Resin composition and product thereof

Abstract

Disclosed is a resin composition comprising 100 parts by weight of a maleimide resin and 0.3 to 10.0 parts by weight of an organic phosphine compound having a structure represented by formula (1) wherein-R-comprises a substituted or unsubstituted phenylidene group, biphenylidene group or naphthylidene group. Also disclosed is the use of the resin composition in the preparation of an article comprising a prepreg, a resin film, a laminate printed circuit board or a cured insulator, as well as an article at least partially made from the resin composition.

Description

Technical Field

[0001] This application relates to the field of compositions, and more particularly to a resin composition and articles thereof. Background Technology

[0002] In recent years, electronic technology has been developing towards higher integration, lower power consumption, and higher performance, thus placing higher demands on high-performance electronic materials. To ensure the stability and reliability of electronic materials, substrate materials with higher glass transition temperatures or lower coefficients of thermal expansion have been an important development direction for printed circuit boards (PCBs). A high glass transition temperature ensures that PCBs maintain stable electrical characteristics in high-temperature environments, while a low coefficient of thermal expansion ensures that PCBs maintain minimal dimensional changes with temperature variations, preventing connection failures between components. Therefore, developing a suitable high-performance substrate material with both high glass transition temperature and low coefficient of thermal expansion is a current active goal in the industry.

[0003] In addition, while ensuring that the material can achieve high glass transition temperature and low thermal expansion rate, how to balance the flow characteristics of the material in the semi-cured state and the normal appearance in the cured state is also a problem that the industry needs to work hard to solve. 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 this application is to provide a resin composition that can overcome at least one of the above-mentioned technical problems, and articles made using this resin composition.

[0005] In one aspect, this application provides a resin composition comprising 100 parts by weight of maleimide resin and 0.3 to 10.0 parts by weight of an organophosphorus compound, wherein the organophosphorus compound has the structure shown in formula (1).

[0006]

[0007] Wherein, –R– includes substituted or unsubstituted benzoyl, biphenylyl, or naphthyl groups, or is composed of them.

[0008] In one aspect, this application provides the use of the resin composition in the preparation of articles including prepregs, resin films, laminates, printed circuit boards, or cured insulators.

[0009] In one aspect, this application provides an article comprising a prepreg, a resin film, a laminate, a printed circuit board, or a cured insulator, wherein at least a portion of the article is made of the resin composition.

[0010] The resin compositions or articles thereof provided in some embodiments of this application can improve one or more aspects such as glass transition temperature, coefficient of thermal expansion, in-plate resin flow, resin flow rate, and substrate edge striations. Attached Figure Description

[0011] Figure 1 This is a schematic diagram of the appearance of a copper-free substrate with a dendritic stripe distribution.

[0012] Figure 2 This is a schematic diagram of the appearance of a copper-free substrate without dendritic stripes. Detailed Implementation

[0013] To further illustrate the technical means and effects adopted by this application in order to achieve the intended purpose, the following detailed description of the specific implementation methods, structures, features and effects of this application is provided in conjunction with the accompanying drawings and preferred embodiments.

[0014] Terms and Definitions

[0015] To enable those skilled in the art to understand the features and effects of this application, the terms and expressions mentioned in the specification and claims are generally explained and defined below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding this application, and in case of conflict, the definitions in this specification shall prevail.

[0016] In this document, singular terms refer to one or more. For example, "element" or "a single element" both refer to one or more elements. As used herein, the term "multiple" refers to at least two.

[0017] In this document, the terms “comprising,” “including,” “having,” “containing,” or any other similar terms are open-ended transitional phrases intended to encompass non-exclusive inclusions, indicating that a combination (e.g., an apparatus, composition, method, etc.) includes the listed elements (e.g., units of an apparatus, components of a composition, substantial steps of a method, etc.) but does not exclude other elements. 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 expressly listed but which are generally inherent to the composition or article. Unless expressly stated to the contrary, 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); and both P and Q are true (or exist). In this document, the term "substantially composed of..." when used to define compositions and methods means excluding other elements that have any substantial effect on the combination for the stated purpose, but does not exclude other elements that do not substantially affect the basic and novel features of this application. In this document, the term "composed of..." and other closing conjunctions refer to combinations excluding other elements (units, components, substantial steps, etc.), but unless otherwise stated, do not imply the exclusion of trace amounts of unavoidable impurities. Embodiments defined by each of these conjunctions are within the scope of this application. As a particular embodiment, disclosures including the terms "comprising," "including," "having," "containing," or any other similar terms should also be considered as simultaneous disclosures of corresponding technical solutions including both the terms "substantially composed of..." and "composed of...".

[0018] 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 covering and specifically disclosing 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 disclosing 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 disclosing 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 disclosing 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 application, regardless of its breadth.

[0019] 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 as all ranges specifically disclosed herein consisting of any upper or preferred value and a lower or preferred value of that range, whether or not such ranges are separately disclosed. As used herein, the term "about" means approximately, in about or near a range. When the term "about" is used in conjunction with a numerical range, it modifies the range by extending the limits above or below the provided numerical value. Generally, the term "about" is used herein to mean that the numerical value varies by 10% above or below the provided value. For example, "about 50%" means in the range of 45% to 55%. Furthermore, when a range of numerical values ​​is mentioned herein, unless otherwise stated, the range should include its endpoints and all integers and fractions within the range. It should also be understood that all integers and fractions are considered to be modified by the term "about". In this document, numerical values ​​should be understood to have the precision of the significant digits of the numerical value, provided that the inventive purpose is achieved. For example, the number 40.0 should be understood to cover the range from 39.50 to 40.49.

[0020] In this document, when Markush groups or alternative terms are used to describe features or instances of this application, 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 this application. 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 instances of this application, 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 this application. 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".

