individually or jointly in the resin composition, the two resin compositions should be regarded as completely different chemical substances with completely different chemical positions. For example, for those skilled in the art, since the aforementioned two resin compositions are completely different chemical substances, their products will not have the same properties.

[0052] In this article, "vinyl-containing" means that the compound structure contains ethylene carbon-carbon double bonds (C=C) or their derivative functional groups. Therefore, examples of vinyl-containing compounds may include, but are not limited to, compounds containing vinyl, styryl, allyl, vinylbenzyl, methacrylate and other functional groups in the structure. Unless otherwise specified, the positions of the aforementioned functional groups are not particularly limited, and may be located at the end of a long chain structure, for example. Therefore, for example, a vinyl-containing polyphenylene ether resin represents a polyphenylene ether resin containing vinyl, styryl, allyl, vinylbenzyl, methacrylate and other functional groups, and is not limited thereto.

[0053] Herein, parts by weight represent parts by weight, which may be any weight unit, such as, but not limited to, grams, kilograms, pounds, etc. For example, 100 parts by weight of a vinyl-containing resin may represent 100 grams of a vinyl-containing resin, 100 kilograms of a vinyl-containing resin, or 100 pounds of a vinyl-containing resin, but is not limited thereto. Herein, if the amounts of different components are presented in a proportional relationship, the actual amounts may be any amounts that conform to the proportional relationship.

[0054] The following detailed description is merely illustrative in nature and is not intended to limit the present invention and its use. In addition, this article is not limited by any theory described in the above prior art or invention summary or the following detailed description or examples.

[0055] As mentioned above, the main purpose of the present invention is to provide a resin composition, which comprises:

[0056] Containing vinyl resins; and

[0057] A phosphorus-containing compound having a structure represented by formula (1) or a prepolymer thereof;

[0058] in:

[0059] The phosphorus-containing compound having the structure represented by formula (1) is contained in an amount of 35 to 60 parts by weight relative to 100 parts by weight of the vinyl-containing resin; or the phosphorus-containing compound prepolymer having the structure represented by formula (1) is contained in an amount of 50 to 90 parts by weight relative to 100 parts by weight of the vinyl-containing resin;

[0060]

[0061] Wherein, R1 each independently represents any divalent functional group represented by the following formula (a) to formula (d):

[0062]

[0063] wherein p and q are each independently positive integers, and p+q is between 2 and 11;

[0064] R2 each independently represents any one of the monovalent functional groups shown in the following formula (e) to formula (f):

[0065]

[0066] R3 represents a phenyl group; and

[0067] n represents the number of repetitions of the unit in the brackets, which can make the weight average molecular weight of the phosphorus-containing compound having the structure represented by formula (1) be between 500 and 10,000.

[0068] In the present invention, unless otherwise specified, the type of vinyl-containing resin is not particularly limited, and may include any resin having an ethylenic carbon-carbon double bond or a functional group derived therefrom in its structure. For example, the vinyl-containing resin may include, but is not limited to, a vinyl-containing polyphenylene ether resin, a maleimide resin, a compound having a structure represented by the aforementioned formula (2), a vinyl-containing polyolefin resin, triallyl isocyanurate, or a combination thereof.

[0069] The aforementioned vinyl-containing polyphenylene ether resin may include, but is not limited to, polyphenylene ether resins containing vinyl, allyl, vinylbenzyl or methacrylate. For example, in one embodiment, the aforementioned vinyl-containing polyphenylene ether resin includes vinylbenzyl biphenyl polyphenylene ether resin, methacrylate polyphenylene ether resin (i.e., methacryloyl polyphenylene ether resin), allyl polyphenylene ether resin, vinylbenzyl modified bisphenol A polyphenylene ether resin, vinyl chain extended polyphenylene ether resin, or a combination thereof. For example, the vinyl-containing polyphenylene ether resin may be a vinyl benzyl biphenyl polyphenylene ether resin having a number average molecular weight of about 1200 (e.g., OPE-2st 1200, available from Mitsubishi Gas Chemical Co., Ltd.), a vinyl benzyl biphenyl polyphenylene ether resin having a number average molecular weight of about 2200 (e.g., OPE-2st 2200, available from Mitsubishi Gas Chemical Co., Ltd.), a methacrylate polyphenylene ether resin having a number average molecular weight of about 1900 to 2300 (e.g., SA9000, available from Sabic Corporation), a vinyl benzyl modified bisphenol A polyphenylene ether resin having a number average molecular weight of about 2400 to 2800, a vinyl chain-extended polyphenylene ether resin having a number average molecular weight of about 2200 to 3000, or a combination thereof. The vinyl chain-extended polyphenylene ether resin may include various types of polyphenylene ether resins disclosed in U.S. Patent Application Publication No. 2016 / 0185904 A1, which is incorporated herein by reference in its entirety.

[0070] The maleimide resin may include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide (or oligomer of phenylmethane maleimide), bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 3,3'-dimethyl-5,5'-dipropyl ... bismaleimide), m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, N-2,3-xylylmaleimide, N-2,6-xylylmaleimide, N-phenylmaleimide, vinyl benzyl maleimide The present invention also includes prepolymers of maleimide (VBM), maleimide containing biphenyl structure, maleimide resin containing aliphatic long chain structure, prepolymers of diallyl compound and maleimide resin, prepolymers of polyfunctional amine and maleimide resin (polyfunctional amine includes two or more amine functional groups), prepolymers of acidic phenol compound and maleimide resin, or combinations thereof. Modified products of these components are also included in the interpretation.

[0071] For example, examples of maleimide resins include, but are not limited to, maleimide resins produced by Daiwakasei Industry Co., Ltd. under the trade names of BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000, BMI-5000, BMI-5100, BMI-TMH, BMI-7000, and BMI-7000H, or maleimide resins produced by KI Chemical Co., Ltd. under the trade names of BMI-70, BMI-80, or maleimide resins produced by Nippon Kayaku Co., Ltd. under the trade names of MIR-3000 or MIR-5000. For example, maleimide resins containing aliphatic long chain structures (e.g., containing C5 to C 50 Examples of maleimide resins having aliphatic long chain structures include, but are not limited to, maleimide resins produced by designer molecules under the trade names of BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000 and BMI-6000.

[0072] For example, in one embodiment, the vinyl-containing polyolefin resin described in the present invention includes, for example but not limited to: styrene-butadiene-divinylbenzene terpolymer, styrene-butadiene-maleic anhydride terpolymer, vinyl-polybutadiene-urea oligomer, styrene-butadiene copolymer (for example but not limited to styrene-butadiene-styrene copolymer), hydrogenated styrene-butadiene-styrene triblock copolymer, styrene-isoprene copolymer, maleic anhydride-butadiene copolymer, polybutadiene resin (or butadiene homopolymer) or a combination thereof.

[0073] In one embodiment, the resin composition of the present invention comprises a vinyl resin and a phosphorus-containing compound having a structure shown in formula (1). In another embodiment, the resin composition of the present invention comprises a prepolymer of a vinyl resin and a phosphorus-containing compound having a structure shown in formula (1). In yet another embodiment, the resin composition of the present invention comprises a vinyl resin, a phosphorus-containing compound having a structure shown in formula (1), and a prepolymer of a phosphorus-containing compound having a structure shown in formula (1).

[0074] For example, in one embodiment, the resin composition of the present invention comprises 100 parts by weight of a vinyl-containing resin and 35 to 60 parts by weight of a phosphorus-containing compound having a structure shown in formula (1). In another embodiment, the resin composition of the present invention comprises 100 parts by weight of a vinyl-containing resin and 50 to 90 parts by weight of a prepolymer of a phosphorus-containing compound having a structure shown in formula (1). In yet another embodiment, the resin composition of the present invention comprises 100 parts by weight of a vinyl-containing resin, 35 to 60 parts by weight of a phosphorus-containing compound having a structure shown in formula (1), and 50 to 90 parts by weight of a prepolymer of a phosphorus-containing compound having a structure shown in formula (1).

[0075] The phosphorus-containing compound having the structure shown in formula (1) can be regarded as a reactive phosphorus-containing flame retardant because it has a reactive group and contains a phosphorus atom in the structure. The phosphorus-containing compound having the structure shown in formula (1) can be prepared by methods known to those skilled in the art without excessive experiments. For example, (A) phenylphosphoryl dichloride and (B) a dihydroxy compound (such as but not limited to tetramethylbisphenol A, dihydroxyadamantane, bisphenol TMC or dihydroxy polyphenylene ether resin) can be reacted in the presence of a catalyst (such as but not limited to boron trifluoride ether) and a phase transfer agent (such as but not limited to triphenylbutylphosphonium bromide), and then (C) chlorostyrene or vinylbenzyl chloride is added for end-capping to obtain a phosphorus-containing compound having the structure shown in formula (1), the weight average molecular weight of which is between 500 and 10,000, and the phosphorus content is between 0.5% and 8.5%. In one embodiment, the molar ratio of the reactants (A), (B) and (C) can be between 1:2 and 2.5:3 and 3.5. In one embodiment, the above reaction is carried out at a temperature of 90° C. to 100° C. for 4 to 6 hours to prepare a phosphorus-containing compound having a structure represented by formula (1).

[0076] The phosphorus-containing compound having the structure shown in formula (1) can also be made into a prepolymer by prepolymerization and used in the resin composition of the present invention. For example, the prepolymer can be prepared by prepolymerization of a mixture, and the mixture includes the phosphorus-containing compound having the structure shown in formula (1) and the vinyl-containing polyphenylene ether resin in a molar ratio between 1:2 and 2:1. The prepolymerization can be carried out in the presence of a reaction initiator as needed, such as but not limited to azobisisobutyronitrile (AIBN). The conditions of the prepolymerization are not particularly limited, for example, the mixture can be prepolymerized at a temperature of 60°C to 95°C for 4 to 6 hours to obtain the prepolymer. In one embodiment, the reaction temperature of the prepolymerization is, for example, but not limited to, 60°C, 62°C, 64°C, 65°C, 68°C, 70°C, 80°C, 82°C, 85°C, 88°C, 90°C or 95°C, and specific point values ​​between the above values. Due to space limitations and for the sake of simplicity, this article will no longer exhaustively list the specific point values ​​included in the range. In one embodiment, the reaction time of the prepolymerization reaction is 4 to 6 hours, for example but not limited to 4 hours, 4.5 hours, 5 hours, 5.5 hours or 6 hours, and specific values ​​between the above values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific values ​​included in this range.

[0077] Unless otherwise specified, in the present invention, a prepolymer refers to a product obtained when a monomer (e.g., a phosphorus-containing compound having a structure shown in formula (1) and a vinyl-containing polyphenylene ether resin) undergoes a certain degree of reaction and reaches an intermediate molecular weight state. The molecular weight of this product is greater than the molecular weight of the monomer before the reaction, but less than the molecular weight of the final polymer obtained after the complete reaction. The prepolymer contains reactive functional groups that can be further polymerized to obtain a fully cross-linked or cured high molecular weight product. The prepolymerization reaction of the phosphorus-containing compound having a structure shown in formula (1) and the vinyl-containing polyphenylene ether resin described in the present invention refers to a conversion rate of the phosphorus-containing compound having a structure shown in formula (1) as a monomer or the vinyl-containing polyphenylene ether resin as a monomer greater than 0% and less than 100% (not including 0% and 100%), for example but not limited to a conversion rate between 10% and 90% (including 10% and 90%). A small amount of monomers that do not participate in the prepolymerization (unconverted) can increase the compatibility and cross-linking degree of the prepolymer in the resin composition. Specifically, a monomer conversion rate of 0% means that the monomer has no reaction at all and the aforementioned prepolymer cannot be formed. Similarly, a monomer conversion rate of 100% indicates that the monomer is completely reacted, and thus the aforementioned prepolymer cannot be formed. In order to allow the phosphorus-containing compound having the structure shown in formula (1) and the vinyl polyphenylene ether resin as reactants to undergo a certain degree of prepolymerization reaction to form a prepolymer of intermediate molecular weight, the conversion rate of the prepolymerization reaction of the present invention must be controlled to be greater than 0% and less than 100%, such as between 10% and 90% or between 30% and 80%, such as about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%.

[0078] In addition to the vinyl-containing resin and the phosphorus-containing compound or its prepolymer having the structure shown in formula (1), the resin composition of the present invention may also include additives as needed. For example, the aforementioned additives may include phosphorus-containing maleimide resins or phosphorus-containing copolymers. For example, in one embodiment, compared to 100 parts by weight of vinyl-containing resins, the resin composition of the present invention may also include 5 to 60 parts by weight of phosphorus-containing maleimide resins as needed, such as 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight or 60 parts by weight. For example, in one embodiment, the resin composition of the present invention includes 100 parts by weight of vinyl-containing resins, 35 to 60 parts by weight of phosphorus-containing compounds having the structure shown in formula (1), and 5 to 60 parts by weight of phosphorus-containing maleimide resins. For example, in one embodiment, the resin composition of the present invention includes 100 parts by weight of a vinyl resin, 50 to 90 parts by weight of a prepolymer of a phosphorus-containing compound having a structure represented by formula (1), and 5 to 45 parts by weight of a phosphorus-containing maleimide resin.

[0079] For example, in one embodiment, the phosphorus-containing maleimide resin is obtained by reacting a maleimide resin substituted with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) group with an aromatic phosphonate.

[0080] For example, in one embodiment, the structure of the maleimide resin substituted with a DOPO group is as follows:

[0081]

[0082] For example, in one embodiment, the structure of the aryl phosphonate is as follows:

[0083] Wherein X is vinyl or allyl.

[0084] For example, in one embodiment, a maleimide resin substituted with a DOPO group and an aryl phosphonate are reacted at a molar ratio of 1:1 to 1:3 to prepare a phosphorus-containing maleimide resin. For example, in one embodiment, the number average molecular weight of the phosphorus-containing maleimide resin is between 500 and 5,000.