[0021] The compounds of this application may contain asymmetric or chiral centers and thus exist in different stereoisomeric forms. All stereoisomers of the compounds of this application, including but not limited to diastereomers, enantiomers, and transisomers, and mixtures thereof such as racemic mixtures, should be considered as part of this application.

[0022] In this document, unless otherwise specified, the term "compound" refers to a chemical substance formed by two or more elements linked by chemical bonds, including, but not limited to, small molecule compounds and macromolecules. In this document, the term "compound" should be interpreted not only as a single chemical substance, but also as a class of chemical substances having the same composition or the same properties. Furthermore, in this document, 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.

[0023] In this document, unless otherwise specified, the term "polymer" refers to the product formed by the polymerization reaction of monomers, often including aggregates of many high molecules, each of which is composed of many simple structural units linked by repeated covalent bonds. Monomers are the compounds that synthesize polymers. Polymers can include homopolymers (also known as self-polymers), copolymers, prepolymers, etc., and are not limited to these.

[0024] In this paper, the term "homopolymer" refers to a chemical substance formed by the polymerization, addition polymerization, or condensation polymerization of a single compound. A copolymer refers to a chemical substance 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–), etc.

[0025] In this document, unless otherwise specified, the term "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.

[0026] 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 typically consist of 2 to 5 repeating units.

[0027] In this document, unless otherwise specified, the term "modified product" (also known as "modified product") includes products resulting from the modification of the reactive functional groups of various resins, products resulting from the prepolymerization of various resins with other resins, products resulting from the crosslinking of various resins with other resins, products resulting from the homopolymerization of various resins, products resulting from the copolymerization of various resins with other resins, and so on. For example, 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, but is not limited to these.

[0028] In this document, unless otherwise specified, the terms alkyl, alkenyl, and hydrocarbon are interpreted in the context of their isomers. For example, unless otherwise specified, "propyl" is interpreted to include both n-propyl and isopropyl.

[0029] In this document, unless otherwise specified, the term "resin" can generally be the common name for a synthetic polymer. As used herein, the term "resin" can include, but is not limited to, monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and their polymers. For example, "maleimide resin" as used herein should be interpreted as including at least maleimide monomers (maleimide small molecule compounds), maleimide polymers, combinations of maleimide monomers, combinations of maleimide polymers, and combinations of maleimide monomers and maleimide polymers.

[0030] In this document, unless otherwise specified, the term "polyfunctional" means that the referred molecule (particularly monomers of polymers) includes two or more referred functional groups. For example, "polyfunctional maleimide" includes two or more maleimide functional groups; "polyfunctional amine" includes two or more amino groups; and "polyfunctional phenol" includes two or more phenolic hydroxyl groups.

[0031] In this document, parts by weight represent the number of parts by weight, which can be any unit of weight, such as, but not limited to, kilograms, grams, pounds, etc. For example, 100 parts by weight of maleimide resin means that it can be 100 kilograms of maleimide resin or 100 pounds of maleimide resin.

[0032] Implementation methods of this application

[0033] In one aspect, this application provides a resin composition comprising 100 parts by weight of maleimide resin and 0.3 to 10.0 parts by weight of an organophosphorus compound having the structure shown in formula (1), wherein –R– is a divalent aryl group.

[0034]

[0035] In some embodiments, the divalent aryl group may include substituted or unsubstituted benzoyl, biphenylyl, or naphthyl groups; in particular, the divalent aryl group may be an unsubstituted benzoyl, biphenylyl, or naphthyl group, but is not limited thereto. The benzoxyl group may be 1,2-benzoxyl, 1,3-benzoxyl, or 1,4-benzoxyl, particularly 1,2-benzoxyl; the biphenylxyl group may be 2,2′-biphenylxyl, 2,3′-biphenylxyl, 2,4′-biphenylxyl, 3,3′-biphenylxyl, 3,4′-biphenylxyl, or 4,4′-biphenylxyl, particularly 2,2′-biphenylxyl; and / or the naphthyl group may be 1,2-naphthyl, 1,3-naphthyl, 1,4-naphthyl, 1,5-naphthyl, 1,6-naphthyl, 1,7-naphthyl, 1,8-naphthyl, 2,3-naphthyl, 2,6-naphthyl, or 2,7-naphthyl, particularly 1,8-naphthyl, but is not limited thereto.

[0036] In some embodiments, the benzene ring of the diphenylphosphine group in the organophosphine compound may contain substituents.

[0037] In some embodiments, the substituents on the benzene ring of the aforementioned diphenylphosphine group or the substituents of the divalent aryl group can independently be monovalent alkyl, alkoxy, alkylamine, alkylthio, aryl, benzyl, aryloxy, or benzyloxy having 1 to 13 carbon atoms. For example, they can be methyl, ethyl, propyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, benzyl, methoxy, ethoxy, propoxy, butoxy, phenoxy, benzyloxy, dimethylamino, diethylamino, methylthio, or ethylthio, and are not limited thereto. In some embodiments, the substituents on the benzene ring of the aforementioned diphenylphosphine group or the substituents of the divalent aryl group can independently be monovalent alkyl, alkoxy, or alkylamine having 1 to 4 carbon atoms, or phenyl or benzyl.

[0038] In some embodiments, the organophosphorus compound comprises 1,2-bis(diphenylphosphino)benzene, 2,2′-bis(diphenylphosphino)biphenyl, 1,8-bis(diphenylphosphino)naphthalene, or combinations thereof. 1,2-bis(diphenylphosphino)benzene, 2,2′-bis(diphenylphosphino)biphenyl, and 1,8-bis(diphenylphosphino)naphthalene are respectively as shown in formula (2), formula (3), and formula (4).

[0039] The structures of (3) and (4) are shown.