[0085] In one embodiment, for example, the resin composition of the present invention may further include an inorganic filler, a hardening accelerator, an inhibitor, a solvent, a silane coupling agent, a surfactant, a dye, a toughening agent or a combination thereof as needed. If not otherwise specified, the content of any of the above ingredients may be 1 to 300 parts by weight, such as 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250 or 300 parts by weight, such as 30 to 150 parts by weight, and for example 200 to 300 parts by weight, relative to 100 parts by weight of the vinyl-containing resin.

[0086] The aforementioned inorganic filler can be any one or more inorganic fillers suitable for resin film, prepreg, laminate or printed circuit board production, and specific examples include but are not limited to: silicon dioxide (molten, non-molten, porous or hollow), aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite (boehmite, AlOOH), calcined talc, talc, silicon nitride, calcined kaolin, hollow porous particles or a combination thereof. In addition, the inorganic filler can be spherical, fibrous, plate-like, granular, flaky, needle-like or a combination thereof, and can be selectively pretreated with a silane coupling agent. In some embodiments, the present invention uses silicon dioxide (SC2050) sold by Admatechs.

[0087] For example, compared to 100 parts by weight of the vinyl-containing resin, the amount of the inorganic filler used in the present invention is not particularly limited, and can be, for example, 10 parts by weight to 300 parts by weight, 10 parts by weight to 200 parts by weight, or 80 parts by weight to 150 parts by weight.

[0088] The aforementioned hardening accelerator (including hardening initiator) may include a catalyst such as a Lewis base or a Lewis acid. The Lewis base may include one or more of imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP) and 4-dimethylaminopyridine (DMAP). The Lewis acid may include a metal salt compound, such as a metal salt compound of manganese, iron, cobalt, nickel, copper, zinc, etc., such as a metal catalyst such as zinc octoate and cobalt octoate.

[0089] The hardening accelerator may also include a hardening initiator, such as a peroxide that can generate free radicals. The hardening initiator includes but is not limited to: dibenzoyl peroxide, diisopropyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, di-tert-butyl peroxide, di(tert-butylperoxyisopropyl)benzene, di(tert-butylperoxy)phthalate, di(tert-butylperoxy)isophthalate, tert-butyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, lauroyl peroxide, tert-hexyl peroxypivalate, dibutylperoxyisopropylbenzene, bis(4-tert-butylcyclohexyl)peroxydicarbonate or a combination thereof. For example, compared to 100 parts by weight of the vinyl-containing resin, the content of the hardening accelerator used in the present invention is 0.01 to 5 parts by weight, preferably 0.5 to 2 parts by weight.

[0090] The above-mentioned inhibitor can be any one or more inhibitors suitable for the production of resin film, prepreg, laminate or printed circuit board. The inhibitor plays a role in inhibiting polymerization reaction, and its specific examples are not particularly limited, and can include various molecular inhibitors known in the art, stable free radical inhibitors or combinations thereof. For example, the molecular inhibitors suitable for the present invention include but are not limited to phenol, hydroquinone, 4-tert-butylcatechol, benzoquinone, chloranil, 1,4-naphthoquinone, trimethylquinone, aniline, nitrobenzene, Na2S, FeCl3, CuCl2 or combinations thereof. For example, the stable free radical inhibitors suitable for the present invention include but are not limited to 1,1-diphenyl-2-trinitrophenylhydrazine (DPPH), triphenylmethyl or combinations thereof.

[0091] The main function of adding solvent is to change the solid content of the resin composition and adjust the viscosity of the resin composition. For example, the solvent may include but is not limited to methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide, propylene glycol methyl ether and other solvents or mixed solvents thereof. For example, compared to 100 parts by weight of the vinyl-containing resin, the content of the solvent used in the present invention is preferably 80 to 120 parts by weight.

[0092] The aforementioned silane coupling agent may include various silane compounds (such as but not limited to siloxane compounds) and combinations thereof. Silane compounds may be further divided into aminosilane compounds, epoxysilane compounds, vinylsilane compounds, acrylate silane compounds, methacrylate silane compounds, hydroxyl silane compounds, isocyanate silane compounds, methacryloxy silane compounds and acryloxy silane compounds according to the types of functional groups.

[0093] The main function of adding the surfactant in the present invention is to make the inorganic filler uniformly dispersed in the resin composition.

[0094] The coloring agent suitable for use in the present invention may include, but is not limited to, dyes or pigments.

[0095] The main function of adding a toughening agent is to improve the toughness of the resin composition. The toughening agent may include but is not limited to rubber resin, carboxyl-terminated butadiene acrylonitrile rubber (CTBN), core-shell rubber or a combination thereof.

[0096] The resin composition of the present invention can be made into various products. For example, the product made from the resin composition of the present invention can include a prepreg, a resin film, a laminate or a printed circuit board.

[0097] The product made of the resin composition may be a semi-cured sheet (also known as a prepreg), which includes a reinforcing material and a layered material disposed on the reinforcing material. The layered material is obtained by heating the resin composition at high temperature to form a semi-cured state (B-stage). The baking temperature for making the semi-cured sheet is between 90°C and 150°C, preferably between 100 and 120. The reinforcing material may be any one of a fiber material, a woven fabric, and a non-woven fabric, and the woven fabric preferably includes a glass fiber cloth. The type of glass fiber cloth is not particularly limited, and may be a commercially available glass fiber cloth that can be used for various printed circuit boards, such as E-type glass cloth, D-type glass cloth, S-type glass cloth, T-type glass cloth, L-type glass cloth or Q-type glass cloth, wherein the types of fibers include yarn and roving, etc., and the form may include open fiber or unopen fiber. The aforementioned non-woven fabric preferably includes a liquid crystal resin non-woven fabric, such as a polyester non-woven fabric, a polyurethane non-woven fabric, etc., and is not limited thereto. The aforementioned fabric may also include liquid crystal resin fabric, such as polyester fabric or polyurethane fabric, etc., and is not limited thereto. This reinforcing material can increase the mechanical strength of the prepreg. In a preferred embodiment, the reinforcing material can also be selectively pretreated with a silane coupling agent. The prepreg is subsequently heated and cured (C-stage) to form an insulating layer.

[0098] The product made of the resin composition can be a resin film, which is obtained by baking and heating the resin composition to form a semi-cured state (B-stage). The resin composition can be selectively coated on a polyethylene terephthalate film (PET film), a polyimide film (PI film) or a liquid crystal resin film, and then baked and heated to form a semi-cured state, so that the resin composition forms a resin film. The resin composition can also be coated on a copper foil, and then baked and heated to form a semi-cured state to form a self-adhesive copper foil (RCC, also called a resin film with copper foil).

[0099] The product made of the resin composition may be a laminate, which includes two metal foils and an insulating layer disposed between the metal foils, the insulating layer being obtained by curing the aforementioned prepreg or resin film under high temperature and high pressure conditions (C-stage), wherein the suitable curing temperature may be between 190° C. and 230° C., preferably between 200° C. and 220° C., and the curing time may be between 60 and 180 minutes, preferably between 90 and 120 minutes. The metal foil may include copper, aluminum, nickel, platinum, silver, gold or alloys thereof, for example, the metal foil may be copper foil.

[0100] Preferably, the laminate is a copper clad laminate (CCL).

[0101] The laminate can be further processed through a circuit manufacturing process to form a printed circuit board.

[0102] In one or more embodiments, the article prepared from the resin composition of the present invention may satisfy at least one of the following characteristics, preferably at least two, more or all of the following characteristics:

[0103] The water absorption calculated according to the method described in IPC-TM-6502.6.16.1 is less than or equal to 0.31%, such as between 0.16% and 0.31%, or between 0.21% and 0.28%;

[0104] The dielectric constant measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 3.27, for example, between 2.97 and 3.18, or between 3.02 and 3.27;

[0105] The dielectric loss measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 0.00287, for example, between 0.00204 and 0.00287, or between 0.00225 and 0.00287;

[0106] The elongation measured according to the method described in ASTM D412 is greater than or equal to 6.95%, such as between 6.95% and 9.24%;

[0107] A copper foil pull force greater than or equal to 3.07 lb / in, such as between 3.07 lb / in and 3.39 lb / in, or between 3.15 lb / in and 3.45 lb / in, as measured by the method described in IPC-TM-6502.4.8; and

[0108] The glass transition temperature measured according to the method described in IPC-TM-650 2.4.24.4 is greater than or equal to 182°C, such as between 182°C and 216°C, or between 191°C and 228°C.

[0109] The measurement methods of the above characteristics will be described in detail later in this article.

[0110] The resin compositions of the embodiments of the present invention and the comparative examples of the present invention were prepared using various raw materials from the following sources in the amounts shown in Tables 1 to 10, and were further prepared into various test samples. Among them, the resin compositions of Examples E1 to E17 include vinyl resins and phosphorus-containing compounds having a structure shown in Formula (1), and the resin compositions of Examples E18 to E38 include prepolymers of vinyl resins and phosphorus-containing compounds having a structure shown in Formula (1).

[0111] The chemical raw materials used in the manufacturing examples, synthesis examples, embodiments and comparative examples of the present invention are as follows:

[0112] Phosphorus-containing compounds (1-1) to (1-9): as described in Production Examples 1-1 to 1-9.

[0113] Phenylphosphonic dichloride: commercially available.

[0114] Bisxylenol A (2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane): commercially available.

[0115] 4-Chlorostyrene: commercially available.

[0116] 2,2-bis(4-hydroxyphenyl)adamantanel: commercially available.

[0117] Bisphenol TMC (1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane): commercially available.

[0118] SA90: bishydroxy polyphenylene ether resin, available from Sabic.

[0119] 4-vinylbenzyl chloride: commercially available.

[0120] Bisphenol A (2,2-bis(4-hydroxyphenyl)propane) was purchased from Sigma-Aldrich.

[0121] Methylphosphonic dichloride: commercially available.

[0122] Methacryloyl chloride: commercially available.

[0123] Methacrylate-containing polyphenylene ether resin, referred to as PPO A, as shown in Preparation Example 2.

[0124] OPE-2st 2200: terminal bisvinyl benzyl polyphenylene ether resin, purchased from Mitsubishi Gas Chemical.

[0125] SA9000: polyphenylene ether resin containing methacrylate, purchased from Sabic.

[0126] BMI-70: aromatic bismaleimide resin, purchased from KI Chemicals.

[0127] MIR-5000: bismaleimide, purchased from Nippon Kayaku Co., Ltd.

[0128] The compound having the structure represented by formula (2): as in Preparation Example 3.

[0129] TAIC: triallyl isocyanurate, commercially available.

[0130] Ricon 100: Styrene-butadiene copolymer, available from Cray Valley.

[0131] B-1000: polybutadiene resin, purchased from Nippon Soda.

[0132] Ricon 184MA6: styrene-butadiene-maleic anhydride terpolymer resin, available from Cray Valley.

[0133] H1052: hydrogenated styrene-butadiene-styrene triblock copolymer, available from Asahi KASEI.

[0134] Additive (A): phosphorus-containing maleimide resin, as described in Preparation Example 4-1, having a number average molecular weight between 500 and 5,000.

[0135] Additive (B): phosphorus-containing maleimide resin, as described in Preparation Example 4-2, having a number average molecular weight between 500 and 5,000.

[0136] Additive (C): phosphorus-containing copolymer, as described in Preparation Example 4-3.

[0137] Additive (D): phosphorus-containing copolymer, as described in Preparation Example 4-4.

[0138] SC2050: silicon dioxide, purchased from Admatechs.

[0139] 25B: 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, purchased from NOF Corporation.

[0140] Toluene: commercially available.

[0141] SPV-100: a phosphazene compound, commercially available.

[0142] OPE-2st 1200: terminal bisvinyl benzyl polyphenylene ether resin, purchased from Mitsubishi Gas Chemical.

[0143] Cyclic phosphazene mixture: commercially available, including compounds of the structures shown in the following formula (3-1), formula (3-2) and formula (3-3), wherein the molar ratio of formula (3-1): formula (3-2): formula (3-3) is 50-60:35-45:0-5.

[0144]

[0145] Prepolymer 1 to Prepolymer 13: as described in Synthesis Examples 1 to 13.

[0146] Production Example 1-1

[0147] Phenylphosphoryl dichloride and tetramethylbisphenol A in a molar ratio of 1:2, 0.01wt% to 0.1wt% of a catalyst boron trifluoride diethyl etherate relative to the total weight of the two compounds, 0.5wt% to 1.5wt% of a phase transfer agent triphenylbutylphosphonium bromide (BTPPB) and an appropriate amount of a mixed solvent (toluene and butanone in a weight ratio of 1:1) are added to a stirring tank, first heated to 75°C and stirred until dissolved, then heated to 90-100°C, and an appropriate amount of NaOH and deionized water are added, and the mixture is continuously stirred at a constant temperature for 4-6 hours, then cooled to 70°C, and 3 moles of 4-chlorostyrene relative to phenylphosphoryl dichloride are added, and the stirring at the constant temperature is continued for 4-6 hours. The mixture is then cooled to room temperature for neutralization reaction, and an appropriate amount of phosphoric acid and deionized water are first added. After three extractions, the solvent is removed by distillation under reduced pressure to obtain a brown solid phosphorus-containing compound (1-1) having a skeleton as shown in formula (1), wherein R1 has a structure as shown in formula (a), R2 has a structure as shown in formula (e), and R3 is a phenyl group. The weight average molecular weight is between 800 and 1,000, and the compound belongs to the phosphorus-containing compound having a structure as shown in formula (1) of the present invention.

[0148] Production Example 1-2

[0149] The same as Preparation Example 1-1, except that 2,2-bis(4-hydroxyphenyl)adamantane is used to replace tetramethylbisphenol A to obtain a phosphorus-containing compound (1-2) having a skeleton represented by formula (1), wherein R1 has a structure represented by formula (b), R2 has a structure represented by formula (e), and R3 is a phenyl group. The weight average molecular weight is between 8,500 and 9,500, and the phosphorus-containing compound having a structure represented by formula (1) of the present invention is obtained.