[0040]

[0041] In some embodiments, the maleimide resin may include compounds or mixtures having one or more maleimide functional groups in their molecules. The maleimide resin used in this application is not particularly limited and may be any one or more maleimide resins suitable for making prepregs, resin films, laminates, printed circuit boards, or cured insulators.

[0042] Specific examples of the maleimide resin may include, but are not limited to, 4,4′-diphenylmethane bismaleimide, benzene maleimide oligomer, biphenyl aralkyl type bismaleimide, bismaleimide containing indane structure, 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, 2,3-dimethylbenzenemaleimide, 2,6-dimethylbenzenemaleimide, N-phenylmaleimide, maleimide resin containing aliphatic long-chain structure, or combinations thereof.

[0043] In some embodiments, the maleimide resin may be any one or more maleimide resin prepolymers having one or more maleimide functional groups in their molecules, suitable for the manufacture of prepregs, resin films, laminates, printed circuit boards, or cured insulators. The maleimide resin may include, but is not limited to, prepolymers of diallyl compounds and maleimide resins, prepolymers of polyfunctional amines and maleimide resins, prepolymers of acidic phenolic compounds and maleimide resins, or combinations thereof.

[0044] In some embodiments, 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 oligomer, 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.

[0045] 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.

[0046] 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 C atoms 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.

[0047] For example, commercially available maleimide resins containing aliphatic long-chain structures are as follows:

[0048] BMI-689:

[0049]

[0050] BMI-1400:

[0051]

[0052] Where n is 1 to 10;

[0053] BMI-1500:

[0054]

[0055] The average value of n is 1.3;

[0056] BMI-1700:

[0057]

[0058] Where n is 1 to 10;

[0059] BMI-2500:

[0060]

[0061] The average value of m1 is 3; the average value of m2 is 3;

[0062] BMI-3000, BMI-5000, BMI-6000:

[0063]

[0064] Where n is 1 to 10.

[0065] In some embodiments, 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.

[0066] 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.

[0067] 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-A novolac 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-A novolac epoxy resin.

[0068] In some embodiments, the epoxy resin may include biphenyl-type phenolic epoxy resin, dicyclopentadiene epoxy resin, o-methylphenolic epoxy resin, naphthol-type epoxy resin, or combinations thereof.

[0069] The amount of epoxy resin used is not particularly limited. In some embodiments, the resin composition may contain 5 to 30 parts by weight of epoxy resin relative to 100 parts by weight of maleimide resin.

[0070] In some embodiments, the resin composition may further comprise a diallyl bisphenol resin. The diallyl bisphenol resin may comprise compounds of formula (5) or formula (6) or combinations thereof:

[0071]

[0072] Where R1 is –C(CH3)2–, –CH2– or –SO2–.

[0073] In some embodiments, the diallyl bisphenol resin may include, but is not limited to, diallyl bisphenol A, diallyl bisphenol F, diallyl bisphenol S, bisphenol A diallyl ether, or a combination thereof.

[0074] The amount of diallyl bisphenol resin used is not particularly limited. In some embodiments, the resin composition may contain 5 to 20 parts by weight of diallyl bisphenol resin relative to 100 parts by weight of maleimide resin.

[0075] In some embodiments, the resin composition may further comprise polyolefin resin, maleimide triazine resin, small molecule vinyl-containing resin, small molecule vinyl-containing resin prepolymer, styrene-maleic anhydride resin, phenolic resin, benzo[a]benzene[b] var.[c] At least one of azirmonopolymer resin, cyanate ester resin, polyester resin, polyamide resin, and polyimide resin.

[0076] In some embodiments, the resin composition comprises a polyolefin resin. The polyolefin resin may include, but is not limited to, unsaturated polyolefin resins, hydrogenated unsaturated polyolefin resins, or combinations thereof. The unsaturated polyolefin resin may be any one or more polyolefin resins containing unsaturated carbon-carbon double bonds suitable for making prepregs, resin films, laminates, printed circuit boards, or cured insulators. The unsaturated polyolefin resin may include, but is not limited to, at least one or a combination of styrene-butadiene-divinylbenzene terpolymers, ethylene-divinylbenzene-styrene polymers, maleic anhydride-added styrene-butadiene copolymers, maleic anhydride-added polybutadiene, styrene-butadiene-styrene block polymers, vinyl-polybutadiene-urethane oligomers, styrene-butadiene copolymers, styrene-isoprene copolymers, polybutadiene, ethylene propylene diene monomer (EPDM) rubber, methylstyrene homopolymers, petroleum resins, and cyclic olefin copolymers, but is not limited to these.

[0077] The hydrogenated unsaturated polyolefin resin can be obtained by hydrogenating an unsaturated polyolefin resin. The hydrogenated unsaturated polyolefin resin can be any one or more hydrogenated unsaturated polyolefin resins suitable for making prepregs, resin films, laminates, printed circuit boards, or cured insulators, and does not contain unsaturated carbon-carbon double bonds. The hydrogenated unsaturated polyolefin resin may include at least one or a combination of hydrogenated styrene-butadiene copolymer, hydrogenated styrene-butadiene-styrene block polymer, or hydrogenated styrene-isoprene copolymer, but is not limited thereto.

[0078] In some embodiments, 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.

[0079] In some embodiments, the resin composition comprises a small-molecule vinyl-containing resin. The small-molecule vinyl-containing resin may include vinyl compounds with a molecular weight less than or equal to 1000, particularly those with a molecular weight between 100 and 900, and more preferably those with a molecular weight between 100 and 800. The small-molecule vinyl-containing resin may include, but is not limited to, styrene, divinylbenzene, ethylstyrene, bis(vinylbenzyl)ether, 1,2,4-trivinylcyclohexane (TVCH), bis(vinylphenyl)ethane (BVPE), di(vinylphenyl)hexane, divinylphenyldimethyl ether, divinylphenyldimethylbenzene, triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), or combinations thereof.