[0150] Production Example 1-3

[0151] The same as manufacturing example 1-1, except that bisphenol TMC is used to replace tetramethyl bisphenol A to obtain a phosphorus-containing compound (1-3), which has a skeleton shown in formula (1), wherein R1 has a structure shown in formula (c), R2 has a structure shown in formula (e), and R3 is a phenyl group. Its weight average molecular weight is between 3,000 and 4,000, and it belongs to the phosphorus-containing compound having the structure shown in formula (1) of the present invention.

[0152] Production Example 1-4

[0153] The same as manufacturing example 1-1, except that SA90 is used to replace tetramethyl bisphenol A to obtain a phosphorus-containing compound (1-4), which has a skeleton shown in formula (1), wherein R1 has a structure shown in formula (d), R2 has a structure shown in formula (e), and R3 is a phenyl group. Its weight average molecular weight is between 3,000 and 4,000, and it belongs to the phosphorus-containing compound having the structure shown in formula (1) of the present invention.

[0154] Production Example 1-5

[0155] The same as Preparation Example 1-1, except that 4-chlorostyrene is replaced by 4-vinylbenzyl chloride to obtain a phosphorus-containing compound (1-5) having a skeleton represented by formula (1), wherein R1 has a structure represented by formula (a), R2 has a structure represented by formula (f), and R3 is a phenyl group. The weight average molecular weight is between 3,000 and 4,000, and it belongs to the phosphorus-containing compound having the structure represented by formula (1) of the present invention.

[0156] Production Example 1-6

[0157] The same as manufacturing example 1-1, except that bisphenol A is used to replace tetramethyl bisphenol A to obtain a phosphorus-containing compound (1-6) having a skeleton shown in formula (1), wherein R1 has the structure shown below, R2 has the structure shown in formula (e), and R3 is phenyl, which does not belong to the phosphorus-containing compound having the structure shown in formula (1) of the present invention.

[0158] R1:

[0159] Production Example 1-7

[0160] The same as manufacturing example 1-1, except that methylphosphonyl dichloride is used to replace phenylphosphonyl dichloride to obtain a phosphorus-containing compound (1-7) having a skeleton shown in formula (1), wherein R1 has a structure shown in formula (a), R2 has a structure shown in formula (e), and R3 is methyl, which does not belong to the phosphorus-containing compound having the structure shown in formula (1) of the present invention.

[0161] Production Example 1-8

[0162] The same as manufacturing example 1-1, except that methacryloyl chloride is used to replace 4-chlorostyrene to obtain a phosphorus-containing compound (1-8) having a skeleton shown in formula (1), wherein R1 has a structure shown in formula (a), R2 has a structure shown below, and R3 is phenyl, which does not belong to the phosphorus-containing compound having a structure shown in formula (1) of the present invention.

[0163] R2:

[0164] Production Example 1-9

[0165] The same as manufacturing example 1-1, except that 4-chlorostyrene is not used, and the phosphorus-containing compound (1-9) is obtained, which has a skeleton shown in formula (1), wherein R1 has a structure shown in formula (a), R2 is hydrogen, and R3 is phenyl, which does not belong to the phosphorus-containing compound having the structure shown in formula (1) of the present invention.

[0166] Production Example 2

[0167] Add 400 g (0.2 mol) of SA90, 17.5 g (0.1 mol) of α, α'-dichloroparaxylene, 33.9 g (0.01 mol) of tetrabutylphosphonium bromide and 600 g of toluene into a stirring tank, heat to 75°C and stir to dissolve until mixed evenly. After heating to 95°C, add 45 g (1.125 mol) of NaOH and 33 g of deionized water, and continue stirring for 6 hours. After cooling to 70°C, add 36.6 g (0.35 mol) of methacryloyl chloride and continue stirring for 4 hours. After reacting for 4 hours, cool to room temperature, neutralize, and add 8.8 g (0.09 mol) of phosphoric acid and 165 g of deionized water. After standing, the solution is divided into upper and lower layers. Add 330 g of deionized water and stir, and remove the waste liquid three times. Finally, remove the solvent by vacuum distillation to obtain a methacrylate-containing polyphenylene ether resin, referred to as PPO A.

[0168] Production Example 3

[0169] 296 parts by weight of 2-bromoethylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 70 parts by weight of α,α'-dichloro-p-xylene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 18.4 parts by weight of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were reacted at 130°C for 8 hours, cooled to room temperature, neutralized with sodium hydroxide aqueous solution, and extracted with 1200 parts by weight of toluene. The organic layer was washed with water. The solvent and excess 2-bromoethylbenzene were distilled off under heating and reduced pressure to obtain an intermediate product. Among them, the molar ratio of 2-bromoethylbenzene to α,α'-dichloro-p-xylene can be 4:1; methanesulfonic acid is used as an acidic catalyst, and can be replaced by other acidic catalysts such as hydrochloric acid and phosphoric acid. The reaction conditions can be 40-180°C for 0.5-20 hours.

[0170] 22 parts by weight of the intermediate product, 50 parts by weight of toluene (other aromatic solvents such as xylene may also be used), 150 parts by weight of dimethyl sulfoxide (other aprotic polar solvents such as dimethyl sulfoxide may also be used), 15 parts by weight of water and 5.4 parts by weight of sodium hydroxide (other alkaline catalysts such as potassium hydroxide and potassium carbonate may also be used) are reacted at 40° C. for 5 hours, cooled to room temperature, and then 100 parts by weight of toluene are added. The organic layer is washed with water, and the solvent is distilled off under heating and reduced pressure to obtain a compound having a structure represented by formula (2), wherein m is an integer from 1 to 20.

[0171] Production Example 4-1

[0172] A maleimide resin substituted with a DOPO group (structure as follows, purchased from Liuhe Chemical) and bis(4-allylphenyl)phenylphosphonate (manufactured as described below) in a molar ratio of 1:1 were added to a reaction flask, 0.01-0.1 wt% of zinc octoate and an appropriate amount of butanone relative to the total weight of the aforementioned compounds, and the temperature was raised to 75° C. while stirring until the mixture was uniformly mixed, and then the temperature was raised to 95° C. and reacted at a constant temperature for 6 hours to obtain a phosphorus-containing maleimide resin with a solid content of about 60% to 70%.

[0173] The structure of the maleimide resin substituted with DOPO groups is as follows:

[0174]

[0175] Preparation of bis(4-allylphenyl)phenylphosphonate: 2.0-2.1 mol of 4-allylphenol, 150 ml of dry acetonitrile and 5 ml of triethylamine were added to a reaction flask in sequence, stirred at room temperature and 1 mol of phenylphosphoryl dichloride was added dropwise to the reaction system within 60 minutes. After the addition was completed, the temperature was raised to 85-90°C and reacted for 24 hours. Then, triethylamine hydrochloride was filtered out, the filtrate was concentrated by a rotary evaporator to remove part of the solvent and poured into deionized water to precipitate solids. After suction filtration, the obtained product was washed three times with cold tetrahydrofuran and distilled water respectively, and vacuum dried at 50°C for 48 hours to obtain bis(4-allylphenyl)phenylphosphonate.

[0176] Production Example 4-2

[0177] Basically the same as Preparation Example 4-1, except that bis(4-allylphenyl)phenylphosphonate is replaced with bis(4-vinylphenyl)phenylphosphonate (the preparation method is described below), a phosphorus-containing maleimide resin with a solid content of about 60% to 70% can be obtained.

[0178] Preparation of bis(4-vinylphenyl)phenylphosphonate: 2.0-2.1 mol of p-vinylphenol, 150 ml of dry acetonitrile and 5 ml of triethylamine were added to a reaction flask in sequence, stirred at room temperature and 1 mol of phenylphosphoryl dichloride was added dropwise to the reaction system within 60 minutes. After the addition was completed, the temperature was raised to 85-90°C and reacted for 24 hours. Then, triethylamine hydrochloride was filtered out, the filtrate was concentrated by a rotary evaporator to remove part of the solvent and poured into deionized water to precipitate solids. After suction filtration, the obtained product was washed three times with cold tetrahydrofuran and distilled water respectively, and vacuum dried at 50°C for 48 hours to obtain bis(4-vinylphenyl)phenylphosphonate.

[0179] Production Example 4-3

[0180] 1 mol of divinylbenzene, 1 mol of 1,2-bis(4-vinylphenyl)ethane (BVPE), 1 mol of bis(4-allylphenyl)phenylphosphonate, 0.01-0.1 wt% of zinc octoate relative to the total weight of the aforementioned compounds and an appropriate amount of butanone were added to a reaction bottle in sequence, and the temperature was raised to 75° C. while stirring until the mixture was uniformly mixed, and then the temperature was raised to 95° C. and kept at a constant temperature for 6 hours to obtain a phosphorus-containing copolymer with a solid content of about 60% to 70%.

[0181] Production Example 4-4

[0182] Basically the same as Preparation Example 4-3, except that bis(4-allylphenyl)phenylphosphonate is replaced with bis(4-vinylphenyl)phenylphosphonate, to obtain a phosphorus-containing copolymer with a solid content of about 60% to 70%.

[0183] Synthesis example 1

[0184] The phosphorus-containing compound (1-1) and OPE-2st 1200 (molar ratio of 1:2), 0.01-0.1wt% of azobisisobutyronitrile (AIBN) relative to the total weight of the aforementioned compounds, and an appropriate amount of butanone are added to a three-necked flask, the temperature is raised to 60° C. to 95° C. and the constant temperature stirring is continued for 4-6 hours to obtain a prepolymer solution with a solid content of about 55% to 65%, which is the prepolymer 1 of the present invention.

[0185] Synthesis Example 2 to Synthesis Example 5

[0186] The method is basically the same as Synthesis Example 1, except that the phosphorus-containing compound (1-1) is replaced with phosphorus-containing compounds (1-2) to (1-5), respectively, and prepolymers 2 to 5 of the present invention are obtained after synthesis.

[0187] Synthesis example 6

[0188] The method is basically the same as Synthesis Example 1, except that OPE-2st 1200 is replaced with SA9000, and the prepolymer 6 of the present invention is obtained after synthesis.

[0189] Synthesis Example 7

[0190] The method is basically the same as Synthesis Example 1, except that the molar ratio of the phosphorus-containing compound (1-1) to OPE-2st 1200 is changed from 1:2 to 1:1, and the prepolymer 7 of the present invention is obtained after synthesis.

[0191] Synthesis example 8

[0192] The method is basically the same as Synthesis Example 1, except that the molar ratio of the phosphorus-containing compound (1-1) to OPE-2st 1200 is changed from 1:2 to 2:1, and the prepolymer 8 of the present invention is obtained after synthesis.

[0193] Synthesis example 9

[0194] The method is basically the same as Synthesis Example 1, except that the phosphorus-containing compound (1-1) is replaced with SPV-100, and prepolymer 9 is obtained after synthesis.

[0195] Synthesis example 10

[0196] The method is basically the same as Synthesis Example 1, except that the phosphorus-containing compound (1-1) is replaced with a cyclic phosphazene mixture, and a prepolymer 10 is obtained after synthesis.

[0197] Synthesis example 11

[0198] The method is basically the same as Synthesis Example 1, except that the phosphorus-containing compound (1-1) is replaced by the phosphorus-containing compound (1-6), and prepolymer 11 is obtained after synthesis.

[0199] Synthesis example 12

[0200] The method is basically the same as Synthesis Example 1, except that the phosphorus-containing compound (1-1) is replaced with the phosphorus-containing compound (1-7), and prepolymer 12 is obtained after synthesis.

[0201] Synthesis example 13

[0202] The method is basically the same as Synthesis Example 1, except that the phosphorus-containing compound (1-1) is replaced by the phosphorus-containing compound (1-8), and prepolymer 13 is obtained after synthesis.

[0203] [Table 1] Composition of the resin composition of the embodiment (unit: weight part) and characteristic test results

[0204]

[0205]

[0206] [Table 2] Composition (unit: weight parts) and characteristic test results of the resin composition of the embodiment

[0207]

[0208]

[0209] [Table 3] Composition (unit: weight parts) and property test results of the resin composition of the embodiment

[0210]

[0211]

[0212] [Table 4] Composition (unit: weight parts) and property test results of comparative example resin composition

[0213]

[0214]

[0215] [Table 5] Composition (unit: weight parts) and property test results of the resin composition of the embodiment

[0216]

[0217]

[0218] [Table 6] Composition (unit: weight parts) and characteristic test results of the resin composition of the embodiment

[0219]

[0220]

[0221] [Table 7] Composition (unit: weight parts) and property test results of the resin composition of the embodiment

[0222]

[0223]

[0224] [Table 8] Composition (unit: weight parts) and property test results of the resin composition of the embodiment

[0225]

[0226]

[0227] [Table 9] Composition (unit: weight parts) and property test results of comparative example resin composition

[0228]

[0229]

[0230] [Table 10] Composition (unit: weight parts) and property test results of comparative example resin composition

[0231]

[0232]

[0233] The above characteristics are prepared by referring to the following method to prepare the object to be tested (sample), and then the characteristics are analyzed according to specific conditions.

[0234] 1. Resin film:

[0235] The resin compositions of the aforementioned embodiments and comparative examples (in parts by weight) were respectively used, added into a stirring tank and mixed evenly to form a varnish, which was then coated onto copper foil (trade name MT18Ex, containing 18 micron carrier copper foil and 3 micron thin copper, purchased from Mitsui Metal) to allow the resin composition to adhere evenly, and then heated and baked at a temperature of 100° C. for 10 minutes, and then the 18 micron carrier copper foil was removed, and then the 3 micron thin copper was removed by etching to obtain a resin film with a thickness of 32.5 microns.