[0080] In some embodiments, the resin composition comprises a small-molecule vinyl-containing resin prepolymer. The small-molecule vinyl-containing resin prepolymer may include, but is not limited to, styrene prepolymers, divinylbenzene prepolymers, ethylstyrene prepolymers, di(vinylbenzyl)ether prepolymers, 1,2,4-trivinylcyclohexane prepolymers, di(vinylphenyl)ethane prepolymers, di(vinylphenyl)hexane prepolymers, divinylphenyldimethyl ether prepolymers, divinylphenyldimethylbenzene prepolymers, triallyl isocyanurate prepolymers, triallyl cyanurate prepolymers, or combinations thereof. For example, a styrene prepolymer may represent a styrene content greater than or equal to 50 wt%, or, for example, a styrene prepolymer with a styrene content between 50 wt% and 99 wt%, while the content of the second monomer unit in the styrene prepolymer is less than or equal to 49 wt%, for example, between 1 wt% and 49 wt%. For example, in one embodiment, the styrene prepolymer comprises 55-75 wt% styrene monomer units, 15-35 wt% divinylbenzene monomer units, and 5-30 wt% ethylstyrene monomer units. In another embodiment, the divinylbenzene prepolymer comprises 60 wt% divinylbenzene monomer units, 30 wt% ethylstyrene monomer units, and 10 wt% styrene monomer units. In yet another embodiment, the ethylstyrene prepolymer comprises 60 wt% ethylstyrene monomer units, 30 wt% styrene monomer units, and 10 wt% divinylbenzene monomer units. For example, a styrene prepolymer may also represent a prepolymer in which the styrene content is greater than or equal to the content of any other monomer. For example, in one embodiment, the styrene prepolymer comprises 40 wt% styrene monomer units, 30 wt% divinylbenzene monomer units, and 30 wt% ethylstyrene monomer units.

[0081] In some embodiments, 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.

[0082] In some embodiments, the resin composition includes 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.

[0083] In some embodiments, 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.

[0084] In some embodiments, 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, cyanate ester resins having an Ar–O–C≡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. Preferably, the resin composition does not contain cyanate ester resins. Cyanate ester resins pose a risk of residual bisphenol A (BPA), which is harmful to health.

[0085] In some embodiments, 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.

[0086] In some embodiments, 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.

[0087] In some embodiments, 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.

[0088] In some embodiments, the resin composition further includes at least one of amine curing agents, flame retardants, inorganic fillers, curing accelerators, polymerization inhibitors, colorants, solvents, toughening agents, and silane coupling agents.

[0089] In some embodiments, 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.

[0090] In some embodiments, 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.

[0091] 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.

[0092] 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. DOPO-PN is a DOPO phenolic compound, and DOPO-BPN may be a bisphenolic compound such as DOPO-BPAN (DOPO-bisphenol A novolac), DOPO-BPFN (DOPO-bisphenol F novolac), or DOPO-BPSN (DOPO-bisphenol S novolac).

[0093] In some embodiments, 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.

[0094] The amount of inorganic filler is not particularly limited. In some embodiments, the resin composition may contain 100 to 230 parts by weight of inorganic filler, based on 100 parts by weight of total solid resin (excluding solvent and inorganic filler) in the resin composition. In some embodiments, the weight ratio of the maleimide resin to the inorganic filler may be 1:1.5 to 1:3.0.

[0095] In some embodiments, the resin composition includes a curing accelerator. The curing accelerator may include Lewis bases, Lewis acids, or other catalysts. Lewis bases may include, but are not limited to, imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP), 4-dimethylaminopyridine (DMAP), or combinations thereof. 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. Curing initiators include, but are not limited to, 2,3-dimethyl-2,3-diphenylbutane, dicumyl peroxide, tert-butyl peroxide, tert-butyl peroxyisopropyl carbonate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B), bis(tert-butylperoxyisopropyl)benzene, azobisisobutyronitrile, or combinations thereof.

[0096] In some embodiments, 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.

[0097] In some embodiments, the resin composition includes a dyeing agent. The dyeing agent may include, but is not limited to, dyes or pigments.

[0098] In some embodiments, 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.

[0099] In some embodiments, 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.

[0100] In some embodiments, 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.

[0101] In one aspect, this application provides an article made at least in part of the resin composition. The article is, for example, a component suitable for use in various electronic products, including, but not limited to, prepregs, resin films, laminates, printed circuit boards, or cured insulators. In another aspect, this application provides the use of the resin composition of this application in the preparation of articles. In yet another aspect, this application provides the use of the resin composition of this application in the preparation of prepregs, resin films, laminates, printed circuit boards, or cured insulators. In one aspect, this application provides an article comprising a resin layer made of the resin composition. In yet another aspect, this application provides a method of preparing an article, comprising providing a resin layer made of the resin composition.

[0102] 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.

[0103] In some embodiments, this application 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 some embodiments, this application 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 some embodiments, the reinforcing material can also be pretreated with a silane coupling agent.

[0104] In some embodiments, this application provides a resin film. The resin film may include a semi-cured resin composition. In one aspect, this application provides a method for preparing a resin film, including semi-curing the resin composition, particularly heating the resin composition. The method for preparing the resin film may further include coating the resin composition onto a substrate. In some embodiments, this application provides a resin film assembly, including a substrate and the resin film disposed on the substrate. In one aspect, this application provides a method for preparing a resin film assembly, including providing a substrate and disposing the resin film on the substrate. In some embodiments, disposing the resin film on the substrate includes: 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.

[0105] In some embodiments, this application provides a laminate. The laminate may include at least two metal foils and an insulating layer disposed between the metal foils. In some embodiments, 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 and 180 minutes, particularly 100 to 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).