[0236] 2. Prepreg (PP):

[0237] The resin compositions of the above-mentioned embodiments and comparative examples (in parts by weight) are respectively used, and each component of the above-mentioned resin composition is added into a stirring tank and mixed evenly to form a varnish. The varnish is placed into an impregnation tank, and then a glass fiber cloth (e.g., L-glass fiber cloth (L-glass fiber fabric) with a specification of 1078, purchased from Xinyue Company) is immersed in the above-mentioned impregnation tank to make the resin composition adhere to the glass fiber cloth, and then heated at 100° C. to a semi-cured state (B-Stage) at 120° C. to obtain a semi-cured sheet, whose resin content is about 70%.

[0238] 3. Copper-containing substrate 1 (made of two prepregs pressed together):

[0239] Prepare two 0.5 ounce thick HVLP (Hyper Very Low Profile) copper foils and two 1078-gauge L-glass fiber cloths impregnated with the prepregs made of the samples to be tested, and the resin content of each prepreg is about 70%. The copper foil, two prepregs and copper foil are stacked in order, and pressed for 90 minutes to 120 minutes under vacuum conditions, a pressing pressure of 250 psi to 600 psi and a temperature of 200° C. to 220° C. to form a copper-containing substrate 1. The two prepregs are cured to form an insulating layer between the two copper foils, and the resin content of the insulating layer is about 70%.

[0240] 4. Copper-containing substrate 2 (made of six prepregs pressed together):

[0241] The preparation method is basically the same as that of the copper-containing substrate 1, except that the insulating layer is formed by curing six prepreg sheets.

[0242] 5. Copper-free substrate 1 (made of two prepregs pressed together):

[0243] The copper-containing substrate 1 formed by pressing two prepregs is etched to remove the copper foil on both sides, thereby obtaining a copper-free substrate 1 (formed by pressing two prepregs).

[0244] 6. Copper-free substrate 2 (made of six prepregs pressed together):

[0245] The copper-containing substrate 2 formed by pressing six prepregs is etched to remove the copper foil on both sides, thereby obtaining a copper-free substrate 2 (formed by pressing six prepregs).

[0246] For the aforementioned samples to be tested, each test method and its characteristic analysis items are described as follows.

[0247] PCT (pressure cooking test) water absorption ratio

[0248] A copper-free substrate 2 (made of six prepregs pressed together, with a resin content of about 70%) with a length of 2 inches and a width of 2 inches was selected as the sample to be tested. Each sample to be tested was placed in an oven at 105±10°C for baking for 1 hour and then taken out. After cooling at room temperature (about 25°C) for 10 minutes, the weight of the copper-free substrate was weighed as W1. Then, referring to the method described in IPC-TM-650 2.6.16.1, a pressure cooking test (PCT) was performed to absorb moisture for 5 hours (test temperature 121°C and relative humidity 100%), and the water remaining on the surface of the substrate was wiped dry. After wiping dry, the weight obtained was the weight of the copper-free substrate after water absorption, which was W2. The pressure cooking (PCT) water absorption rate was calculated according to the formula: water absorption rate W (%) = ((W2-W1) / W1) × 100%, and the unit is %. In the art, the lower the PCT water absorption, the better. A PCT water absorption difference greater than or equal to 0.1% indicates that there is a significant difference in the PCT water absorption of different substrates.

[0249] Dielectric constant (Dk)

[0250] In the measurement of the dielectric constant, the copper-free substrate 1 (made of two semi-cured sheets pressed together, with a resin content of about 70%) is selected as the sample to be tested. A microwave dielectrometer (purchased from AET Company of Japan) is used to measure each sample to be tested at room temperature (about 25°C) and a frequency of 10 GHz, referring to the method described in JIS C2565. At a measurement frequency of 10 GHz, for low dielectric constant materials, a difference in Dk values ​​less than 0.1 means that there is no significant difference in the dielectric constant of the substrate (no significant difference means that there is no significant technical difficulty), and a difference in Dk values ​​greater than or equal to 0.1 means that there is a significant difference between the dielectric constants of different substrates (there is a significant technical difficulty).

[0251] Dielectric loss (dissipation factor, Df)

[0252] In the measurement of dielectric loss, the above-mentioned copper-free substrate 1 (made of two semi-cured sheets pressed together, with a resin content of about 70%) is selected as the sample to be tested. A microwave dielectrometer (purchased from AET Company of Japan) is used, and the method described in JIS C2565 is referred to, and each sample to be tested is measured at room temperature (about 25°C) and at a frequency of 10GHz to obtain the dielectric loss. The lower the dielectric loss, the better the dielectric properties of the sample to be tested. At a measurement frequency of 10GHz and a Df value ranging from 0.0010 to 0.0030, a difference in Df value of less than 0.0005 indicates that there is no significant difference in the dielectric loss of the substrate (no significant difference means that there is no significant technical difficulty), and a difference in Df value greater than or equal to 0.0005 indicates that there is a significant difference between the dielectric losses of different substrates (there is a significant technical difficulty).

[0253] Elongation

[0254] The above resin film was selected as the sample to be tested. A universal tensile strength tester was used, and the elongation of the sample at break was measured at a tensile rate of 50.8 mm / min, with reference to the method described in ASTM D412. The unit is %, and the higher the elongation, the better. In this field, an elongation difference greater than or equal to 0.5% indicates that there is a significant difference in the elongation of different samples.

[0255] Copper foil pull (0.5 oz) (Hoz peeling strength, Hoz P / S)

[0256] The above copper-containing substrate 2 (made of six semi-cured sheets pressed together, with a resin content of about 70%) was selected and cut into rectangular samples with a width of 24 mm and a length greater than 60 mm, and the surface copper foil was etched, leaving only a long strip of copper foil with a width of 3.18 mm and a length greater than 60 mm. The universal tensile strength tester was used to measure the force required to pull 0.5 ounces of copper foil away from the surface of the substrate insulation layer at room temperature (about 25°C) with reference to the method described in IPC-TM-6502.4.8, and the unit was lb / in. In this field, the higher the copper foil tension, the better. For copper foil substrates with dielectric loss values ​​measured between 0.0010 and 0.0030 at a frequency of 10 GHz, a difference in copper foil tension greater than or equal to 0.3 lb / in means that there is a significant difference in copper foil tension between different substrates.

[0257] Glass transition temperature (Tg)

[0258] The copper-free substrate 2 (six prepregs pressed together, with a resin content of about 70%) was selected as the sample to be tested. The glass transition temperature of each sample to be tested was measured by a dynamic mechanical analyzer (DMA) with reference to IPC-TM-6502.4.24.4 Glass Transition and Modulus of Materials Used in High Density Interconnection (HDI) and Microvias-DMA Method, in degrees Celsius. The measuring temperature range was 50 to 400 degrees Celsius, with a temperature rise rate of 2 degrees Celsius per minute. The higher the glass transition temperature, the better.

[0259] By referring to the test results in Tables 1 to 11, the following phenomena can be clearly observed.

[0260] The resin compositions of Comparative Examples C1 to C4 use other phosphorus-containing compounds different from the phosphorus-containing compound with the structure represented by formula (1), and the products fail to meet the requirements in at least one of the properties such as PCT water absorption, dielectric constant, dielectric loss, elongation, copper foil tensile force and glass transition temperature.