[0106] The multilayer board can be further processed into a circuit board, such as a printed circuit board, through circuit fabrication processes. One method of manufacturing the printed circuit board according to this application involves using a double-sided copper-clad laminate (e.g., product EM-890, available from Taikoo Electronics 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 a surface texture and 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.

[0107] In some embodiments, this application provides a cured insulator. In some embodiments, this application 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 some embodiments, the semi-curing of the resin composition is achieved by heating to a semi-curing temperature. The semi-curing temperature may be between 100°C and 200°C. In some embodiments, the single curing of the resin composition or the curing of the semi-cured resin composition is achieved by 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 and 180 minutes, particularly between 100 and 150 minutes. The curing may further include applying pressure to the resin composition or the semi-cured resin composition.

[0108] The cured insulator may include the cured resin composition. In some embodiments, this application 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 include coating the resin composition onto a substrate, and / or semi-curing the resin composition to form a resin film.

[0109] The cured insulator may include the cured resin composition containing reinforcing material in a cured state. In some embodiments, this application provides a method for preparing a cured insulator, including: curing the prepreg, particularly heating the prepreg. The method for preparing a cured insulator may further include disposing a resin composition on a reinforcing material, prepreg, particularly heating the resin composition, to form a prepreg comprising the reinforcing material and a prepreg layer.

[0110] 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.

[0111] 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.

[0112] In some embodiments, the article of this application has one, more, or all of the following characteristics:

[0113] - The glass transition temperature measured according to the method described in IPC-TM-650 2.4.24.4 is greater than or equal to 325°C;

[0114] - The glass transition temperature measured according to the method described in IPC-TM-650 2.4.24.5 is greater than or equal to 260°C;

[0115] - The Z-axis thermal expansion coefficient measured according to the method described in IPC-TM-650 2.4.24.5 is less than or equal to 0.80%;

[0116] - The amount of adhesive flowing inside the product (e.g., a sample with adhesive flow inside the board) after pressing is greater than or equal to 8.0 mm;

[0117] - The resin flow rate measured according to the method described in IPC-TM-650 2.3.17 is greater than or equal to 30%;

[0118] - No copper substrate, no edge stripes.

[0119] Example

[0120] The following specific embodiments are merely illustrative in nature and are not intended to limit this application or its uses. Furthermore, this document is not limited to any theory described in the foregoing prior art, invention content, specific implementation methods, or embodiments. Unless otherwise stated, the methods, materials, and conditions used in the embodiments are conventional methods, materials, and conditions in the art.

[0121] raw material

[0122] The structures and sources of the various raw materials used in the following embodiments are as follows:

[0123] -BMI-2300: Benzene maleimide oligomer, purchased from Daiwa Chemical Co., Ltd.

[0124] -MIR-3000: Biphenyl aryl bismaleimide, purchased from Nippon Kayaku Co., Ltd.

[0125] -X9-470: Contains indene-structured bismaleimide, purchased from DIC.

[0126] -BMI-5100: 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, purchased from Daiwa Chemical Co., Ltd.

[0127] -BMI-4000: Bisphenol A diphenyl ether bismaleimide, purchased from Daiwa Chemical Co., Ltd.

[0128] -1,2-Bis(diphenylphosphine): purchased from Aladdin.

[0129] -2,2′-Bis(diphenylphosphine)biphenyl: purchased from Aladdin.

[0130] -2,2′-bis(diphenylphosphino)-1,1′-binaphthyl: purchased from Aladdin.

[0131] -1,2-Di(diphenylphosphine)ethane: purchased from Aladdin.

[0132] - Triphenylphosphine: Purchased from Aladdin.

[0133] -2-PZ: Diphenylimidazole, purchased from Shikoku Kasei.

[0134] -NC-3000H: Biphenyl-type phenolic epoxy resin, purchased from Nippon Kayaku Co., Ltd.

[0135] -HP-7200H: Dicyclopentadiene epoxy resin, purchased from Nippon Kayaku Co., Ltd.

[0136] -CNE200: o-methylphenol phenolic epoxy resin, purchased from Changchun Chemical Co., Ltd.

[0137] -NC-7000L: Naphthol-type epoxy resin, purchased from Nippon Kayaku Co., Ltd.

[0138] - Diallyl Bisphenol A: Purchased from Sichuan Dongcai Technology Co., Ltd.

[0139] - Diallylbisphenol S: Purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0140] - Bisphenol A dielyl ether: purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0141] -SC-2050-SXJ: Spherical silica with an aminosilane coupling agent surface treated, purchased from Admatechs.

[0142] -Butanone: Commercially available, source is not limited.

[0143] Cyclohexanone: Commercially available, source is not limited.

[0144] Preparation of resin composition

[0145] The resin compositions of Examples E1 to E12 and Comparative Examples C1 to C9 of this application were prepared according to the amounts in Table 1, and further processed into various test samples or articles. Blanks in the table represent "0".

[0146] Table 1. Composition of the resin compositions of Examples E1 to E12 and Comparative Examples C1 to C9 (unit: parts by weight)

[0147]

[0148]

[0149] In Table 1, "Z" represents the total amount of all components in the resin compositions of each group of examples or comparative examples, excluding (i.e., not containing) inorganic fillers and solvents. "Z*1.0" in the table represents that the amount of inorganic filler added is 1.0 times the aforementioned Z. For example, Z*1.5 in Example E1 represents an amount of inorganic filler added of 151.5 parts by weight (101 parts by weight multiplied by 1.5).

[0150] In Table 1, the amount of methyl ethyl ketone (MEK) and cyclohexanone added as "appropriate amount" represents the amount of solvent used to completely dissolve the solid resin (e.g., maleimide resin) in the resin composition. For resin compositions using both MEK and cyclohexanone, "appropriate amount" means that the total amount of these two solvents results in the overall solid content of the resin composition being the ideal solid content, for example, but not limited to, 70% by weight.

[0151] The preparation methods of the resin compositions of Examples E1 to E12 and Comparative Examples C1 to C9 are as follows.

[0152] Preparation of varnish (or gelling agent)

[0153] Each component of Examples E1 to E12 or Comparative Examples C1 to C9 is added to a mixing tank according to the amounts in Table 1 and stirred until uniformly mixed to form a resin composition, which is called resin varnish.

[0154] Taking Example E1 as an example, 100 parts by weight of maleimide resin BMI-2300 were added to a stirrer containing an appropriate amount of butanone and cyclohexanone, and stirred until the solid components were completely dissolved. Then, “Z*1.5” parts by weight of spherical silica SC-2050-SXJ (i.e., 151.5 parts by weight) were added and stirred until completely dispersed. Then, 1 part by weight of 1,2-bis(diphenylphosphine)benzene (dissolved in an appropriate amount of solvent first) was added and stirred for 1 hour to obtain the varnish of resin composition E1.

[0155] In addition, in accordance with the ingredient amounts listed in Table 1 and the method for preparing the varnish of Example E1, varnishes of other Examples E2 to E12 and Comparative Examples C1 to C9 were prepared.

[0156] Preparation of prepreg 1 (using 2116E-glass fiber cloth)

[0157] The resin composition varnishes of Examples E1 to E12 or Comparative Examples C1 to C9 were placed in an impregnation tank in batches. Glass fiber cloth (e.g., E-glass fiber cloth of specification 2116) was passed through the impregnation tank to attach the resin composition to the glass fiber cloth. The mixture was then heated at 150°C to a semi-cured state (B-Stage) to obtain semi-cured sheet 1 (resin content about 52%).

[0158] Preparation of prepreg 2 (using 1080E-glass fiber cloth)

[0159] The resin composition varnishes of Examples E1 to E12 or Comparative Examples C1 to C9 were placed in an impregnation tank in batches. A glass fiber cloth (e.g., E-glass fiber cloth of specification 1080) was passed through the impregnation tank to adhere the resin composition to the glass fiber cloth. The cloth was then heated at 150°C to a semi-cured state (B-Stage) to obtain semi-cured sheet 2 (resin content approximately 70%).

[0160] Preparation of copper foil substrate 1 (formed by laminating eight prepreg sheets 1)

[0161] Two 12-micron-thickness reverse-treat copper foils (RTF copper foils) and eight prepregs 1 made from various resin compositions are prepared in batches. The copper foils, eight prepregs 1, and copper foils are stacked in that order and pressed under vacuum at 230°C for 120 minutes to form each copper foil substrate 1. The eight stacked prepregs 1 are then cured (C-stage) to form an insulating layer between the two copper foils; the resin content of the insulating layer is approximately 52%.

[0162] Preparation of copper-free substrate 1 (formed by laminating eight prepreg sheets 1)

[0163] The copper foil substrate 1 (made by pressing eight prepreg sheets 1 together) is etched to remove the copper foil on both sides to obtain a copper-free substrate 1, which is made by pressing eight prepreg sheets 1 together and has a resin content of about 52%.

[0164] Product testing and property analysis

[0165] 1. Glass transition temperature (Tg) test

[0166] The "copper-free substrate 1" prepared using the resin compositions of the aforementioned embodiments or comparative examples was used as the test sample for dynamic mechanical analysis (DMA). The sample was heated at a rate of 2°C per minute within a temperature range from 35°C to 400°C, and the glass transition temperature (in °C) of each test sample was measured according to the method described in IPC-TM-650 2.4.24.4.

[0167] Similarly, the "copper-free substrate 1" prepared from the resin compositions of the aforementioned embodiments or comparative examples was used as the test sample for thermomechanical analysis (TMA). The sample was heated at a rate of 10°C per minute within a temperature range from 35°C to 350°C, and the glass transition temperature (in °C) of each test sample was measured according to the method described in IPC-TM-650 2.4.24.5.

[0168] In this field, a higher glass transition temperature is preferred. A difference in glass transition temperature greater than or equal to 5°C indicates a significant difference in glass transition temperature between different substrates (presenting significant technical challenges).

[0169] For example, an article made according to the resin composition disclosed in this application has a glass transition temperature (DMA-Tg) greater than or equal to 325°C, for example, between 325°C and 392°C, measured with reference to the method described in IPC-TM-650 2.4.24.4; and a glass transition temperature (TMA-Tg) greater than or equal to 260°C, for example, greater than or equal to 262°C, or for example, between 262°C and 295°C, measured with reference to the method described in IPC-TM-650 2.4.24.5.

[0170] 2. Ratio of thermal expansion (or dimensional change rate) dimensional change)

[0171] The "copper-free substrate 1" prepared using the resin compositions of the aforementioned embodiments or comparative examples was used as the test sample for thermomechanical analysis (TMA). The sample was heated at a rate of 10°C per minute, from 35°C to 265°C, and the Z-axis dimensional change rate of each test sample (50°C to 260°C, in %) was measured according to the method described in IPC-TM-650 2.4.24.5.

[0172] In this field, the lower the percentage of the measured dimensional change rate, the better. When the coefficient of thermal expansion is ≤1.2%, a difference in the coefficient of thermal expansion greater than or equal to 0.05% is considered significant (significant technical difficulty).

[0173] A large dimensional change rate indicates a high Z-axis thermal expansion rate of the substrate. For copper foil substrates, a high thermal expansion rate can easily lead to problems such as displacement at circuit connection points (e.g., but not limited to blind or buried vias) during the manufacturing process of printed circuit boards, reducing yield, or board explosion, reducing reliability.