[0261] The amount of the phosphorus-containing compound having the structure shown in formula (1) used in the resin compositions of Comparative Examples C5 to C6 is not within the range of 35 to 60 parts by weight (compared to 100 parts by weight of the vinyl-containing resin), and the products fail to meet the requirements in at least one of the properties such as PCT water absorption, dielectric constant, dielectric loss, elongation, tensile force on copper foil and glass transition temperature.

[0262] The resin compositions of Examples E14 to E17 contain phosphorus-containing maleimide resin, and the products have better PCT water absorption, dielectric constant, dielectric loss, elongation, copper foil tension and glass transition temperature.

[0263] The resin compositions of comparison examples C7, C8, C11 to C13 use prepolymers other than the prepolymer of the phosphorus-containing compound having the structure represented by formula (1), and the products fail to meet the requirements in at least one of the properties such as PCT water absorption, dielectric constant, dielectric loss, copper foil tensile force and glass transition temperature.

[0264] The amount of the prepolymer of the phosphorus-containing compound having the structure shown in formula (1) used in the resin compositions of Comparative Examples C9 to C10 is not within the range of 50 to 90 parts by weight (compared to 100 parts by weight of the vinyl-containing resin), and the products fail to meet the requirements in at least one of the properties such as PCT water absorption, dielectric constant, dielectric loss, tensile force on copper foil and glass transition temperature.

[0265] The resin compositions of Examples E34 to E37 contain phosphorus-containing maleimide resin, and the products have better PCT water absorption, dielectric constant, dielectric loss, copper foil tension and glass transition temperature.

[0266] All of the embodiments E1 to E38 can further improve at least one of the properties of PCT water absorption, dielectric constant, dielectric loss, elongation, copper foil tension and glass transition temperature compared to all of the comparative examples C1 to C13. In addition, by observing the embodiments E1 to E17 (including vinyl resin and phosphorus-containing compounds having the structure shown in formula (1)) and the embodiments E18 to E38 (including vinyl resin and phosphorus-containing compounds having the structure shown in formula (1)), it can be found that if the resin composition uses a prepolymer of a phosphorus-containing compound having the structure shown in formula (1), then compared to the technical solution of using a phosphorus-containing compound having the structure shown in formula (1), further property improvements can be obtained in one or more aspects, such as but not limited to PCT water absorption, copper foil tension and / or glass transition temperature. For example, by comparing the embodiment E38 and the embodiment E9 side by side, it can be found that the technical solution of using a prepolymer of a phosphorus-containing compound having the structure shown in formula (1) can obtain further property improvements in glass transition temperature.

[0267] The above embodiments are essentially only for auxiliary explanation and are not intended to limit the embodiments of the application or the applications or uses of the embodiments. In this article, the term "exemplary" means "serving as an example, example or illustration". Any exemplary embodiment in this article is not necessarily interpreted as being better or more advantageous than other embodiments.

[0268] In addition, although at least one exemplary embodiment or comparative example has been proposed in the aforementioned embodiments, it should be understood that the present invention can still have a large number of variations. It should also be understood that the embodiments described herein are not intended to limit the scope, use or configuration of the requested application object in any way. On the contrary, the aforementioned embodiments will provide a simple guide for those skilled in the art to implement one or more of the embodiments. Furthermore, various changes can be made to the functions and arrangements of the components without departing from the scope defined by the claims, and the claims include known equivalents and all foreseeable equivalents at the time of filing the present patent application.

Claims

1. A resin composition, characterized in that The resin composition comprises: Containing vinyl resins; and A phosphorus-containing compound having a structure represented by formula (1) or a prepolymer thereof; in: The phosphorus-containing compound having the structure represented by formula (1) is contained in an amount of 35 to 60 parts by weight relative to 100 parts by weight of the vinyl-containing resin; or the phosphorus-containing compound prepolymer having the structure represented by formula (1) is contained in an amount of 50 to 90 parts by weight relative to 100 parts by weight of the vinyl-containing resin; Wherein, R1 each independently represents any divalent functional group represented by the following formula (a) to formula (d): wherein p and q are each independently positive integers, and p+q is between 2 and 11; R2 each independently represents any one of the monovalent functional groups shown in the following formula (e) to formula (f): R3 represents a phenyl group; and n represents the number of repetitions of the unit in the brackets, which can make the weight average molecular weight of the phosphorus-containing compound having the structure represented by formula (1) be between 500 and 10,000.

2. The resin composition according to claim 1, characterized in that The vinyl-containing resin includes vinyl-containing polyphenylene ether resin, maleimide resin, a compound having a structure shown in formula (2), vinyl-containing polyolefin resin, triallyl isocyanurate or a combination thereof. wherein m is an integer from 1 to 20.

3. The resin composition according to claim 1, characterized in that The prepolymer of the phosphorus-containing compound having a structure shown in formula (1) is prepared by prepolymerization of a mixture, and the mixture comprises the phosphorus-containing compound having a structure shown in formula (1) and a vinyl-containing polyphenylene ether resin in a molar ratio between 1:2 and 2:

1.

4. The resin composition according to claim 3, characterized in that The mixture is prepolymerized at a temperature of 60° C. to 95° C. for 4 to 6 hours to prepare a prepolymer of the phosphorus-containing compound having a structure represented by formula (1).

5. The resin composition according to claim 3, characterized in that The conversion rate of the prepolymerization reaction is between 10% and 90%.

6. The resin composition according to claim 1, characterized in that The resin composition includes 100 parts by weight of a vinyl resin and 35 to 60 parts by weight of a phosphorus-containing compound having a structure represented by formula (1).

7. The resin composition according to claim 1, characterized in that The resin composition includes 100 parts by weight of a vinyl resin and 50 to 90 parts by weight of a prepolymer of a phosphorus-containing compound having a structure represented by formula (1).

8. The resin composition according to claim 1, characterized in that The resin composition further comprises a phosphorus-containing maleimide resin.

9. The resin composition according to claim 8, characterized in that The resin composition comprises 100 parts by weight of a vinyl resin, 35 to 60 parts by weight of a phosphorus-containing compound having a structure represented by formula (1), and 5 to 60 parts by weight of a phosphorus-containing maleimide resin.

10. The resin composition according to claim 8, characterized in that The resin composition comprises 100 parts by weight of a vinyl resin, 50 to 90 parts by weight of a prepolymer of a phosphorus-containing compound having a structure represented by formula (1), and 5 to 45 parts by weight of a phosphorus-containing maleimide resin.

11. The resin composition according to claim 1, characterized in that The resin composition further comprises an inorganic filler, a hardening accelerator, an inhibitor, a solvent, a silane coupling agent, a surfactant, a colorant, a toughening agent or a combination thereof.

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

13. The article according to claim 12, characterized in that The products refer to IPC-TM-650 The water absorption calculated by the method described in 2.6.16.1 is less than or equal to 0.31%.

14. The article of claim 12, wherein: The elongation of the article measured according to the method described in ASTM D412 is greater than or equal to 6.95%.

15. The article of claim 12, wherein: The copper foil tensile force of the product measured according to the method described in IPC-TM-6502.4.8 is greater than or equal to 3.07 lb / in.

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