[0174] For example, an article made according to the resin composition disclosed in this application has a Z-axis thermal expansion coefficient less than or equal to 0.80%, for example less than or equal to 0.79%, or for example between 0.35% and 0.79%, as measured by the method described in IPC-TM-6502.4.24.5.

[0175] 3. Adhesive leakage inside the board

[0176] First, prepare a copper-containing substrate (EM-827) as the copper core board (available from Zhongshan Taiguang Electronic Materials Co., Ltd., which uses 7628E-glass fiber cloth and 1 ounce (oz) HTE copper foil). The thickness of the copper core board is 28 mil. The surface copper foil of this copper core board is treated with a known browning process to obtain a browned core board. Prepare the aforementioned browned core board with a thickness of 28 mil and dimensions of 18 inches in length and 16 inches in width.

[0177] Prepare a "precured sheet 2" made from the resin composition of the aforementioned embodiments or comparative examples, and punch a diamond-shaped opening with a length and width of 4 inches in the center of the precured sheet 2 using a known punching machine.

[0178] A copper-containing multilayer board is obtained by sequentially stacking a 0.5 oz HTE copper foil (reverse pressing, i.e., the bright side of the copper foil contacts the prepreg), a prepreg 2 (with the aforementioned diamond-shaped opening), and a browned core board, and then pressing and curing it under vacuum, high temperature (200°C) and high pressure (360 psi) conditions for 2 hours.

[0179] Remove the copper foil backing from the surface of this copper-containing multilayer board to obtain an in-board adhesive flow sample.

[0180] Take a sample of the glue flow inside the board, and use the sides of a 4-inch × 4-inch rhombus as the baseline. Divide each side into 4 equal parts with 3 bisecting points. Measure the glue flow at each of the 12 points (i.e., the vertical glue flow distance at each of the 12 points), and calculate the average glue flow at the 12 points to obtain the glue flow (average value) inside the board, in millimeters (abbreviated as mm in the following text).

[0181] In this field, the greater the measured intra-board flow rate, the better the flowability of the prepreg. A difference in intra-board flow rate greater than or equal to 1.0 mm is considered a significant difference (indicating significant technical difficulty).

[0182] Generally, the in-board adhesive flow is preferably between 6.0mm and 20.0mm, and more preferably between 8.0mm and 18.0mm. An in-board adhesive flow of less than 6.0mm indicates insufficient adhesive flow, which may result in ineffective adhesive filling of vias when using prepreg for layering, easily leading to adhesive shortages or board bursting.

[0183] 4. Resin flow rate (RF)

[0184] The "precursor sheet 2" prepared by the resin composition of the aforementioned embodiments or comparative examples was used as the test sample, and the precursor sheet 2 was punched into four 4-inch × 4-inch rhombuses using a known punching machine.

[0185] The glue flow rate (in %) of each sample was measured according to the method described in IPC-TM-650 2.3.17.

[0186] In this field, a higher measured adhesive flow rate indicates better flowability of the prepreg, and a difference in adhesive flow rate greater than or equal to 1% is considered significant (presenting significant technical difficulty). For this specification of prepreg, the adhesive flow rate is preferably between 30% and 40%.

[0187] 5. Stripes on the edge of the substrate

[0188] Prepare a "copper-free substrate 1" (made by laminating eight prepreg sheets) using the resin compositions of the aforementioned embodiments or comparative examples. Determine the surface condition of the insulating layer of the copper-free substrate 1 by visual inspection. If a dendritic distribution appears on the edge of the board, it indicates that the components in the resin composition have poor compatibility or large differences in flowability, resulting in unevenness.

[0189] A schematic diagram of the appearance of a copper-free substrate with dendritic stripe distribution is shown below. Figure 1 The more dendritic stripes there are, the more severe the unevenness; a normal copper-free substrate without dendritic stripes is shown in the diagram below. Figure 2 .

[0190] The presence of dendritic distribution on the substrate can cause uneven characteristics (poor reliability) in the subsequently manufactured printed circuit boards, such as poor dielectric properties, low heat resistance, uneven thermal expansion, or poor interlayer bonding. Therefore, substrates with dendritic distribution must be scrapped directly, resulting in a significant reduction in yield.

[0191] The results of testing and characterization of articles made using the resin compositions of the various embodiments and comparative examples of this application, including glass transition temperature (DMA-Tg) obtained by dynamic mechanical analysis, glass transition temperature (DMA-Tg) obtained by thermomechanical analysis, coefficient of thermal expansion (temperature range of 50°C to 260°C), resin flow within the board, resin flow rate, and edge stripes of the substrate, are shown in Table 2.

[0192] Table 2. Test and property analysis results of resin composition articles from various embodiments and comparative examples of this application.

[0193] Property Test unit E1 E2 E3 E4 E5 E6 E7 E8 E9 E10 E11 E12 DMA-Tg ℃ 392 389 375 340 345 370 376 372 377 330 325 372 TMA-Tg ℃ 295 292 288 270 271 282 288 282 286 265 262 280 thermal expansion coefficient ％ 0.35 0.40 0.53 0.60 0.56 0.57 0.51 0.55 0.56 0.78 0.79 0.60 Adhesive flow inside the board mm 12.0 13.0 15.0 12.0 14.0 18.0 11.0 8.5 16.0 18.0 10.0 15.0 Adhesive flow rate ％ 32 33 35 32 35 40 31 30 36 39 31 35 substrate edge stripes none none none none none none none none none none none none

[0194]

[0195] Based on the test results in Table 2, the following phenomena can be observed:

[0196] - By comparing Example E1 and Comparative Examples C7 to C9 respectively, it can be confirmed that by using maleimide resin and organophosphorus compounds within the scope of this application, compared with organophosphorus compounds outside the scope, the articles prepared by this application can simultaneously achieve one, more or all of the following technical effects: increasing glass transition temperature, reducing thermal expansion coefficient, increasing in-plate glue flow, increasing glue flow rate, and substrate without edge stripe characteristics.

[0197] - By comparing Examples E3, E6-E8 with Comparative Examples C4-C5, it can be confirmed that the present application uses 100 parts by weight of maleimide resin and 0.3 to 10.0 parts by weight of organophosphorus compound. Compared with resin compositions outside the dosage range, the articles prepared by the present application can simultaneously achieve one, more or all of the following technical effects: increasing glass transition temperature, reducing thermal expansion coefficient, increasing in-plate glue flow, increasing glue flow rate, and substrate without edge stripe characteristics.

[0198] - By comparing Examples E1 to E12 with Comparative Examples C1 to C9, it can be confirmed that by using 100 parts by weight of maleimide resin in combination with 0.3 parts by weight to 10.0 parts by weight of organophosphorus compound, the substrate produced can simultaneously achieve the technical effects of an in-board glue flow of 8.0 mm or more, a glue flow rate of 30% or more, and no edge stripes on the substrate. Conversely, Comparative Examples C1 to C9, which do not use the technical solution of this application, cannot simultaneously achieve the aforementioned technical effects.

[0199] Although at least one embodiment or comparative example has been presented in the foregoing detailed description, it should be understood that numerous variations are possible with respect to this application. It should also be understood that the embodiments described herein are not intended to limit the scope of the claims in any way. Rather, the foregoing detailed description will provide a simple guide for those skilled in the art to implement one or more embodiments of this application. Furthermore, various changes can be made to the function and arrangement of the elements without departing from the scope defined by the claims, and the claims include known equivalents and all foreseeable equivalents at the time of filing of this patent application.

Claims

1. A resin composition, characterized in that, include: 100 parts by weight of maleimide resin; as well as 0.3 to 10.0 parts by weight of organophosphorus compounds, The organophosphorus compound described herein has the structure shown in formula (1). Wherein, –R– includes substituted or unsubstituted benzoyl, biphenylyl, or naphthyl groups.

2. The resin composition according to claim 1, characterized in that, The organophosphine compounds include 1,2-bis(diphenylphosphino)benzene, 2,2′-bis(diphenylphosphino)biphenyl, 1,8-bis(diphenylphosphino)naphthalene, or combinations thereof.

3. The resin composition according to claim 1, characterized in that, The maleimide resin includes 4,4′-diphenylmethane bismaleimide, benzene maleimide oligomer, biphenyl aralkyl type bismaleimide, bismaleimide containing indane structure, 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, 2,3-dimethylbenzenemaleimide, 2,6-dimethylbenzenemaleimide, N-phenylmaleimide, maleimide resin containing aliphatic long-chain structure, or combinations thereof.

4. The resin composition according to claim 1, characterized in that, The resin composition further includes an epoxy resin.

5. The resin composition according to claim 4, characterized in that, The epoxy resin includes bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD ​​epoxy resin, phenolic epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentadiene epoxy resin, phosphorus-containing epoxy resin, p-xylene epoxy resin, naphthalene-type epoxy resin, benzofuran-type epoxy resin, isocyanate-modified epoxy resin, or combinations thereof.

6. The resin composition according to claim 4, characterized in that, The resin composition contains 5 to 30 parts by weight of the epoxy resin.

7. The resin composition according to claim 4, characterized in that, The resin composition further comprises diallyl bisphenol resin. The diallyl bisphenol resins include compounds of formula (5) or formula (6) or combinations thereof: Where R1 is –C(CH3)2–, –CH2– or –SO2–.

8. The resin composition according to claim 7, characterized in that, The resin composition contains 5 to 20 parts by weight of the diallyl bisphenol resin.

9. The resin composition according to claim 1, characterized in that, The resin composition further includes polyolefin resin, maleimide triazine resin, small molecule vinyl-containing resin, small molecule vinyl-containing resin prepolymer, styrene-maleic anhydride resin, phenolic resin, benzoxazine resin, cyanate ester resin, polyester resin, polyamide resin, polyimide resin, or combinations thereof.

10. The resin composition according to claim 1, characterized in that, The resin composition does not contain cyanate resin.

11. The resin composition according to claim 1, characterized in that, The resin composition further includes amine curing agents, flame retardants, inorganic fillers, curing accelerators, polymerization inhibitors, colorants, solvents, toughening agents, silane coupling agents, or combinations thereof.

12. The resin composition according to claim 11, characterized in that, The weight ratio of the maleimide resin to the inorganic filler is 1:1.5 to 1:3.

0.

13. The resin composition according to any one of claims 1 to 12, wherein the resin composition is used to prepare articles, wherein the articles include prepregs, resin films, laminates, printed circuit boards, or cured insulators.

14. An article comprising a prepreg, a resin film, a multilayer printed circuit board, or a cured insulator, characterized in that, At least a portion of the article is made of the resin composition as described in any one of claims 1 to 12.

15. The article of claim 14, characterized in that, The glass transition temperature of the product, measured according to the method described in IPC-TM-650 2.4.24.4, is greater than or equal to 325°C.

16. The article of claim 14, characterized in that, The glass transition temperature of the product, measured according to the method described in IPC-TM-650 2.4.24.5, is greater than or equal to 260°C.

17. The article of claim 14, characterized in that, The product's Z-axis thermal expansion coefficient, measured according to the method described in IPC-TM-650 2.4.24.5, is less than or equal to 0.80%.

18. The article of claim 14, characterized in that, The amount of adhesive flowing inside the board after the product is pressed is greater than or equal to 8.0 mm.

19. The article of claim 14, characterized in that, The adhesive flow rate of the product measured according to the method described in IPC-TM-650 2.3.17 is greater than or equal to 30%.

20. The article of claim 14, characterized in that, The product contains no copper substrate and has no edge stripes.

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